U.S. patent application number 14/663965 was filed with the patent office on 2015-07-09 for silicon/germanium nanoparticles and inks having low metal contamination.
The applicant listed for this patent is NanoGram Corporation. Invention is credited to Igor Altman, Shivkumar Chiruvolu, Bernard M. Frey, Weidong Li, Guojun Liu, Robert B. Lynch, Gina Elizabeth Pengra-Leung, Uma Srinivasan.
Application Number | 20150191616 14/663965 |
Document ID | / |
Family ID | 45352936 |
Filed Date | 2015-07-09 |
United States Patent
Application |
20150191616 |
Kind Code |
A1 |
Chiruvolu; Shivkumar ; et
al. |
July 9, 2015 |
SILICON/GERMANIUM NANOPARTICLES AND INKS HAVING LOW METAL
CONTAMINATION
Abstract
Laser pyrolysis reactor designs and corresponding reactant inlet
nozzles are described to provide desirable particle quenching that
is particularly suitable for the synthesis of elemental silicon
particles. In particular, the nozzles can have a design to
encourage nucleation and quenching with inert gas based on a
significant flow of inert gas surrounding the reactant precursor
flow and with a large inert entrainment flow effectively
surrounding the reactant precursor and quench gas flows. Improved
silicon nanoparticle inks are described that has silicon
nanoparticles without any surface modification with organic
compounds. The silicon ink properties can be engineered for
particular printing applications, such as inkjet printing, gravure
printing or screen printing. Appropriate processing methods are
described to provide flexibility for ink designs without surface
modifying the silicon nanoparticles.
Inventors: |
Chiruvolu; Shivkumar; (San
Jose, CA) ; Altman; Igor; (Fremont, CA) ;
Frey; Bernard M.; (Livermore, CA) ; Li; Weidong;
(San Jose, CA) ; Liu; Guojun; (Suzhou, CN)
; Lynch; Robert B.; (Livermore, CA) ;
Pengra-Leung; Gina Elizabeth; (San Jose, CA) ;
Srinivasan; Uma; (Mountain View, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NanoGram Corporation |
Milpitas |
CA |
US |
|
|
Family ID: |
45352936 |
Appl. No.: |
14/663965 |
Filed: |
March 20, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13858240 |
Apr 8, 2013 |
9006720 |
|
|
14663965 |
|
|
|
|
13070286 |
Mar 23, 2011 |
8895962 |
|
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13858240 |
|
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|
|
61359662 |
Jun 29, 2010 |
|
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Current U.S.
Class: |
494/37 |
Current CPC
Class: |
C09D 11/52 20130101;
C09D 7/67 20180101; H01L 23/4828 20130101; H01L 31/03762 20130101;
H01L 31/0747 20130101; C08K 9/02 20130101; H01L 2924/0002 20130101;
B01J 2219/0869 20130101; H01L 31/00 20130101; B01J 2219/0871
20130101; C09D 5/24 20130101; C09D 11/101 20130101; C01B 33/02
20130101; C09D 11/38 20130101; H01L 21/02581 20130101; H01L
31/03682 20130101; Y02E 10/52 20130101; C08K 3/36 20130101; H01L
21/02532 20130101; H01L 31/182 20130101; Y02E 10/546 20130101; H01L
31/1864 20130101; H01L 21/02579 20130101; B01J 2219/0875 20130101;
C09D 7/68 20180101; Y02P 70/50 20151101; C09D 11/037 20130101; H01L
21/02601 20130101; B82Y 30/00 20130101; C08K 3/08 20130101; Y02E
10/548 20130101; C09D 11/322 20130101; B01J 19/121 20130101; H01L
21/02573 20130101; H01L 31/02363 20130101; H01L 21/02628 20130101;
C09D 7/80 20180101; C09D 11/36 20130101; B01D 21/262 20130101; H01L
23/53276 20130101; H01L 2924/0002 20130101; H01L 2924/00
20130101 |
International
Class: |
C09D 11/38 20060101
C09D011/38; C09D 11/36 20060101 C09D011/36; B01D 21/26 20060101
B01D021/26; C01B 33/02 20060101 C01B033/02 |
Claims
1. A method for forming a high purity dispersion comprising silicon
nanoparticles and a liquid, the method comprising: centrifuging an
initial dispersion of silicon nanoparticles and the liquid, and
separating the high purity dispersion from settled
contaminants.
2. The method of claim 1 wherein the silicon nanoparticles were
formed by laser pyrolysis with a silane precursor.
3. The method of claim 1 wherein the silicon nanoparticles have an
average primary particle size of no more than about 100 nm.
4. The method of claim 1 wherein the silicon nanoparticles have an
average primary particle size of no more than about 50 nm and a
z-average secondary particle size of no more than about 250 nm.
5. The method of claim 4 wherein the primary particles have a
distribution in diameters such that at least about 95 percent of
the particles have a diameter greater than about 35 percent of the
average diameter and less than about 280 percent of the average
diameter.
6. The method of claim 1 wherein the initial dispersion has a
silicon nanoparticle concentration of at least about 0.05 weight
percent.
7. The method of claim 1 wherein the initial dispersion has a
silicon nanoparticle concentration of at least about 0.5 weight
percent.
8. The method of claim 1 wherein the silicon nanoparticles are
doped.
9. The method of claim 8 wherein the silicon nanoparticles have a
dopant concentration from about 0.25 atomic percent to about 15
atomic percent.
10. The method of claim 1 further comprising performing sonication
to form the initial dispersion.
11. The method of claim 10 wherein mixing with shear is performed
in addition to sonication to form the initial dispersion.
12. The method of claim 1 wherein the decontaminated silicon
nanoparticle dispersion is stable without visible settling for at
least a week.
13. The method of claim 1 wherein the liquid comprises
terpineol.
14. The method of claim 13 wherein the liquid further comprises a
second solvent.
15. The method of claim 1 wherein the liquid comprises alcohol.
16. The method of claim 1 wherein the decontaminated dispersion has
a viscosity that depends on shear rate.
17. The method of claim 1 wherein the decontaminated dispersion has
a viscosity from about 10 Pas to about 300 Pas.
18. The method of claim 1 wherein the level of total metal
contamination is no more than about 5 parts per million.
19. The method of claim 1 wherein the nanoparticles comprise no
more than about 200 parts per billion of iron by weight.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of copending U.S. patent
application Ser. No. 13/858,240 filed Apr. 8, 2103, entitled
"Silicon/Germanium Nanoparticles and Inks Having Low Metal
Contamination," which is a continuation of Ser. No. 13/070,286, now
U.S. Pat. No. 8,895,962B2 to Chiruvolu et al. filed Mar. 23, 2011,
entitled "Silicon/Germanium Nanoparticle Inks, Laser Pyrolysis
Reactors for the Synthesis of Nanoparticles and Associated
Methods", which claims priority to copending U.S. provisional
patent application 61/359,662 filed Jun. 29, 2010 to Chiruvolu et
al., entitled "Silicon/Germanium Nanoparticle Inks, and Associated
Methods," each of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The invention pertains to the synthesis of inorganic
nanoparticles, such as doped silicon nanoparticles, with a
desirable nozzle design for a laser pyrolysis reactor. The
invention further pertains to silicon nanoparticle dispersions that
can be formulated as desirable inks, such as inkjet inks, gravure
printing inks or printing pastes.
BACKGROUND OF THE INVENTION
[0003] Silicon is an important commercial material. Many
applications of silicon are based on the semiconducting properties
of silicon. The semiconducting properties and electron mobilities
of silicon can be altered using dopants. The formation of
semiconductor devices generally involves the formation of regions
of the device with selectively doped silicon in which the dopants
alter the electrical conduction properties or other desired
properties. Through the selected doping process different domains
of the device can be formed that provide functionalities for
particular device to exploit the semiconductor properties, such as
a diode junction formed with separate materials with a p-type
dopant and an n-type dopant. For example, n-type dopants provide
excess electrons that can populate the conduction bands, and the
resulting materials are referred to as n-type semiconductors.
P-type dopants provide electron deficiencies or holes and are used
to form p-type semiconductors. Through appropriate doping, a wide
range of devices can be formed, such as transistors, diodes and the
like.
[0004] The wide ranges of semiconductor applications generate
commercial relevance for silicon materials in many forms. For
example, the formation of large area thin film transistors or the
like generates a demand for alternative semiconductor processing
approaches. Also, with increasing energy costs and increasing
demand for energy, the market for solar cells has been
correspondingly increasing. A majority of commercial solar cells
comprise photoconducting silicon semiconductors, and differential
doping of the semiconductor facilitates harvesting of the
photocurrent. At the same time with increasing performance demands,
there are strong pressures to keep costs down so that improvements
in material processing is very desirable as an approach to address
performance issues while keeping costs at acceptable levels.
Germanium is a semiconducting material that can be an alternative
to silicon with similar semiconducting properties. Also, silicon
and germanium can form semiconducting alloys with each other.
SUMMARY OF THE INVENTION
[0005] In a first aspect, the invention pertains to a dispersion
comprising at least about 1 weight percent elemental
silicon/germanium nanoparticles having an average primary particle
diameter of no more than about 50 nanometers, wherein the
dispersion is a good dispersion, and the silicon particles are free
of non-solvent based chemically bonded organic surface
modification.
[0006] In a further aspect, the invention pertains to a dispersion
comprising at least about 1 weight percent elemental
silicon/germanium nanoparticles having an average primary particle
diameter of no more than about 50 nanometers, wherein the
dispersion is a good dispersion, and having total metal
contamination of no more than about 1 parts per million by
weight.
[0007] In another aspect, the invention pertains to a collection of
silicon/germanium nanoparticles having an average primary particle
diameter of no more than about 100 nm and a level of total metal
contamination of no more than about 5 parts per million.
[0008] In additional aspects, the invention pertains to a paste
comprising at least about 5 weight percent elemental
silicon/germanium nanoparticles having an average primary particle
size of no more than about 50 nm, from about 0.25 weight percent to
about 15 weight percent of a first solvent having a boiling point
from about 55.degree. C. to about 160.degree. C., and from about 65
weight percent to about 94.75 weight percent of a second solvent
having a boiling point of at least about 175.degree. C., wherein
the paste has a viscosity from about 10 Pas to about 300 Pas.
[0009] In other aspects, the invention pertains to an ink
comprising at least about 1 weight percent elemental
silicon/germanium nanoparticles having an average primary particle
size of no more than about 30 nm, from about 10 weight percent to
about 60 weight percent alcohol, from about 30 to about 80 weight
percent of a polar aprotic solvent, wherein the ink has a viscosity
from about 0.1 mPas to about 100 mPas and a surface tension from
about 20 dynes/cm to about 70 dynes/cm.
[0010] Moreover, the invention pertains to a method for preparing
an ink with elemental silicon/germanium nanoparticles. The method
can comprise adding a second solvent to an initial dispersion of
elemental silicon nanoparticles dispersed in a first solvent to
form the ink which is a good dispersion of the nanoparticles in a
blend of the solvents. In some embodiments, the elemental silicon
nanoparticles are free from non-solvent based chemically bonded
surface modification with an organic compound. Generally, the first
solvent and the second solvent blend to form a single phase.
[0011] Furthermore, the invention pertains to a method for forming
a screen printing paste with a selected viscosity based on
adjusting the nanoparticle concentration wherein the screen
printing paste comprises elemental silicon/germanium nanoparticles.
The method generally comprises dispersing the nanoparticles in a
solvent comprising a blend of a first solvent having a boiling
point from about 55.degree. C. to about 160.degree. C. and a second
solvent having a boiling point of at least about 175.degree. C. to
form the paste, in which the paste has a particle concentration
from about 10 weight percent to about 20 weight percent and the
paste has a viscosity at a shear rate of 2 s.sup.-1 from about 10
Pas to about 800 Pas.
[0012] Additionally, the invention pertains to a method for
printing a desired thickness of a silicon nanoparticle ink wherein
the ink comprises at least about 1 weight percent elemental
silicon/germanium nanoparticles having an average primary particle
diameter of no more than about 50 nanometers and wherein the ink is
a good dispersion. The method generally comprises printing a first
time the silicon nanoparticle ink to form a first silicon
nanoparticle deposit, and repeating the printing one or more times
as appropriate to get a desired thickness of the nanoparticle ink
deposit.
[0013] In further aspects, the invention pertains to a laser
pyrolysis reactor comprising a reaction chamber, a light source and
associated optical elements configured to deliver a light beam
through the reaction chamber, a reactant delivery system comprising
reactant reservoirs, a nozzle configured to deliver one or more
reactants from the reactant delivery system into the reaction
chamber, and a collection system configured to receive the flow
from the reaction chamber that originated from the nozzle. In some
embodiments, the nozzle comprises an inner inert gas channel, an
intermediate reactant channel surrounding the inner inert gas
channel and an outer inert gas channel surrounding the intermediate
reactant channel, wherein the inner inert gas channel and the outer
inert gas channel are operably connected to an inert gas
source.
[0014] In some aspects, the invention pertains to a method for
synthesizing nanoparticles by laser pyrolysis, in which the method
comprising reacting a reactant flow using a light beam to drive the
reaction. In some embodiments, a reactant flow is initiated from a
nozzle with reactants flowed through an annular ring with inert
gases flowed through an inner flow channel in center and through an
outer gas channel surrounding the reactant flow wherein the
reactant flow substantially completely flows through a light beam
such that energy from the light beam drives the reaction to form
product particles.
[0015] In additional aspects, the invention pertains to a laser
pyrolysis reactor comprising a reaction chamber, a light source and
associated optical elements configured to deliver a light beam
through the reaction chamber, a reactant delivery system comprising
reactant reservoirs, a nozzle configured to deliver one or more
reactants from the reactant delivery system into the reaction
chamber, and a collection system configured to receive the flow
from the reaction chamber that originated from the nozzle. In some
embodiments, the nozzle comprises a reactant channel having a width
and a length, one or more quench gas channels oriented to provide
flow along the length of the reactant channel and one or more
entrainment gas channels oriented along the length of the inert gas
channels, wherein the one or more quench gas channels and the one
or more entrainment gas channels are operably connected to an inert
gas source and the reactant channel is operably connected to the
reactant delivery system and wherein the entrainment inlets have an
area at least about 25% larger than the area of the quench gas
channels.
[0016] In other aspects, the invention pertains to a method for
synthesizing nanoparticles by laser pyrolysis, in which the method
comprises reacting a reactant flow using a light beam to drive the
reaction. In some embodiments, a reactant flow is initiated from a
nozzle with reactants flowed through a reactant inlet with inert
gases flowed through a quench gas inlet approximately surrounding
the flow from the reactant inlet and an inert entrainment gas flows
through an outer gas channel approximately surrounding the inert
quench gas flow wherein the reactant flow substantially completely
flows through a light beam such that energy from the light beam
drives the reaction to form product particles. The entrainment gas
flow can be at a volume at least about 25% greater than the inert
quench gas flow and the entrainment gas flow leaving the nozzle at
a greater velocity than the inert quench gas flow.
[0017] Also, the invention pertains to a laser pyrolysis apparatus
comprising a reaction chamber, a light source and associated
optical elements configured to deliver a light beam through the
reaction chamber, a reactant delivery system comprising reactant
reservoirs, a nozzle configured to deliver one or more reactants
from the reactant delivery system into the reaction chamber, and a
collection system configured to receive the flow from the reaction
chamber that originated from the nozzle. In some embodiments, at
least a portion of the interior of the reaction chamber, at least a
portion of the nozzle exposed to the interior of the reaction
chamber or reactant flow, at least a portion of the collection
system exposed to flow from the reaction chamber, or a combination
thereof is coated with a polymer, ceramic material or combinations
thereof such that flow within apparatus has reduced exposure to
metal contaminants from the apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a schematic representation of a laser pyrolysis
apparatus having three reactant inlet nozzles.
[0019] FIG. 2 is a schematic representation of a reactant delivery
system.
[0020] FIG. 3 is a perspective side view of a reactant inlet nozzle
comprising annular flow channels.
[0021] FIG. 4 is a partially exploded perspective side view of the
reactant inlet nozzle depicted in FIG. 3, shown in a partially
disassembled configuration.
[0022] FIG. 5 is a perspective sectional view of the reactant inlet
nozzle depicted in FIG. 3, in which the section is taken along line
5-5 of FIG. 3.
[0023] FIG. 6 is a sectional side-view of the reactant inlet nozzle
depicted in FIG. 3, in which the same section is shown as in FIG. 5
and in which the dimensions of the flow channels and corresponding
structure is expanded to facilitate viewing.
[0024] FIG. 7A is a top plan view of the reactant inlet nozzle
depicted in FIG. 3.
[0025] FIG. 7B is a top plan view of an alternative embodiment of a
reactant inlet nozzle comprising flow tubes having an oval
cross-sectional shape.
[0026] FIG. 8 is a perspective view of a laser pyrolysis apparatus
comprising a single reactant inlet nozzle and a single collection
apparatus.
[0027] FIG. 9 is a sectional side view of a reactant inlet nozzle
comprising adjacent rectangular flow channels, in which the cross
section is taken along line 9-9 of FIG. 10.
[0028] FIG. 10 is a top plan view of the reactant inlet nozzle
depicted in FIG. 9.
[0029] FIG. 11 is a side plan view of the reactant inlet nozzle
depicted in FIG. 9.
[0030] FIG. 12 is a top plan view of the opening of reactant inlet
nozzle depicted in FIG. 9, showing only the flow channels.
[0031] FIG. 13 is a schematic representation of a printed
substrate.
[0032] FIG. 14 is a TEM micrograph of a silicon particles
comprising about 0.39 at % phosphorous dopant taken at a first
magnification.
[0033] FIG. 15 is a TEM micrograph of silicon particles comprising
about 0.39 at % phosphorous dopant taken at a second
magnification.
[0034] FIG. 16 is a TEM micrograph of silicon particles comprising
about 2.5 at % phosphorous dopant taken at a first
magnification.
[0035] FIG. 17 is a TEM micrograph of silicon particles comprising
about 2.5 at % phosphorous dopant taken at a second
magnification.
[0036] FIG. 18 is a TEM micrograph of silicon particles comprising
about 2.3 at % to about 2.7 at % phosphorous dopant taken at a
first magnification.
[0037] FIG. 19 is a TEM micrograph of silicon particles comprising
about 2.3 at % to about 2.7 at % phosphorous dopant taken at a
second magnification.
[0038] FIG. 20 is a TEM micrograph of silicon particles comprising
about 2.3 at % to about 2.7 at % phosphorous dopant taken at a
third magnification.
[0039] FIG. 21 is a TEM micrograph of silicon particles comprising
about 39 at % boron dopant taken at a first magnification.
[0040] FIG. 22 is a TEM micrograph of silicon particles comprising
about 39 at % boron dopant taken at a second magnification.
[0041] FIG. 23 is a TEM micrograph of silicon particles comprising
about 39 at % boron dopant taken at a third magnification.
[0042] FIG. 24 is a plot of secondary particle size versus
intensity obtained from DLS measurements on a dispersion of silicon
particles with an average primary particle size of 25 nm.
[0043] FIG. 25 is a plot of secondary particle size versus
intensity obtained from DLS measurements on a dispersion comprising
and silicon particles with an average primary particle size of 9
nm.
[0044] FIG. 26 is a plot of secondary particle size versus
intensity obtained from DLS measurements on a dispersion comprising
ethylene glycol.
[0045] FIG. 27 is a plot of secondary particle size versus
intensity obtained from DLS measurements on a dispersion comprising
terpineol and silicon particles
[0046] FIG. 28 is a stroboscopic image of inkjetting of a first ink
from one nozzle.
[0047] FIG. 29 is a photographic image a cured printed ink
drop.
[0048] FIG. 30 is a graph containing plots of shear rate versus
shear stress for inks comprising different solvent blends.
[0049] FIG. 31(a) is a stroboscopic image of a second ink.
[0050] FIG. 31(b) is a stroboscopic image of the printed line from
FIG. 31(a) taken one hour after printing.
[0051] FIG. 32 is a graph containing plots of laser fluence versus
sheet resistance at various pulse widths measured on an ink
layer.
[0052] FIG. 33 is a plot of pulse duration versus fluence threshold
measured on various sintered ink layers.
[0053] FIG. 34 is a composite of optical micrograph images of
various sintered ink layers.
[0054] FIG. 35 is a graph containing plots of depth versus
phosphorous concentration for various sintered ink layers.
[0055] FIG. 36 is a plot of sheet resistance versus minority
carrier diffusion length for various sintered ink layers.
[0056] FIG. 37 is a schematic representation of a diode.
[0057] FIG. 38 is a schematic representation of a laser sintering
pattern forming individual cells on a spin-coated ink layer.
[0058] FIG. 39 is a plot of voltage versus current for a cell
depicted in FIG. 38.
[0059] FIG. 40 is a plot of time versus viscosity for a paste
comprising silicon particles.
[0060] FIG. 41 is a plot of shear rate versus viscosity for a paste
comprising silicon particles.
[0061] FIG. 42 is a plot of viscosity versus time for a paste over
simulated screen printing conditions.
[0062] FIG. 43 is an optical microscope image of a line printed
with a first width with a paste comprising n++ doped silicon
particles.
[0063] FIG. 44 is an optical microscope image of a broader line
printed with a second width with a paste comprising n++ doped
silicon particles.
[0064] FIG. 45 is an optical microscope image of a line printed
with a paste comprising p++ doped silicon particles.
[0065] FIG. 46 is a plot of concentration versus viscosity at a
shear rate of 2 s.sup.-1.
[0066] FIG. 47 is a plot of concentration versus viscosity at a
shear rate of 1000 s.sup.-1.
[0067] FIG. 48 is a graph containing plots of particle size versus
relative intensity generated by DLS analysis on ink samples that
were not centrifuged.
[0068] FIG. 49 is a graph containing plots of particle size versus
relative intensity generated by DLS analysis on ink samples that
were centrifuged.
[0069] FIG. 50 is a graph containing plots of particle size versus
relative intensity generated by DLS analysis on inks that were
processed with planetary milling or bath sonication.
[0070] FIG. 51 is a graph containing plots of particle size versus
relative intensity generated by DLS analysis on inks that were
processed with probe sonication for various time periods.
DETAILED DESCRIPTION OF THE INVENTION
[0071] To simplify processing to form high quality
silicon/germanium semiconducting material with a low level of
contaminants and generally with a significant dopant level, it has
been found that good dispersions of silicon nanoparticles can be
formed without stabilizing the dispersions using non-solvent
organic compositions chemically bonded to the particle surfaces.
Solvents interact with the native particle surfaces with varying
interactions as described further below. The dispersions with
unmodified silicon particles can be formulated at high
concentrations of silicon particles and the properties of the
dispersions can be appropriately adjusted for a desired printing
ink, such as an inkjet ink, other printing ink or a printing paste.
Printable silicon/germanium inks provide significant potential
processing advantages for the formation of semiconductor devices.
The inks can be used for the delivery of dopant elements in a
desirable form for driving into a substrate and/or the deposited
silicon particles can be sintered into a component of a device. For
further processing of the inks after deposition, e.g., printing, of
the ink, it can be desirable to incorporate small nanoparticles
into the inks, and desirable nozzle designs for a laser pyrolysis
reactor are described for the synthesis of high quality silicon
nanoparticles with small particle diameters, optionally with a high
degree of doping. The silicon nanoparticles as well as
corresponding inks can be formulated with very low levels of metal
contaminants, which makes it possible to form particles with
controlled low dopant levels in a meaningful way. The ability to
print silicon nanoparticles, such as highly doped nanoparticles,
using high quality inks can provide significant processing
advantages for printed electronics, solar cell component formation
and other semiconductor applications.
[0072] With respect to desirable nozzles for silicon nanoparticle
production with laser pyrolysis, in some embodiments the nozzle has
an annular configuration that provides quenching of the particles
with an inert gas delivered from the nozzle shortly after synthesis
of the particles. Additional nozzle embodiments have a relative
small path length of the light beam through the reactant flow and
an entraining inert gas flow that facilitates particle nucleation
and quenching. The availability of good quality particles
facilitates the corresponding formation of good quality inks.
[0073] Several improvements are described herein relating to
different stages of the ink formulation process starting with the
synthesis of elemental silicon nanoparticles. For example, laser
pyrolysis apparatus designs provide for the synthesis of highly
uniform silicon nanoparticles at commercially significant rates,
which can have a very low level of total metal contaminants on the
order of 10 parts per million by weight and similarly a very low
level of iron contamination. Using the improved apparatuses
described herein, high dopant levels can be achieved while forming
very uniform silicon nanoparticles. The resulting silicon/germanium
nanoparticles are suitable for the formation of high concentration
dispersions of the nanoparticles. The highly concentrated
dispersions have been formulated without modifying the surface of
the particles with organic compositions, while being able to
achieve desired ink properties over a broad range.
Silicon/germanium refers to silicon, germanium, alloys thereof or
mixtures thereof. To simplify the discussion, elemental germanium
and alloys of germanium with silicon are generally not explicitly
discussed. While the discussion below focuses on silicon, the
analogous processing of and compositions with germanium and alloys
with silicon follows from the discussion based on the similar
chemistries of the elements.
[0074] As described herein, elemental silicon inks can be
formulated for suitable printing processes for commercial
applications. The ability to form good dispersions without chemical
modification of the silicon nanoparticle surfaces with an organic
compound simplifies processing of the particles after printing. For
appropriate embodiments, if there are no organic components bonded
to the particles to remove, the silicon nanoparticles can be
processed for the formation of semiconductor components with
reduced processing to achieve equivalent low levels of
contaminants. Also, the ability to form the dispersions without
organic chemical modification of the silicon nanoparticles can
reduce the processing steps to form the inks. Furthermore, the
processing to form organic modification of the particles involves
the use of additional chemicals that can introduce further
contaminants to the particle dispersion. Based on improved
processing techniques, the particles can be transferred between
solvents or formulated with desired solvent blends for production
of desired ink formulations, which can be formed with very low
levels of contamination. Processing techniques for the inks into
corresponding devices can be selected based on the particular
application.
[0075] Solvents generally interact with solutes with various
interactions, such as hydrogen bonding, polar interactions as well
as various interactions that can have ranges of bonding versus
non-bonding characteristics. These various states of interaction
are at equilibrium within the solution/dispersion. Inorganic
nanoparticles, such as silicon nanoparticles, are a particular type
of solute. In general, for organic molecules, solvated
bio-macromolecules, solvated inorganic species and even inorganic
nanoparticles, the solute-solvent interactions are generally
complex and in many circumstances not completely understood. The
degree of interactions with the solvent can cover a range of
binding strengths with corresponding degrees of reversibility of
the interactions, such as with dry of the solvent. With the
reference to un-modified silicon particles herein, this reference
does not take into account any potential solvent interactions with
the particles.
[0076] It has been proposed that ethanol and ethylene glycol form
reactive species in solution with silicon particles. This
interaction seems to be significantly pH dependent and to also
depend on the degree of oxidation of the particle surfaces as well
as the presence of dissolved oxygen in the solvent. This phenomenon
is described further in Ostraat et al., "The Feasibility of Inert
Colloidal Processing of Silicon Nanoparticles," J. of Colloidal and
Interface Science, 283 (2005) 414-421, incorporated herein by
reference. In the experience of the current inventors, observations
suggest that isopropyl alcohol forms interactive species with the
particle surfaces, but that the isopropyl alcohol is effectively
completely removed through evaporation suggesting that any
solvent-particle interactions are reversible under conditions of
solvent removal. Other observations suggest that ethylene glycol
and propylene glycol may be more difficult to completely remove
with solvent evaporation. However, it is clear that the
solvent-particle interactions are generally of a different
character from strong bonding interactions of specific surface
modification compositions that have been described for modifying
the particle surfaces to alter the solvent interactions with the
modified particle surfaces. In particular, the specific solvent
modifying compositions used to modify the solvent interactions are
generally designed to be effectively irreversible under conditions
in the ink in order to support dispersion in different types of
solvents.
[0077] Laser pyrolysis is a desirable technique for the production
of crystalline silicon nanoparticles, although in principle inks
described herein can be formulated with silicon submicron particles
from other sources that can correspondingly produce high quality
and uniform particle. In some embodiments of particular interest,
the particles are synthesized by laser pyrolysis in which light
from an intense light source drives the reaction to form the
particles from an appropriate precursor flow. Lasers are a
convenient light source for laser pyrolysis, although in principle
other intense, non-laser light sources can be used. The particles
are synthesized in a flow that initiates at a reactant nozzle and
ends at a collection system. Laser pyrolysis is useful in the
formation of particles that are highly uniform in composition and
size. The ability to introduce a range of precursor compositions
facilitates the formation of silicon particles with selected
dopants, which can be introduced at high concentrations.
[0078] Due to the versatility, laser pyrolysis is an excellent
approach for efficiently producing a wide range of nanoscale
particles with a selected composition and a narrow distribution of
average particle diameters. Specifically, laser pyrolysis has been
successfully used for the synthesis of a wide range of complex
inorganic particles, including, for example, compositions with
multiple metal/metalloid elements as well as doped materials. In
the laser pyrolysis process, the dopant element(s) are introduced
into the reactant stream such that the elements can be incorporated
into the product particles. The dopant elements can be delivered
into the reactant stream as a suitable composition. The reactant
stream can comprise gas precursors, vapor precursors and/or aerosol
precursors. Laser pyrolysis can be used to form doped silicon
particles with a wide range of selected dopants or combinations of
dopants. For the doping of semiconductor substrates, desirable
dopants include, for example, B, P, Al, Ga, As, Sb and combinations
thereof. The general use of laser pyrolysis for the formation of a
range of materials including doped silicon nanoparticle is
described in published U.S. Pat. No. 7,384,680 to Bi et al.,
entitled "Nanoparticle Production and Corresponding Structures,"
incorporated herein by reference.
[0079] Due to the nature of the laser pyrolysis process, high
dopant levels can be achieved within the product submicron silicon
particles. Specifically, dopant levels of several atomic percent
can be achieved, as described further below. The ability to achieve
high dopant levels make the corresponding inks particularly
desirable for applications where dopants are transferred to a
semiconducting material from the silicon nanoparticles, or for the
formation directly of components of devices with high dopant levels
through the sintering of the silicon nanoparticles. The high dopant
levels can be achieved while also having control of average primary
particle diameters and while achieving dispersible nanoparticles
with good uniformity.
[0080] Laser pyrolysis can effectively produce uniform particles
due to rapid quenching of the product particles as the particles
leave the reaction zone. Laser pyrolysis has a particular advantage
relative to flame techniques for the synthesis of inorganic
particles that are not metal/metalloid oxides since flame processes
generally have oxygen present to drive the flame. For the synthesis
of silicon particles in comparison with ceramic particles, such as
oxides, nitrides or carbides, quenching of the product particles is
particularly sensitive to limit fusing of the particles within the
flow. Enhanced quenching of reactant flow for laser pyrolysis
reactors with a rectangular nozzle is described in published U.S.
patent application 2009/0020411 to Holunga et al., entitled "Laser
Pyrolysis With In-Flight Particle Manipulation for Powder
Engineering," incorporated herein by reference. Alternative
desirable nozzle designs are described herein based on short path
lengths of the light beam through the reactant flow to achieve
greater uniformity of the reaction across the reactant flow. These
alternative nozzle designs provide a relatively high yield with
respect to reactant flow and reduce effects of light beam
attenuation.
[0081] In some embodiments, the nozzle has an annular or similar
configuration having the reactive flow going around an interior
inert gas flow and a surrounding inert gas flow. The nozzle
configuration provides for efficient quenching of the silicon
particles without any direct interaction with the reactant flow
downstream from the reaction zone. Also, the nozzle has a
convenient design to maintain silicon nanoparticle production for
long term commercial quantities at moderate rates. In further
embodiments, the nozzle has a reactant inlet with an approximately
rectangular shape that is oriented with the length of the inlet
oriented at an angle to the light path, such as perpendicular, to
maintain a relatively small light path through the reactant
stream.
[0082] For the improved nozzle designs, an inert quench gas flow is
supplied to surround the reactant flow. Also, in some embodiments,
a distinct entrainment flow of inert gas can be provided around
both the reactant flow and the inert quench gas flow. The
entrainment flow can facilitate particle nucleation and/or more
efficient quenching of the particles. The entrainment flow
generally has a higher velocity than the other flows and a
relatively large flow volume. However, the velocity differences of
adjacent flows exiting the nozzle are generally not too large to
reduce turbulence that can result from shear between adjacent
flows. Thus, the design of the nozzles to generate an inert
quenching gas flow adjacent to a reactant flow and further a
distinct entrainment inert gas flow surrounding the inert quench
gas flow provides for improved synthesis of silicon nanoparticles
due to the assistance of the entrainment gas flow to facilitate
particle nucleation and subsequent quenching of the particles.
[0083] An early description of the synthesis of crystalline silicon
nanoparticles using laser pyrolysis and a silane precursor is
described in Chapter 3 by Haggerty et al. "Sinterable Powders from
Laser-Driven Reactions," in Laser-Induced Chemical Processes, ed.
by J. I. Steinfeld, Plenum Press 1981, pages 165-241, incorporated
herein by reference. See also, Cannon et al., "Sinterable Ceramic
Powders from Laser-Driven Reaction: I, Process Description and
Modeling," J. Am. Ceramic Society 65 (7), 324 (1982), and Cannon et
al., "Sinterable Ceramic Powders from Laser-Driven Reaction: II,
Powder Characteristics and Process Variables," J. Am. Ceramic
Society 65 (7), 330 (1982), both of which are incorporated by
reference. The formation of doped silicon nanoparticles and
nanostructured coatings is described in U.S. Pat. No. 7,575,784 to
Bi et al., entitled Coating Formation by Reactive Deposition,"
incorporated herein by reference. The use of doped silicon
particles formed by laser pyrolysis is described in published U.S.
patent application 2008/0160265 to Hieslmair et al., entitled
"Silicon/Germanium Particle Inks, Doped Particles, Printing and
Processes for Semiconductor Applications," incorporated herein by
reference.
[0084] In addition to the design of improved nozzles, the laser
pyrolysis apparatus and processes have been redesigned to achieve
exceedingly low metal contaminations for silicon nanoparticles.
Specifically, the precursors can be supplied in extremely purified
forms, and the product particles are collected and handled in a
controlled environment with very clean polymer containers to reduce
or eliminate metal contaminants resulting from handling the
particles. Furthermore, metal contaminant levels may be further
reduced through the coatings of appropriate reaction chamber
components with appropriate coatings, such as polymers, e.g.,
polytetrafluoroethylene, or ceramics, e.g., as silica or silicon
nitride. Based on these improved designs, silicon nanoparticles can
be synthesized with a very high level of purity with respect to
metal elements. Thus, most metal concentrations can be reduced to
levels of no more than about 20 parts per billion by weight (ppb)
for inks with a 10 weight percent particle concentration, and total
metal contamination can be reduced to levels of no more than about
100 ppb by weight ink. With respect to the particles, the
contamination of the particles can be estimated from the particle
concentration of a dispersion and the contamination level of the
dispersion. The particles can have a metal contamination
concentration of any individual metal of no more than about 300 ppb
and a total metal contaminant level of no more than about 1 parts
per million by weight (ppm). To further remove contaminants in the
formation of the dispersions, centrifugation can be used to remove
contaminants from the dispersions with the pure silicon
nanoparticles remaining disbursed in the liquid.
[0085] The properties of dispersions of nanoparticles, among other
factors, depend significantly on the interactions of the particle
surface and the liquid solvent that is functioning as the
dispersant. To help control this interaction, molecules can be
chemically bonded to the surface of the silicon particles. In
general, the molecules bonded to the surface of the silicon
particles are organic, although the compounds can comprise silicon
based moieties and/or other functional groups in addition to
organic moieties. The character of the bonded molecules can then be
selected to facilitate the formation of a good dispersion in a
selected solvent or blend of solvents. Some of the desired ink
formulations can take advantage of surface modification of the
silicon particles, and surface modification is described further
below. Surface modification of silicon particles is also described
further in published U.S. patent application 2008/0160265 to
Hieslmair et al., entitled "Silicon/Germanium Particle Inks, Doped
Particles, Printing and Processes for Semiconductor Applications,"
incorporated herein by reference.
[0086] The surfaces of the silicon particles generally have various
degrees of oxidation and/or hydrogenation, which can depend on the
synthesis conditions as well as the handling of the particles
following synthesis, and such hydrogenation or oxidation is not an
organic modification of the particles. Silicon nanoparticles are
generally crystalline, and silicon submicron particles produced by
laser pyrolysis generally have a high level of crystallinity. In
general, the particle surface represents a termination of the
particle lattice, and the bonds of the surface silicon atoms bond
appropriately to avoid dangling bonds. The surface can terminate
with distorted structures to accommodate multiple bonds between
silicon atoms or bonds with other atoms, such as bridging oxygen
atoms, --OH bonds or --H bonds. For silicon particles formed with
silane precursors, there are generally quantities of hydrogen
available during the formation of particles that can result in some
degree of hydrogenation of the silicon. Contact with air may result
in some oxidation of the surface.
[0087] In some embodiments, it can be desirable for the silicon
particles used in the dispersion to be free from chemical
modification with an organic composition. While, in principle, the
organic moieties can be removed during processing after printing or
other deposition of the silicon ink prior to use of the deposited
silicon particles for device formation, the presence of the organic
moieties in the inks can lead to carbon contamination of the
silicon materials after processing of the silicon into a component.
The electrical properties of the material can be strongly dependent
on the presence of impurities. Therefore, the ability to process
the inks with silicon particles without chemically bonded organic
moieties can simplify processing and reduce average contaminant
levels, or in certain cases may also provide a more flexible device
fabrication process flow. Furthermore, processing steps related to
the chemical modification with an organic moiety as well as steps
related to removal of the chemical modifications clearly can be
eliminated if the particles are not chemically modified with
organic moieties.
[0088] It has been found that good dispersions can be formed of
silicon nanoparticles formed using laser pyrolysis. The dispersions
can be formed at high concentrations, and the properties of the
dispersions can be engineered over desirable ranges based on
particular applications. In particular, the solvent properties for
forming the initial dispersion are significant to be able to form
the dispersions of the particles without surface modification.
Appropriate mixing, sonication or the like can be supplied to
facilitate the initial dispersion of the particles. The
characteristics of the initial dispersion can be evaluated through
an examination of secondary particle properties, such as Z-average
particle size and particle size distribution, measured in the
dispersion using generally light scattering, which are measures of
the size of the dispersed particles in the liquid.
[0089] Once an initial good dispersion is formed with the silicon
nanoparticles in an appropriate solvent to form the good
dispersion, the solvent or blends thereof can be manipulated to
form an overall ink with selected properties while maintaining the
good dispersion of the particles. Specifically, techniques have
been developed for more versatile exchange of solvents or formation
of solvent blends such that a desirable solvent system can be
selected for a particular printing approach. With the ability to
provide highly uniform silicon nanoparticles in high concentration
dispersions with selected solvents, inks can be formulated that can
be printed using desirable approaches. After printing, the inks can
be used to form components of semiconductor devices or as a dopant
source to be driven into an underlying semiconductor material. In
particular, the silicon inks can be used for forming components of
solar cells or of electronic devices, such as thin film
transistors. In some embodiments, the particles can be incorporated
directly into a component of an ultimate product. The good
dispersion can be characterized with respect to the secondary
particle sizes and distributions. Dispersions that are too
concentrated for direct measurement of secondary particle sizes can
be diluted, for example, to a 1 weight percent concentration for
the secondary particle characterization. In particular, it can be
desirable for the Z-average particle size to be no more than about
250 nm and in further embodiments no more than about 150 nm.
[0090] The engineering of a desired ink can involve several
parameters. For example, a desired ink generally comprises a
solvent or blend of solvents with desired properties. Many ink
formulations advantageously comprise a blend of solvents to achieve
target ink properties. The use of a blend of solvents can be
particularly effective for the formation of an ink with desired
properties for processing. In general, if a blend of solvents is
used, the solvents form a single liquid phase either due to
miscibility or solubility of the solvents relative to each other. A
starting point for ink formulations involves the formation of well
dispersed silicon particles. Once the particles are well dispersed,
the resulting dispersion can be appropriately modified to form a
selected ink. Solvent can be removed by evaporation to increase the
particle concentration. A good dispersion is characterized by the
nanoparticles remaining suspended, with no significant particle
settling, for at least an hour without application of additional
mixing. At higher particle concentrations of the inks, the
secondary particle sizes cannot be directly measured by optical
methods. But the higher concentration inks can be evaluated by the
lack of particle settling, i.e., remaining a good dispersion, and
by diluting the concentrated ink to a concentration where the
secondary particle size can be measured.
[0091] For many ink formulations, the inks have a relatively large
particle concentration, for example, at least about 0.5 weight
percent or possibly significantly higher. With improved processing
techniques and ink formulations described herein, the inks can be
formulated with high silicon particle concentrations and with
desirable rheological, i.e., fluid, properties. Suitable inks are
described for inkjet printing, gravure printing and screen printing
with a paste consistency, and other inks can be similarly
formulated based on this teaching. To obtain desired thickness of
deposited inks, a coating or printing process can be repeated to
form multiple layers of the ink with a corresponding greater
thickness.
[0092] For silicon nanoparticles inks for most printing
applications, it can be desirable to use a blend of solvents.
Similarly, convenient processing approaches can be adapted for the
formation of inks with a blend of organic liquids that can be
referred to as solvents for convenience. Specifically, the blend of
solvents generally comprises a first low boiling temperature
solvent, generally having a boiling point of no more than about
160.degree. C. and a second high boiling temperature solvent,
generally having a boiling point of at least about 175.degree. C.
The solvents are generally selected to form a single liquid phase
upon mixing. The lower boiling solvent can be removed upon printing
of the ink to stabilize the printed material, and the higher
boiling solvent can be removed upon further processing of the
printed material.
[0093] For processing to form the desired inks, the particles are
generally dispersed in the low boiling solvent to form a good
dispersion. The silicon nanoparticles formed using laser pyrolysis
can be well dispersed in alcohols. The second high boiling point
solvent can be added to the initial silicon nanoparticle
dispersion. A portion of the low boiling point solvent can be
evaporated to achieve the desired overall solvent composition, and
particle concentration. The solvent blend can be selected to
maintain a good dispersion of the silicon particles at the selected
concentrations of particles, and the solvents should also be
selected to achieve the desired viscosities, surface tensions
and/or other desired ink properties.
[0094] The silicon particle inkjet inks generally have a relatively
low viscosity with a relatively large particle loading over
reasonable ranges of shear. In some embodiments, one of the
solvents for the inkjet ink generally comprises an alcohol, and
another solvent can be an aprotic polar solvent. For inkjet inks,
it is generally desirable for the ink to comprise at least about 5
weight percent silicon particles.
[0095] The silicon inks can also be formulated for gravure
printing. In gravure printing, the ink is spread onto a printing
plate that has depressions to hold the ink at selected locations.
After any excess ink is removed, the printing plate is pressed onto
the printing surface to transfer the ink to the surface in the
pattern established by the printing plate. The printing plate can
be shaped as a roller to facilitate the transfer process. The
silicon inks for gravure printing are generally between the values
for an inkjet ink and a screen printing paste.
[0096] The silicon ink pastes, such as screen printing pastes,
generally have very high viscosities. The pastes generally comprise
a low boiling point solvent that evaporates upon printing of the
paste. The pastes further comprise a high boiling temperature
solvent that can be selected to provide desirable paste properties
and to be consistent with materials used for forming the printing
screens. The printing screens are generally used repeatedly, so the
screen printing paste should be selected to avoid significantly
damaging the screens or masks with use.
[0097] In general, the silicon inks can be deposited by any
suitable deposition approach, and as noted above, the inks can be
correspondingly formulated for a particular deposition approach.
For example, suitable deposition approaches include, for example,
coating approaches and direct patterning approaches, such as
printing. With proper formulation of the silicon inks, appropriate
coating approaches, such as spin coating, spray coating or the
like, can be used to form a layer of the ink. In general, any
reasonable printing technique can be used, such as inkjet printing,
gravure printing or screen printing, and the inks can be
appropriately formulated. In general, any reasonable substrate can
be used for deposition of the silicon nanoparticle inks. In some
embodiments, the substrate can comprise a semiconductor, such as
silicon, and the ink can be used to supply dopant elements and/or
to form a component of a device on the substrate. In alternative
embodiments, the substrate can comprise a polymer sheet onto which
the silicon ink is deposited. Other inorganic materials, such as
dielectrics and electrical conductors, can also be used as
substrates for silicon ink deposition.
[0098] In some embodiments, printing processes can effectively
supply compositions in patterns over large areas quickly and
efficiently. For semiconductor applications, the use of printing
techniques described herein may eliminate one or more
photolithography steps that may be involved in more traditional
processing approaches to achieve the desired patterning. The
silicon inks can be formulated for various printing approaches with
appropriate attention to processing efficiencies, desired
resolutions of the printed structures, capital equipment
availability and other appropriate issues.
[0099] For circuit formation, the substrate can comprise
semiconductor materials, such as silicon, germanium or alloy
thereof, or in other embodiments, a polymer substrate. A printing
process can deposit the ink at specific locations along the
substrate surface. This allows the selective placement of silicon
particles with or without a dopant along the substrate, such as for
formation of specific circuit components. Similarly, the placement
of doped silicon particles along a substrate can provide a dopant
source that can provide a dopant that can be driven into the
adjacent substrate for the formation of circuit components. Other
patterning approaches can be used with the inks alone or combined
with a printing approach, or no patterning can be used, as
appropriate for a specific application.
[0100] For printed circuit applications, once a doped silicon ink
is deposited at selected locations, the particles can be sintered
or otherwise fused at the deposited position on the substrate to
form a corresponding structure or domain. This can be done, for
example, by heating the substrate in an oven to relatively high
temperatures, such as 750.degree. C. to 1250.degree. C. to obtain a
solid mass from the particles in intimate contact with the
substrate surface. Nanoparticles may melt or flow at lower
temperatures than larger particles so that the use of nanoparticles
can facilitate the process with oven based heating. These
temperatures are still below the melting point of bulk silicon, so
that rapid thermal annealing can be used on silicon substrates and
other relatively high temperature substrates. However, in some
embodiments, improved control of the process as well as energy
saving can be obtained through the application of light energy,
such as from a laser or incoherent light source, to melt the
particles at the deposited position along the substrate without
generally heating the substrate or only heating the substrate to
lower temperatures. This photonic curing process may be suitable
for some lower melting substrates.
[0101] Printed circuit applications of particular interest include,
for example, display circuits in which electrical connections for
display elements cover a relatively large area while involving
moderate resolution to distinguish the elements. The display
circuits can be formed through the printing process and subsequent
processing to form the circuitry for controlling the display
element. The display circuits can comprise thin film transistors
that can comprise components formed with the silicon inks described
herein.
[0102] The formation of desirable solar cell elements on a thin
silicon foil is described further in published U.S. patent
application 2008/0202576A to Hieslmair et al., entitled "Solar Cell
Structures, Photovoltaic Panels and Corresponding Processes,"
incorporated herein by reference. The '576 application describes
forming shallow doped regions in some embodiments. These shallow
doped regions can be conveniently formed by printing the doped
silicon and using heat and/or light, such as from a laser or flash
lamp, to fuse the doped silicon into corresponding doped contacts.
This processing can further lead to dopant drive-in to supply
dopant in the initial silicon material. Also, the doped silicon
particles described herein can be also used to deliver the dopant
atoms to the underlying silicon substrate. Also, other similar
solar cell elements can be formed on other silicon or other
semiconducting substrates for solar cell applications. Dopant
drive-in and silicon particle fusing is described further in
copending U.S. provisional patent application 61/438,064 to Liu et
al, entitled "Silicon Substrates With Doped Surface Contacts Formed
From Doped Silicon Inks and Corresponding Processes," incorporated
herein by reference. If the silicon particles are used solely as a
dopant source, the remains of the particles can be removed
following processing if desired.
[0103] As described herein, high quality dispersions of silicon,
with or without dopants, provides the ability for effective
deposition of silicon nanoparticles, and in some embodiments the
nanoparticles can be printed to form moderate resolution
structures. Due to the enhanced ability to control the properties
of the inks, the silicon can be printed rapidly and with a selected
printing technique, for example, using inkjet printing, gravure
printing, screen printing or other desired approach. The ability to
introduce silicon with selected dopants over a wide range of
compositions provides the ability to form a corresponding wide
range of devices based on the silicon particles. The dopants can be
selected based on the particle device to be formed and the
corresponding desired electrical properties for the element or
component. Using a selected printing process, silicon particles
with different dopants can be selectively placed at different
locations along the substrate surface.
Laser Pyrolysis Synthesis of Silicon Particles and Improved Nozzle
Design
[0104] Laser pyrolysis is an effective method for the synthesis of
high quality inorganic submicron particles. With appropriate design
of the laser pyrolysis apparatus, highly uniform silicon
nanoparticles can be synthesized with high levels of dopants. A
multichannel nozzle design has been developed that provides for
more effective control of silicon nanoparticle synthesis to support
the production of small silicon nanoparticles with a high degree of
uniformity. In particular, in some embodiments, the nozzle provides
a core of inert gas as well as a blanket of inert gas surrounding
the outside of the reactive flow such that the blending of the
flows following the reaction zone results in effective quenching of
the particles. In additional or alternative embodiments, a
generally rectangular nozzle can be used with a short path length
of the light beam through the reactant stream to reduce effects of
light beam attenuation. In general, an entrainment flow with
relatively high velocity relative to the reactant flow and a high
flow rate can be used to surround the reactant flow and an inert
quenching gas flow to facilitate the confinement of the reactant
flow and quenching gas. As described further below, the effective
control of the particle synthesis can be directed at the synthesis
in some embodiments of uniform silicon nanoparticles with an
average primary particle diameter no more than about 50 nm.
[0105] For convenience, light-based pyrolysis is referred to as
laser pyrolysis since this terminology reflects the convenience of
lasers as a radiation source and is a conventional term in the art.
Laser pyrolysis approaches discussed herein incorporate a reactant
flow that can involve gases, vapors, aerosols or combinations
thereof to introduce desired elements into the flow stream. The
versatility of generating a reactant stream with gases, vapor
and/or aerosol precursors provides for the generation of particles
with a wide range of potential compositions.
[0106] Designs of laser pyrolysis apparatuses for larger scale
particle production have been based on the use of an inlet that has
an extended dimension of the reactant inlet and a chamber that
conforms to the inlet dimensions. An axis pointing along the
extended dimensions of the opening of the nozzle inlet generally
has been aligned roughly parallel to the line along the propagation
direction of the light beam through the reaction chamber so that
essentially the entire reaction flow can pass through the light
beam. The slit type inlet provides for increased reactant flux
through the light beam. This design is described, for example, in
U.S. Pat. No. 5,958,348 to Bi et al. (the '348 patent), entitled
"Efficient Production of Particles by Chemical Reaction,"
incorporated herein by reference. However, it has been found that
light beam attenuation along the parallel nozzle can result in low
yields and an undesirable reduction in uniformity along the length
of the nozzle, especially for elemental silicon particle synthesis.
Alternative nozzle designs are described herein that can produce
appropriate production rates for doped silicon nanoparticles with
very good uniformity and with high dopant levels. In particular,
the nozzles can be designed for rapid quenching of the flow
following reaction along with confinement of the reactive flow with
quenching gas, which is particularly significant for silicon
nanoparticles with average primary particle diameters of no more
than about 50 nm, which involves particular attention to particle
quenching in the flow.
[0107] Improvements in the laser pyrolysis nozzle design provides
for the synthesis of more uniform elemental silicon nanoparticles
with selectable particle sizes and optionally high dopant levels.
In particular, the improved nozzles can have separate flows of
reactants and inert gas within strong flows of inert entraining gas
that has a relatively greater flow volume and flow velocity to help
to confine the inner flows. In general, the entrainment gas flow
has a velocity out of the nozzle of at least about 5 percent
greater than the reactant flow, and the volume of entrainment gas
is generally at least about 10% greater than the flow of inert
quenching gas.
[0108] The overall nozzle configuration influences the reactant
inlet properties. For example, the reactant inlet shape can range
from an annular shape to a rectangular shape. For annular shaped
reactant inlets and the like, a central channel can be used for the
delivery of inert quench gas. For a particular nozzle, the path
length of the light beam through the reactant flow should be
relatively small so that the effects of light beam attenuation can
be better managed. The reaction can be controlled to produce
uniform particles with a selected average particle size.
[0109] In some embodiments with a reactant inlet oriented around a
central inner quenching gas channel, inner shielding gas and outer
shielding gas can be supplied with an annular or similar
non-circular reactant inlet with inert shielding gas fed in the
interior of the nozzle and around the outside of the reactant flow.
An entrainment inert gas flow can also be supplied through a
separate ring of the nozzle. The use of an annular reactant inlet
can provide for a more uniform reactant flow across dimensions of
the flow, and the greater uniformity of the flow correspondingly
provides for greater uniformity of the resulting product particles.
This nozzle design can be used for the synthesis of a wide range of
inorganic nanoparticles using laser pyrolysis, although herein the
nozzle is exemplified for synthesis of elemental silicon
nanoparticles and corresponding doped particles.
[0110] In additional embodiments, the reactant inlet has an
approximately rectangular shape or similar slit shape. In contrast
with the design described in the '348 patent cited above, the
reactant inlet is oriented with the inlet length perpendicular or
at an angle to the light beam such that path length of the light
beam through the reactant flow is relatively small so that effects
of beam attenuation is significantly reduced. An entrainment inert
gas flow can confine the reaction to facilitate the particle
formation.
[0111] The reactant flow from the reactant nozzle generally is
oriented to pass essentially entirely through a light beam, such as
a laser beam. Since the absorption of light drives the reaction of
the reactant flow within a small reactant zone, it is desirable for
the entire or approximately the entire reactant flow to pass
through the light beam so that the product particles maintain a
desired high level of uniformity. The reaction zone generally
overlaps with the location of the intersection of the reactant flow
with the light beam, and the particles quench relatively rapidly
after leaving the reaction zone. The light beam generally can be
directed to cross the reaction chamber and strike a beam dump, such
as a power meter. A plurality of improved quenching nozzles can be
aligned in a single chamber such that a light beam passes
sequentially through the reactant flow from the nozzles. The use of
a plurality of aligned nozzles correspondingly can be used to
increase the throughput through a single chamber.
[0112] The reaction conditions can determine the qualities of the
particles produced by laser pyrolysis. The reaction conditions for
laser pyrolysis can be controlled relatively precisely in order to
produce particles with desired properties. For example, the
reaction chamber pressure, flow rates, composition and
concentration of reactants, radiation intensity, radiation
energy/wavelength, type and concentration of inert diluent gas or
gases in the reaction stream, temperature of the reactant flow can
affect the composition and other properties of the product
particles, for example, by altering the time of flight of the
reactants/products in the reaction zone and the quench rate. Thus,
in a particular embodiment, one or more of the specific reaction
conditions can be controlled. The appropriate reaction conditions
to produce a certain type of particles generally depend on the
design of the particular apparatus. Specific conditions used to
produce selected silicon nanoparticles in particular apparatuses
are described below in the Examples. Furthermore, some general
observations on the relationship between reaction conditions and
the resulting particles can be made.
[0113] Reactant velocity of the reactant gas stream is inversely
related to particle size so that increasing the reactant velocity
tends to result in smaller particle sizes. A significant factor in
determining particle size is the concentration of product
composition condensing into product particles. Reducing the
concentration of condensing product compositions generally reduces
the particle size. The concentration of condensing product can be
controlled by dilution with non-condensing, e.g., inert,
compositions or by changing the pressure with a fixed ratio of
condensing product to non-condensing compositions, with a reduction
in pressure generally leading to reduced concentration and a
corresponding reduction in particle size and vice versa, or by
combinations thereof, or by any other suitable means. Light power
also influences particle size with increased light power favoring
larger particle formation for lower melting temperature materials
and smaller particle formation for higher melting temperature
materials.
[0114] The use of a radiation, e.g., light, beam, to drive the
reaction can result in a localized reaction zone that leads to high
uniformity of the particles. Beyond the reaction zone, the product
flow comprises product particles, unreacted reactants, reaction
by-products and inert gases. The product flow can continue to a
collector at which at least a significant portion of the product
particles are harvested from the flow. An effectively continuous
supply of reactants initiate a reactant flow directed to the
reaction zone. Removal of product particles from the product flow
prior to venting during the course of the reaction characterizes
the reaction process within the flowing reactant system.
[0115] To perform laser pyrolysis, one or more reactants can be
supplied in gas phase or vapor phase. Suitable gaseous reactants
for elemental silicon particle formation and dopant reactants are
described below. Alternatively or additionally, one or more
reactants can be supplied as an aerosol. The use of an aerosol
provides for the use of a wider range of precursors for laser
pyrolysis than are suitable for vapor delivery only. Suitable
control of the reaction conditions with the selected reactant flow
results in submicron/nanoscale particles with a narrow particle
size distribution.
[0116] A representative laser pyrolysis apparatus for use with the
nozzle designs described herein is shown in FIG. 1. In the
embodiment in FIG. 1, the apparatus comprises a reactant delivery
system 102, a reaction chamber 104, an optical system 106 to
deliver a light beam and a collection system 108. Reactant delivery
system 102 can comprise a reactant source 110, reactant inlet
nozzles 112, 114, 116 and a manifold 118. Reactant inlet nozzles
112, 114, 116 are configured to initiate a reactant flow through
reaction chamber 104, and manifold 116 is configured to deliver
reactant flow from reactant source 110 to reactant inlet nozzles
112, 114, 116. Collection system 108 can comprise exhaust conduits
120, 122, 124 that direct the product flow from reaction chamber
104, and exhaust conduits 120, 122, 124 can be positioned such that
the flow from reactant inlet nozzles 112, 114, 116 inherently
follows a path roughly towards the exhaust conduits 120, 122, 124.
As shown in FIG. 1, reactant inlet nozzles 112, 114, 116 for
reaction chamber 104 are placed on the bottom of reaction chamber
104 and exhaust conduits 120, 122, 124 are placed along the top of
reaction chamber 104. In alternative or additional embodiments,
these positions can be reversed with reactant inlet nozzles 112,
114, 116 positioned along the top of reaction chamber 104 and
exhaust conduits 120, 122, 124 positioned along the bottom of
reaction chamber 104. Similarly, a fraction of a set of inlet
nozzles can be placed along the top of the reaction chamber and a
fraction of the inlet nozzles can be placed along the bottom of the
reaction chamber.
[0117] As shown in FIG. 1, reaction chamber 104 has the approximate
shape of a rectangular parallelepiped, although other shapes, such
as a generally cylindrical shape, can be used as appropriate. As
noted above, the embodiments of particular interest described
herein comprise nozzles with a series of flow channels and a
reactant inlet configured to surround an inert gas flow, as
described in more detail below. As shown in FIG. 1, the laser
pyrolysis apparatus is configured with three reactant inlet nozzles
112, 114, 116 flowing through a single reaction chamber 104. In
alternative or additional embodiments, the reaction chamber can be
configured with a single reactant inlet nozzle, two reactant inlet
nozzles, four reactant inlet nozzles or more than four reactant
inlet nozzles. In general, the number of reactant inlet nozzles may
be constrained due to the attenuation of the light beam as it
passes through the flow from other reactant inlet nozzles. As shown
in FIG. 1, reactant inlet nozzles 112, 114, 116 are collinear such
that a light beam can pass through the flow from all of the
reactant inlet nozzles 112, 114, 116 although if the optical path
is adjusted appropriately, other reactant inlet nozzle
configurations can be used.
[0118] Reaction chamber 104 can be constructed, for example, from
metal components, such as stainless steel or the like. In some
embodiments, portions of the interior of reaction chamber 104 can
be coated with a polymer, such as polytetrafluoroethylene,
polycarbonate, polyamides or other suitable polymer or combinations
thereof, or with a ceramic composition, such as silica, silicon
nitride, other suitable ceramic composition or combinations
thereof. Coating of a metal reaction chamber and/or the reactant
inlet nozzle or portions thereof may reduce metal contaminants n
the product flow. In addition, the reaction chamber and/or nozzle
components can be formed from ceramics, such as silica or quartz,
to provide low contaminant levels while maintaining a durable
apparatus.
[0119] Optical system 106 can comprise a light source 126, optical
element 128, and a beam dump 130 or the like. In operation, light
emitted from light source 126 pass through optical element 128 and
into reaction chamber 104. Light emitted from light source 126 that
is not absorbed in reaction chamber 104 by the reactant stream then
passes into beam dump 130 where the optical path is terminated.
Light source 126 can comprise a laser or other intense light
source. While laser pyrolysis can be performed with radiation at a
variety of optical frequencies, convenient light sources operate in
the infrared portion of the electromagnetic spectrum, although
other wavelengths can be used, such as the visible and ultraviolet
regions of the spectrum. Excimer lasers can be used as ultraviolet
sources. CO.sub.2 lasers are particularly useful sources of
infrared light. Suitable CO.sub.2 lasers are commercially
available. Beam dump 130 can comprise commercial power meters. An
appropriate power meter for a CO.sub.2 laser is available from
Coherent Inc., Auburn, Calif. Optical element 128 can comprise
lenses mirrors, windows, or the like. Optical element 128 can be
used to control the optical path of the output beam generated from
light source 126. For example, a cylindrical lens can be used to
focus the beam in a single dimension. In such an example, the
thickness of the beam along the vertical dimension can be narrowed
without narrowing the beam in the horizontal dimension so as to
allow a wider reactant flow can pass through the beam.
Alternatively or additionally, telescopic optics can be used as
described in published U.S. patent application 2005/0200036A to
Mosso et al., entitled "Particle Production Apparatus,"
incorporated herein by reference. While the embodiment of an
optical system depicted in FIG. 1 comprises only one optical
element, in other embodiments an optical system can comprise a
plurality of optical elements. In general, optical system 106 can
further comprise light tubes 132, 133 that enclose the beam
generated from light source 126 on its path to the beam dump.
Additionally, light tubes 132, 133 can also provide the spacing of
optical elements away from reaction chamber 104 to reduce
contamination of the optical element 128 with compositions flowing
through reaction chamber 104. Appropriate flows of inert shielding
gas can also be flowed into light tubes 132, 133 to reduce
contamination of optical elements 128.
[0120] Collection system 108 can comprise filter elements 134, 136,
138, a negative pressure device 140, and conduits 120, 122, 124.
Filter elements 134, 136, 138 can comprise filter mediums that
divides a clean plenum downstream from the filter element and a
product plenum upstream from the filter element. Alternatively,
filter elements 134, 136, 138 can comprise electrostatic collectors
to remove particles from the flow. A bag style collector suitable
for a laser pyrolysis apparatus is described further in U.S. Pat.
No. 6,270,732 to Gardner et al., entitled "Particle Collection
Apparatus and Associated Methods," incorporated herein by
reference. Suitable negative pressure devices can comprise, for
example, a blower, a pump, such as a mechanical pump or vacuum
pump, an aspirator or other suitable devices that can maintain a
desired pressure and flow through the apparatus. The collection
system can further comprise a scrubber or the like to remove any
unreacted precursor compositions and/or reaction byproducts prior
to venting the exhaust gas.
[0121] A representative reactant delivery system is shown in FIG.
2. In general, a reactant delivery system can be configured with a
plurality of different precursor sources. The configuration shown
schematically in FIG. 2 can be designed for the synthesis of
silicon particles with an optional selected dopant. Suitable
silicon precursors include, for example, gaseous compounds. Dopant
precursors can be gaseous compounds and/or liquid or solid
compounds with sufficient vapor pressure. Precursor compounds can
optionally be delivered with a carrier gas, and mass flow
controllers can be used to control the flow through the system. In
some embodiments, a flash evaporator can be used to deliver a
selected partial pressure of a compound with excellent control and
reproducibility. The reactant flow can also be optionally combined
with an inert diluent gas to modulate the reaction conditions.
[0122] FIG. 2 shows an embodiment of reactant delivery system 160
in relation to a reaction chamber 162. Reactant delivery system 160
is suitable for the delivery of the reaction precursor component of
a reaction stream to an inlet nozzle such as reactant inlet nozzles
112, 114, 166 depicted in FIG. 1. In particular, reactant delivery
system 160 is suitable for the delivery of vapor/gaseous reactants.
As shown in FIG. 2, reactant delivery system 160 comprises a gas
delivery subsystem 164 and a vapor delivery subsystem 166 that both
join a mixing subsystem 168. Gas delivery subsystem 164 can
comprise one or more gas sources, such as a gas cylinder or the
like for the delivery of gases into the reaction chamber. As shown
in FIG. 2, gas delivery subsystem 164 comprises reactant gas
sources 170, 172, inert gas source 174, and an optional light
absorbing gas source 176 that can supply a light absorbing gas for
laser pyrolysis. A reactant stream comprising light absorbing gas
can be desirable if a reaction precursor does not sufficiently
absorb the intense light. In other embodiments, gas delivery
subsystem 164 can comprise a different number of gas sources such
that desired reactant gases and/or other gases can be selected as
desired.
[0123] The gases combine in a gas manifold 178 where the gases can
mix. Gas manifold 178 can have a pressure relief valve 180 for
safety. Inert gas source 174 can be also used to supply inert gas
to the interior of light tubes 182, 184 used to reduce
contamination of any optical elements associated with the light
tubes. Mass flow controllers can be used to regulate the flow of
gases to gas manifold 178.
[0124] Vapor delivery subsystem 166 comprises a plurality of flash
evaporators 186, 188, 190. Although shown with three flash
evaporators, vapor delivery subsystem can comprise, for example,
one flash evaporator, two flash evaporators, four flash evaporators
or more than four flash evaporators to provide a desired number of
vapor precursors that can be selected for delivery into reaction
chamber 162 to form desired inorganic particles. Each flash
evaporator can be connected to a liquid reservoir to supply liquid
precursor in suitable quantities. Suitable flash evaporators are
available from, for example, MKS Equipment or can be constructed
from readily available components. The flash evaporators can be
programmed to deliver a selected partial pressure of the particular
precursor. The vapors from the flash evaporator are directed to a
manifold 192 that directs the vapors to a common feed line 194. The
vapor precursors mix within manifold 192 and common feed line 194.
A flash evaporator can be replaced by a solid precursor delivery
apparatus, which can heat a solid to generate a vapor that can then
be delivered with a carrier gas if desired. The carrier gas can be,
for example, an infrared absorber, a secondary reactant, an inert
gas or mixtures thereof.
[0125] The gas compositions from gas delivery subsystem 164 and
vapor compositions from vapor delivery subsystem 166 are combined
within mixing subsystem 168. Mixing subsystem 168 can be a manifold
that combines the flow from gas delivery subsystem 164 and vapor
delivery subsystem 166. In the mixing subsystem 168, the inputs can
be oriented to improve mixing of the combined flows of different
vapors and gases at different pressures. The mixing block can have
a slanted termination to reduce backflow into lower pressure
sources. A conduit 196 leads from mixing subsystem 168 to a
reactant inlet nozzle 198 and ultimately to reaction chamber 162.
Where the reactant delivery system comprises a plurality of
reactant inlet nozzles, such as in the embodiment of a laser
pyrolysis apparatus depicted in FIG. 1, conduit 196 can comprise a
manifold to deliver a portion of the reactant stream to each of the
reactant inlet nozzles or each reactant delivery nozzle can be
configured with a distinct reactant delivery system, such as
reactant delivery system 160.
[0126] Reactant delivery system 160 can be configured to deliver a
selected reactant composition based on a supply with a range of
precursors and other reactants to tune a particular inorganic
particle composition without refitting the unit since a number of
precursors supplies can be integrated together within the unit
simultaneously. For the formation of complex materials and/or doped
materials, a significant number of reactant sources and,
optionally, separate reactant ducts can be used for
reactant/precursor delivery. For example, as many as 25 reactant
sources and/or ducts are contemplated, although in principle, even
larger numbers could be used. For the formation of doped elemental
silicon particles, generally only a silicon precursor and a more
modest number of dopant sources can be used in the reactant
delivery system.
[0127] Referring to FIG. 2, a heat controller 200 can be used to
control the temperature of various components through conduction
heaters or the like throughout the vapor delivery subsystem 166,
mixing subsystem 194 and/or conduit 196 to reduce or eliminate any
condensation of precursor vapors. A suitable heat controller is
model CN132 from Omega Engineering (Stamford, Conn.). Overall
precursor flow can be controlled/monitored by a DX5 controller from
United Instruments (Westbury, N.Y.). The DX5 instrument can be
interfaced with mass flow controllers (Mykrolis Corp., Billerica,
Mass.) controlling the flow of one or more vapor/gas precursors.
Pressure sensors can be used to monitor the chamber pressure, and
appropriate control systems, feedback devices and the like can be
used to control the operation of the system. Valves, such as
automated valves, can also be used to control the flow and pressure
within the system. The automation of the unit can be integrated
with a controller from Brooks-PRI Automation (Chelmsford, Mass.). A
description of a comparable reactant delivery system for a laser
pyrolysis with alternative reactor and nozzle designs is provided
in published U.S. patent application 2009/0020411A to Holunga et
al., entitled "Laser Pyrolysis With In-Flight Particle Manipulation
for Powder Engineering," incorporated herein by reference.
[0128] FIGS. 3-6 show an embodiment of a reactant inlet nozzle 220
separated from a reaction chamber. Reactant inlet nozzle 220 can be
desirable for the formation of silicon nanoparticles and can also
be used effectively for the synthesis of other nanoparticles using
laser pyrolysis. Furthermore, reactant inlet nozzle 220 has the
advantage of a robust design that is amenable to the exchange of
elements for cleaning, repair, or for modification of the reactant
flow. FIG. 3 depicts reactant inlet nozzle 220 in an assembled
configuration, and FIG. 4 depicts a partially exploded view of
reactant inlet nozzle 220. FIGS. 5 and 6 depict cross-sectional
views of nozzle 220 in an assembled configuration. Reactant inlet
nozzle 220 comprises flow elements 222, 224, 226, 228 in a nested
configuration. Reactant nozzle 220 can also desirably comprise
sealing plate 229. Sealing plate 229 comprises trough 265, bolt
holes 266 and a central hole 267. Sealing plate 262 is designed to
secure reactant inlet nozzle 220 to a reaction chamber with bolts
that extend through bolt holes 266. A portion of flow element 238
extends through central hole 267 such that the nozzle extends into
the reaction chamber for the delivery of reactants in a reactant
flow. A seal can be established between sealing plate 262 and flow
element 238, for example, with a rubber or polymer gasket, with a
weld or other appropriate method. A rubber gasket, other polymer
gasket or the like can be placed within trough 265 to affect a seal
between sealing plate 262 and the reaction chamber upon connection
of the nozzle to a reactor.
[0129] Each flow element 222, 224, 226, 228 comprises a support hub
230, 232, 234, 236, a flow tube 238, 240, 242, 244, and an access
port 246, 248, 250, 252. In this embodiment, each support hub
approximately forms a cylindrical block with a central channel, and
each flow tube approximately forms a cylinder. Each flow element is
constructed such that the corresponding flow tube rests within a
recess within the central channel of the corresponding support hub.
Each access port extends through the block to the central channel
of the corresponding support hub and forms a delivery channel
within the lumen of the corresponding flow tube, which may be
bounded by the exterior of an inner flow tube except for flow tube
238, which is at the center of the nozzle. In a nested
configuration, flow elements 222, 224, 226, 228 are assembled such
that the flow tubes form a nozzle comprising concentric cylinders
with a common central axis. Referring to FIGS. 3-6, access port 246
extends through the bottom of support hub 230 and forms a delivery
channel between the exterior of support hub 230 and flow tube 238.
Access ports 248, 250, 252 extend through the side of corresponding
support hubs 232, 234, 236 and form delivery channels between the
exterior of each support hub 232, 234, 236 and the central channel
of the respective support hub.
[0130] Reactant inlet nozzle 220 is configured in a nested
configuration. Flow element 226 is placed in contact with the
opposite surface of flow element 228, relative to sealing plate
262, such that flow tube 242 extends into the lumen of flow tube
244. Flow element 224 is placed in contact with the opposite
surface of flow element 226, relative to sealing plate 262, such
that flow tube 240 extends into the lumen of flow tubes 242, 244.
Flow element 222 is placed in contact with the opposite surface of
flow element 224, relative to sealing plate 262, such that flow
tube 238 extends into the lumen of flow tubes 240, 242, 244. Nested
flow tubes 238, 240, 242, 244 form an annular nozzle 253 comprising
an inner lumen defined by flow tube 238 and an outer lumen defined
by flow tube 244. Furthermore, in this embodiment, the relative
orientation of each flow element 222, 224, 226, 228 of reactant
inlet nozzle 220 about the common long axis of flow tubes 238, 240,
242, 244 can be desirably configured such that access ports 250,
248 are rotated 90.degree. and 180.degree., respectively, from
access ports 242 to provide for convenient connection of supply
tubes to the access ports. However, in other embodiments of a
reactant inlet nozzle, other relative orientations of the flow
elements can be used as desirable. Reactant inlet nozzle 220 can
further comprise bolts 254 that secure together flow elements 222,
224, 226, 228 and as well as fix the relative orientation of flow
elements 222, 224, 226, 228 about the common long axis of flow
tubes 238, 240, 242, 244.
[0131] Sealing elements 256, 258, 260 are located between flow
elements 222, 224, between flow elements 224,266, and between flow
elements 226,228, respectively. Sealing elements 256, 258, 260 are
designed to provide a fluid tight seal at the interface between
adjacent flow elements 222, 224, 226, 228. Sealing elements 256,
258, 260 can be formed from rubber o-rings, other polymer materials
or the like.
[0132] The diameters of flow tubes 238, 240, 242, 244 generally are
designed to have the dimensions of reactant stream roughly match
the dimensions of the light beam positioned to intersect with the
reactant stream. In particular, approximately the entire reactant
stream should flow through the beam, so that the inner diameter of
annular flow channel contributing the reactant stream generally is
approximately the same width or somewhat smaller than the width of
the light beam in the vicinity of nozzle 253. In some embodiments
of particular interest, inert gas flows through tubes 238, 242,
244, and reactants and other diluents flow through tube 240. The
inner diameter of the flow tube corresponding to the reactive
stream component comprising reaction precursors generally can have
dimensions from about 3.0 inches (76.2 mm) to about 0.05 inches
(1.27 mm), in additional embodiments from about 2.0 inches (50.8
mm) to about 0.075 inches (1.91 mm) and in further embodiments from
about 2.0 inches (50.8 mm) to about 0.1 inches (2.54 mm). The outer
diameter of the flow tube 238 corresponding to the reactive stream
component comprising an inner shielding gas supply tube can be from
about 0.20 to about 0.85 and in further embodiments from about 0.25
to about 0.75 times the inner diameter of the tube providing the
reactive flow. The outer diameter of the annular nozzle 253
generally can be from about 4 times to about 1.5 times, and in
further embodiments from the 3.5 times to about 2 times the outer
diameter of the flow tube providing the component of the reactant
stream comprising the reactive flow, in which the outer diameter is
the sum of the inner diameter and the wall thickness. A person of
ordinary skill in the art will recognize that additional ranges of
tube dimensions within the explicit ranges above are contemplated
and are within the present disclosure. The lengths of the tubes are
selected to position the flow near the light beam based on the
particular reactor configuration. The components of the flow
elements can be formed from suitable metals, such as stainless
steel or other suitable metal.
[0133] It can be desirable to flow inert entrainment gas between
the inner wall of flow tube 244 and the outer wall of flow tube
242. To perform the entrainment function, the entrainment gas flow
generally has a somewhat higher gas velocity out from the nozzle
and a significant flow volume. To achieve the desired flow volume
of the entrainment gas at reasonable gas velocities, the area of
the annulus contributing the entrainment gas flow generally is
relatively large. In particular, the area of the inlet opening for
the entrainment gas between flow tubes 242, 244 can be at least
about 10% larger than the area between flow tubes 240 and 242
providing for inert quenching gas flow, in further embodiments from
about 12% to about 500% larger and in additional embodiments from
about 15% to about 200% larger than the area between flow tubes 240
and 242. Similarly, in use, the entrainment flow volumes of at
least about 50% greater, in some embodiment from about 60% larger
to about 1000% greater and in further embodiments from about 75%
greater to about 750% greater than the flow volume of quenching
inert gas. A person of ordinary skill in the art will recognize
that additional ranges of flow areas within the explicit ranges
above are contemplated and are within the present disclosure.
Additional desirable nozzle designs are described below that
generally incorporate flow channels for inert quenching gas and
distinct channels for inert entrainment gas, and the relationships
of the areas of the inlets for these flow channels can be based on
the ranges provided above for the embodiment in FIGS. 3-6.
[0134] The walls of inner flow tubes 238,240,242 can be relatively
thin. If the walls of the inner flow tubes are thin, the respective
flows from the flow tubes have a desired interaction within the
reaction chamber. In particular, with a thin wall of a flow tube,
interfacial shear is enhanced between the adjacent flows especially
if the flows are adjusted to result in similar velocities of the
flow, and the interfacial shear can help particle quenching. With
respect to the thickness of the inner walls of the flow tubes, the
walls can have a thickness from about 0.0025 inches (0.0635 mm) to
about 0.050 inches (1.27 mm), in further embodiments from about
0.003 inches (0.0762 mm) to about 0.040 inches (1.02 mm), and in
other embodiments form about 0.0035 inches (0.0889 mm) to about
0.030 inches (0.762 mm). The outer flow tube can have a thicker
wall to provide for protection of the assembled nozzle without
altering the flow significantly since there is no adjacent flow at
the outer wall of the nozzle. A person of ordinary skill in the art
will recognize that additional ranges of tube thickness within the
explicit ranges above are contemplated and are within the present
disclosure.
[0135] Reactant inlet nozzle 220 provides an easy to assemble
design with significant flexibility for delivery of reactants with
appropriate shielding gas. Access ports 246, 248, 250, 252 provide
for connection of the nozzle to a reactant delivery system with
selected connections to provide for delivery of reactive
compositions, inert gases combinations thereof or the like through
corresponding flow tubes 238, 240, 242, 244. Reactant inlet nozzle
220 can be disassembled for cleaning and/or replacement of one
component. Thus, the dimensions of flow tubes 238, 240, 242, 244
can be modified to correspondingly alter the flow. While reactant
inlet nozzle 220 is shown with four flow tubes 238, 240, 242, 244,
the design of reactant inlet nozzle 220 allows for the simple
modification for two flow tubes by leaving out two flow elements
from assembly, three flow tubes by leaving out two flow elements
from the assembly, or five or more flow tubes by including
additional flow elements within the assembly, each additional flow
element comprising a support hub, a flow tube, and an access port,
as described above. Furthermore, a flow tube designed to provide
shielding gas can have a rod or other cover, such as a porous
sintered metal cap, over the opening of the flow tube to restrict
the flow such that less inert shielding gas is needed to maintain
the velocity of the shielding gas flow, which is established to
provide little interfacial shear at the interface between the
precursor flow and the shielding gas flow.
[0136] In operation, components of a flow stream are supplied to
reactant inlet nozzle 220 though each access port 246, 248, 250,
252. The component of the flow stream supplied to access port 246
travels through the lumen of flow tube 238. The component of the
flow stream supplied to access ports 248, 250, 252 travel through
the annular flow channels formed between flow tubes 238, 240,
between flow tubes 240, 242, and between flow tubes 242, 244,
respectively. Each flow stream component exits reactant inlet
nozzle 220 at top of annular nozzle 253, which is placed within a
reaction chamber.
[0137] Generally, different components of a reactant flow stream
are supplied to different nozzle access ports. For example, with
respect to reactant inlet nozzle 220, it can be desirable to
distribute the components of the reactant stream such that the
component comprising reaction precursors are supplied to access
port 248, while the components comprising an inner inert gas, an
outer inert gas, and an entrainment gas flow are supplied to access
ports 246, 250, 252, respectively. A reactant delivery system
similar to reactant delivery system 160, depicted in FIG. 2, can be
used to supply reaction precursors to access port 248. The inner
inert gas, outer inter gas, and entrainment gas can be supplied to
access ports 246, 250, 252 from suitable gas reservoirs that allow
for delivery of the corresponding gasses over appropriate pressure
ranges. However, other distributions of reactant stream components
to access ports 246, 248, 250, 252 can also be desirable.
[0138] While reactant inlet nozzle 220 provides significant
advantages, alternative designs which provide similar nested flow
channels can be adapted around the concepts provided in this
embodiment of a reactant inlet nozzle. For example, while the
support hub design is convenient and versatile, the design can be
replaced with an integral machined unit that provides equivalent
flow channels and access ports. Furthermore, while flow tubes with
a circular cross section perpendicular to the central axis of the
flow tube provide for good flow properties, other cross sectional
shapes can be used, such as a square or rectangular shape,
optionally with rounded corners. Other flow tube shapes can be
similarly used. In general, regardless of the shape, the reactant
stream from annular nozzle 253 passes through the light beam within
the reaction chamber, and it is desirable for the width of the
reactant stream be selected such that essentially the entire
reactant stream passes through the light beam based on the width of
the light beam passing through the reaction chamber.
[0139] As shown in FIGS. 3-6, the flow tubes are approximately
cylindrical. This design provides for flow behavior that can be
estimated, and this design provides for convenient manufacturing.
However, alternative shapes can be used that can be expected to
provide roughly comparable behavior. Referring to FIG. 7A, the top
view of nozzle 220 of FIG. 3-6 is shown with circular edges of the
flow tubes. Referring to FIG. 7B, a top-view of an alternative
embodiment is depicted looking down into the flow channels for flow
tubes with an oval shaped cross section. The arrows in FIGS. 7A and
7B show the general direction of the light beam path relative to
the edge of the nozzle. A rectangular nozzle without an inner inert
quenching gas flow but with a small optical path length through the
reactant flow is described in detail below.
[0140] An alternative embodiment of a laser pyrolysis apparatus is
shown in FIG. 8. Referring to FIG. 8, a laser pyrolysis apparatus
290 includes reaction chamber 292, particle transfer element 294,
and a particle collection system 296. Reaction chamber 292
interfaces with reactant inlet nozzle 298 at a bottom surface 300
of reaction chamber 292 where reactant delivery system 302 connects
with reaction chamber 292. Particle transfer element 294 connects
along a top surface 304 with reaction chamber 292. In this
embodiment, the reactants are delivered from the bottom of reaction
chamber 292 while the products are collected from the top of
reaction chamber 292. Reactant inlet nozzle 298 can have a nozzle
structure with the annular channels similar to the configuration
shown in FIGS. 5 and 6.
[0141] First light tube 306 is configured to direct a light beam
path through reaction chamber 292 along the length of the chamber.
First light tube 306 comprises a cylindrical lens 308 oriented to
focus along the direction oriented along a normal between top
surface 304 to bottom surface 300 of reaction chamber 292 while not
focusing the light along the direction parallel to a table top 310.
Inert gas is directed into a first tube 307 from gas tubing to keep
contaminants away from optical components. First light tube 306
connects directly or indirectly with a light source at flange 312.
The light beam path continues through reaction chamber 292 to a
second light tube 314. Second light tube 314 is terminated with a
window 316 that directs the beam to a beam dump 318, for example, a
light meter. In operation, the light beam, generally from a
CO.sub.2 laser, intersects a reactant stream generated from
reactant inlet nozzle 298.
[0142] Particle transfer element 294 can comprise an attachment
plate 320, a flow conduit 322 and cooling collar 324. Attachment
plate 320 provides for secure fastening of particle transfer
element 294 to a top plate 326. Cooling collar 324 is secured with
a gas tight seal to flow conduit 322 with a fastening band or the
like, although, in other embodiments, flow collar 504 can be welded
or otherwise fastened to form a gas tight seal. Furthermore,
cooling collar 324 provides for flow of product stream from flow
conduit 322 to particle collection system 296. Cooling collar 324
is designed to reduce the temperature of the product stream flowing
therein, for example, by mixing the product stream with an inert
gas supplied from the exterior of cooling collar 324. A cooling
collar design using gas jets is described in detail in U.S. patent
application publication number 2009/0020411A1 to Holunga et al.,
entitled "Laser Pyrolysis with In-Flight Particle Manipulation for
Powder Engineering," incorporated herein by reference. In
operation, product stream flows from reaction chamber 292, through
flow conduit 322 and cooling collar 324, to particle collection
system 296.
[0143] Particle collection system 296 comprises flow tube 328,
collection chamber 330 and container 332. Flow tube 328 provides a
fluid connection between cooling collar 324 and collection chamber
330. Collection chamber 330 can comprise a single bag collector
which uses a flexible bag to separate a product plenum from a clean
plenum. Back pulse system 334 provides occasional back pulses of
gas to remove product powders from the bag membrane so that the
powders fall to the bottom of collection chamber 330. The bottom of
collection chamber 330 is connected with valve 336 that is
releasably connected to container 332. When valve 336 is open
powder can fall into container 332. To remove and replace container
332, valve 336 can be closed. Collection chamber 330 also leads to
a vent 340 that generally is connected to a scrubber and a pump.
Other collection systems can be used in place of the single bag
collector if desired.
[0144] FIGS. 9-11 show an alternate embodiment of a reactant inlet
nozzle. Reactant inlet nozzle 360 comprises a plurality of adjacent
rectangular flow channels. Reactant inlet nozzle 360 can be
desirable for the formation of silicon nanoparticles and can also
be used effectively for the synthesis of other nanoparticles using
laser pyrolysis. Reactant inlet nozzle 360 can be advantageous
because it can promote homogenous reaction conditions in the
reactant stream during product particle formation. In particular,
the reactant inlet nozzle design depicted in FIGS. 9-11 can help
reduce attenuation of the laser beam across the reactant stream.
FIG. 9 depicts a side-view cross section of reactant inlet nozzle
360. FIGS. 10 and 11 depict a top view and a side-view,
respectively, of reactant inlet nozzle 360. A top view of just the
flow channels is shown in FIG. 12 along with an arrow indicating
the light beam path is shown in FIG. 12. FIG. 12 provides clarity
with respect to the intended orientation of the nozzle within the
reactor.
[0145] Referring to FIGS. 9-11, reactant inlet nozzle 360 comprises
sealing plate 362 and flow element 364. Sealing plate 362 comprises
trough 366 and bolt holes 368. Sealing plate 362 is secured at a
flange to the lower portion of flow element 364 and is designed to
secure reactant inlet nozzle 360 to a reaction chamber via bolt
holes 368. A rubber gasket or the like can be place within trough
366 to affect an improved seal between sealing plate 362 and the
reaction chamber.
[0146] Flow element 364 comprises flow channels 370, 372, 374, 376,
378 and access ports 380, 382, 384, 386, 388. Flow channels 370,
372, 374, 376, 378 have a substantially rectangular cross-sectional
shape in a plane parallel to the top surface of sealing plate 362
in the orientation of the figure. Access ports 380, 382, 384, 386,
388 provide flow channels between the exterior of flow element 364
and corresponding flow channels 370, 372, 374, 376, 378. Reactant
inlet nozzle 360 can also comprise component delivery tubes 390,
392, 394, 396, 398 that can be secured to corresponding access
ports 380, 382, 384, 386, 388 and are routed through holes in
sealing plate 362. Flow element 364 and deliver tubes 390, 392,
396, 398 can be formed from suitable metals, such as stainless
steel or other suitable metal. In operation, components of the
reaction stream are delivered through component delivery tubes 390,
392, 394, 396, 398, through corresponding access ports 380, 382,
384, 386, 388, and into corresponding flow channels 370, 372, 374,
376, 378.
[0147] Generally, different components of a flow stream are
supplied to the respective access ports. With respect to reactant
inlet nozzle 360, it can be desirable to distribute the components
of the reactant flow stream such that the component comprising
reaction precursors as well as possible diluents and the like are
supplied to access port 394. In some embodiments, inert gasses can
be supplied to access ports 392, 396 and inert entrainment gasses
can be supplied to access ports 390, 398. Reaction stream
components supplied to access ports 392, 396 may or may not be
supplied from the same source and may or may not have the same
composition and/or flow characteristics. Similarly, reaction stream
components supplied to access ports 390, 398 may or may not be
supplied from the same source and may or may not have the same
composition and/or flow characteristics. In other embodiments,
different distributions of flow stream components across access
ports can be desirable.
[0148] The dimensions of flow channels 370, 372, 374, 376, 378 can
be desirably selected to roughly match the dimensions of the light
beam positioned to intersect with the reaction stream. In
particular, approximately the entire reactant stream should flow
through the beam, so that the length of the flow channels (marked
as "L" in FIG. 10), i.e. the dimension of the flow channels that is
perpendicular to the optical path of the light beam through the
reactant stream and perpendicular to the flow of the flow stream
that emanates out from the edge of the nozzle, generally is
approximately the same width or somewhat smaller than the light
beam in the vicinity or reactant inlet nozzle 360. Generally, the
length of the flow channels is from about 0.5 cm to about 20 cm and
in further embodiments from about 1 cm to about 10 cm. A person of
ordinary skill in the art will recognize that additional ranges of
flow channel dimensions within the explicit ranges above are
contemplated and are within the present disclosure. The lengths of
the tubes are selected to position the flow near the light beam
based on the particular reactor configuration.
[0149] The walls of flow channels 370, 372, 374, 376, 378 (i.e. the
surfaces of flow element 364 that form the flow channels) can be
relatively thin. If the walls of the inner flow tubes are thin, the
respective flows from the flow tubes have a desired interaction
within the reaction chamber. In particular, with a thin wall
between adjacent flow channels, interfacial shear is enhanced
between the adjacent flows especially if the flows are adjusted to
result in similar velocities of the flow, and the interfacial shear
can help particle quenching. The thickness of walls between
adjacent flows can be from about 0.05 mm to about 1.5 mm and in
additional ranges from about 0.1 mm to about 1 mm. A person of
ordinary skill in the art will recognize that additional ranges of
flow channel dimensions within the explicit ranges above are
contemplated and are within the present disclosure. The outer wall
of the flow channels can be made thicker to provide protection to
the overall nozzle structure since the thickness of the outer wall
generally does not influence the flow. The height of the nozzle can
be selected to position the flow near the light beam based on the
particular reactor configuration.
[0150] Similarly, the dimensions of flow element 364 can be
desirably selected to promote homogeneous reaction condition in the
region of the reaction zone. In particular, the width "W" of
reactant flow path 374 (as noted in FIG. 9), i.e. the dimension of
the flow element that is perpendicular to the optical path of the
light bean through the reactant stream, is selected to reduce the
attenuation of the light beam along the optical path through the
reactant stream. The width of the reactant flow path can be from
about 0.1 mm to about 2 cm, in further embodiments from about 1.5
mm to about 1.5 cm and in additional embodiments from about 0.25 mm
to about 1 cm. A person of ordinary skill in the art will recognize
that additional ranges of flow channel dimensions within the
explicit ranges above are contemplated and are within the present
disclosure. The optical path values above can generally correspond
with appropriate optical path distances for the nozzle
configurations having an inner quench gas channel, such as shown in
FIGS. 3-7. But in these other configurations the largest optical
paths have components separated by the inner inert gas channel such
that the light beam is attenuated going through the far portion of
the flow due to absorption of light after the beam has passed
through the closer section of the reactant flow. The effects of
attenuation of the light beam may be reduced in the nozzle design
in FIGS. 9-11. While the nozzle in FIGS. 9-11 is depicted with five
flow channels symmetrically placed around an inner reactant
precursor flow, additional embodiments can be formed with a single
flow channel, with three flow channels, with seven flow channels or
with more than seven flow channels.
[0151] Flow element 364 can have flow channels and access ports can
be machined from a single block of material. Referring to FIG. 10,
the flow channels can be machined in a central portion of the
block, leaving un-machined regions of lateral support 400. However,
in other embodiments, the flow element can be fabricated with wall
elements that are removable. In such a design, the space between
wall elements forms a portion of a rectangular flow channel.
Removable wall elements are advantageous because they allow for the
exchange of elements for cleaning, repair, or for modification of
the reactant flow. In such embodiments, a flow element can comprise
a frame providing the outer walls of the nozzle and a plurality of
parallel, rectangular plates that can be secured with slots, spacer
elements or other structural elements to maintain the selected
spacing within the nozzle. A region defined by the surfaces of
adjacent plates and the inner carrier surfaces between adjacent
plates forms a rectangular flow channel. The number of rectangular
plates and groves used in the construction corresponds to the
number of flow channels. For example, if three flow channels are
desired, three parallel groves are formed on each inner carrier
surface and a rectangular plate is disposed between each of the
three corresponding groves. If four flow channels are desired, four
parallel groves are formed on each inner carrier surface and a
rectangular plate is disposed between each of the four
corresponding groves. Notwithstanding the specifics of the
embodiment, any embodiment of a flow element wherein the wall
elements are removable and wherein the spaces between the wall
elements form rectangular flow channels designed to deliver
components of a reactant stream can be desirable.
[0152] While the improved nozzle designs can used for the synthesis
for a range of desired inorganic particles, based on a particular
interest in the synthesis of elemental silicon particles with an
optional dopant, additional discussion is devoted to these
materials. A basic feature of successful application of laser
pyrolysis for the production of desirable silicon particles is the
generation of a reactant stream containing one or more silicon
precursor compounds and optionally one or more dopant precursor
compounds. As noted above, these approaches can be similarly used
for the synthesis of germanium particles, and suitable germanium
precursors are presented below. In some embodiments, a radiation
absorber can be included in the flow, but for elemental silicon
particles, suitable silicon precursors can be used that directly
absorb infrared laser light. Dopant precursors can be introduced
into the reactant flow for incorporation into the silicon
particles. With respect to combined vapor and aerosol delivery
approaches, a silicon precursor can be delivered as a vapor/gas,
while one or more dopant precursors are delivered as an aerosol.
However, for many desirable dopants, suitable dopant precursors can
be delivered as a gaseous composition. The dopant elements can be
delivered into the reactant stream as a suitable composition. For
the doping of semiconductor substrates, desirable dopants include,
for example, B, P, Al, Ga, As, Sb and combinations thereof.
[0153] Dopants can be introduced at desired concentrations by
varying the composition of the reactant stream. A dopant element or
a combination of dopant elements are introduced into the silicon
host material by appropriately selecting the composition in the
reactant stream and the processing conditions. Thus, submicron
particles incorporating selected dopants, including, for example,
complex blends of dopant compositions, can be formed. Generally,
the conditions in the reactor should be sufficiently reducing to
produce the elemental silicon or alloys for the product
nanoparticles. Generally the silicon particles are crystalline, and
the dopant can be an intercalation or alloying element. Based on
the nozzle designs described herein, high quality silicon
nanoparticles can be produced at desirable rates with or without
dopants.
[0154] Suitable silicon precursors for elemental silicon particle
formation include, for example, silane (SiH.sub.4), disilane
(Si.sub.2H.sub.6), trisilane (Si.sub.3H.sub.8), silicon
tetrachloride (SiCl.sub.4), trichlorosilane (SiCl.sub.3H), and
SiCl.sub.2H.sub.2. Silane, SiH.sub.4, is a convenient precursor for
laser pyrolysis since it absorbs infrared light from a CO.sub.2
laser and decomposes to form crystalline silicon particles upon
decomposition. The higher order silanes similarly decompose to form
elemental silicon, i.e. Si.sup.0, silicon in its elemental state.
Thus, with silane as a precursor, a secondary reactant source may
not be used, and a separate infrared absorber is not needed.
Corresponding germanes (GeH.sub.4 and Ge.sub.2H.sub.6) can be used
as precursors. An inert gas can be used to moderate the reaction.
Suitable inert gases include for example, Ar, He N.sub.2 or
mixtures thereof.
[0155] Suitable precursors for aerosol delivery of gallium include,
for example, gallium nitrate (Ga(NO.sub.3).sub.3). Arsenic
precursors include, for example, AsCl.sub.3, which is suitable for
vapor delivery, and As.sub.2O.sub.5, which is suitable for aerosol
precursor delivery in aqueous or alcohol solutions. Suitable boron
precursors comprise, for example, diborane (B.sub.2H.sub.6),
BH.sub.3, and the like, and suitable combinations of any two or
more thereof. Suitable aluminum precursors include, for example,
aluminum hydride (AlH.sub.3), aluminum s-butoxide
(Al(OC.sub.4H.sub.9).sub.3), trimethyl aluminum
(Al(CH.sub.3).sub.3, trimethyl ammonia aluminum
Al(CH.sub.3).sub.3NH.sub.3, and the like, and suitable combinations
of any two or more thereof. Suitable phosphorous precursor
compositions for vapor delivery comprise, for example, phosphine
(PH.sub.3), phosphorus trichloride (PCl.sub.3), phosphorous
pentachloride (PCl.sub.5), phosphorus oxychloride (POCl.sub.3),
P(OCH.sub.3).sub.3, and the like, and suitable combinations of any
two or more thereof. Suitable antimony precursors include, for
example, stibine (SbH.sub.3) and antimony trichloride (SbCl.sub.3),
which is soluble in alcohol.
Particle Properties
[0156] The desirable silicon nanoparticle dispersions described
herein are based in part on the ability to form highly uniform
silicon nanoparticles with or without dopants. As described above,
laser pyrolysis is a particularly suitable approach for the
synthesis of highly uniform silicon submicron particles or
nanoparticles. Also, laser pyrolysis is a versatile approach for
the introduction of desired dopants at a selected concentration,
such as high dopant concentrations. Also, the surface properties of
the silicon particles can be influenced by the laser pyrolysis
process, although the surface properties can be further manipulated
after synthesis to form desired dispersions. Small and uniform
silicon particles can provide processing advantages with respect to
forming dispersions/inks.
[0157] In some embodiments, the particles have an average diameter
of no more than about one micron, and in further embodiments it is
desirable to have particles with smaller particle sizes to
introduce desired properties. For example, nanoparticles with a
small enough average particle size are observed to melt at lower
temperatures than bulk material, which can be advantageous in some
contexts. Also, the small particle sizes provide for the formation
of inks with desirable properties, which can be particularly
advantageous for inkjet printing since larger particles may clog
some inkjet heads. Generally, the dopants and the dopant
concentration are selected based on the desired electrical
properties of the subsequently fused material or to provide a
desired degree of dopant migration to an adjacent substrate.
[0158] In particular, laser pyrolysis is useful in the formation of
particles that are highly uniform in composition, crystallinity,
when appropriate, and size. A collection of submicron/nanoscale
particles may have an average diameter for the primary particles of
no more than about 500 nm, in some embodiments from about 2 nm to
about 100 nm, alternatively from about 2 nm to about 75 nm, in
further embodiments from about 2 nm to about 50 nm, in additional
embodiments from about 2 nm to about 25 nm, and in other
embodiments from about 2 nm to about 15 nm. A person of ordinary
skill in the art will recognize that other ranges within these
specific ranges are covered by the disclosure herein. In
particular, for some applications, smaller average particle
diameters can be particularly desirable. Particle diameters and
primary particle diameters are evaluated by transmission electron
microscopy. Primary particles are the small visible particulate
units visible in the micrograph without reference to the
separability of the primary particles. If the particles are not
spherical, the diameter can be evaluated as averages of length
measurements along the principle axes of the particle.
[0159] As used herein, the term "particles" refer to physical
particles, which are unfused, so that any fused primary particles
are considered as an aggregate, i.e. a physical particle. For
particles formed by laser pyrolysis, if quenching is applied, the
particles can be effectively the same as the primary particles,
i.e., the primary structural element within the material. Thus, the
ranges of average primary particle sizes above can also be used
with respect to the particle sizes. If there is hard fusing of some
primary particles, these hard fused primary particles form
correspondingly larger physical particles. The primary particles
can have a roughly spherical gross appearance, or they can have rod
shapes, plate shapes or other non-spherical shapes. Upon closer
examination, crystalline particles may have facets corresponding to
the underlying crystal lattice. Amorphous particles generally have
a spherical aspect.
[0160] Because of their small size, the particles tend to form
loose agglomerates due to van der Waals and other electromagnetic
forces between nearby particles. Even though the particles may form
loose agglomerates, the nanometer scale of the particles is clearly
observable in transmission electron micrographs of the particles.
The particles generally have a surface area corresponding to
particles on a nanometer scale as observed in the micrographs.
Furthermore, the particles can manifest unique properties due to
their small size and large surface area per weight of material.
These loose agglomerates can be dispersed in a liquid to a
significant degree and in some embodiments approximately completely
to form dispersed primary particles.
[0161] The particles can have a high degree of uniformity in size.
Laser pyrolysis generally results in particles having a very narrow
range of particle diameters. As determined from examination of
transmission electron micrographs, the primary particles generally
have a distribution in sizes such that at least about 95 percent,
and in some embodiments 99 percent, of the particles have a
diameter greater than about 35 percent of the average diameter and
less than about 280 percent of the average diameter. In additional
embodiments, the particles generally have a distribution in sizes
such that at least about 95 percent, and in some embodiments 99
percent, of the primary particles have a diameter greater than
about 40 percent of the average diameter and less than about 250
percent of the average diameter. In further embodiments, the
primary particles have a distribution of diameters such that at
least about 95 percent, and in some embodiments 99 percent, of the
primary particles have a diameter greater than about 60 percent of
the average diameter and less than about 200 percent of the average
diameter. A person of ordinary skill in the art will recognize that
other ranges of uniformity within these specific ranges are
contemplated and are within the present disclosure.
[0162] Furthermore, in some embodiments essentially no primary
particles have an average diameter greater than about 5 times the
average diameter, in other embodiments about 4 times the average
diameter, in further embodiments 3 times the average diameter, and
in additional embodiments 2 times the average diameter. In other
words, the primary particle size distribution effectively does not
have a tail indicative of a small number of particles with
significantly larger sizes. This is a result of the small reaction
region to form the inorganic particles and corresponding rapid
quench of the inorganic particles. An effective cut off in the tail
of the size distribution indicates that there are less than about 1
particle in 10.sup.6 has a diameter greater than a specified cut
off value above the average diameter. High primary particle
uniformity can be exploited in a variety of applications.
[0163] High quality particles can be produced that are
substantially unfused. However, for the production of very small
primary particle sizes, e.g., less than 10 nm average diameter, at
higher production rates, the primary particles can involve
substantial fusing into a nanostructured material. These particles
can still be dispersed into a liquid to produce desired ranges of
secondary particle size. Even though the particles with very small
primary particle diameters may have significant fusing, these
particles may still be desirable for applications in which the
small primary particle size and corresponding high surface areas
can facilitate dopant drive-in and/or fusing of the deposited inks
into corresponding structures.
[0164] The silicon particles can further be characterized by BET
surface areas. The surface area measurements are based on gas
adsorption onto the particle surfaces. The theory of BET surface
area was developed by Brunauer et al., J. Am. Chem. Soc. Vol. 60,
309 (1938). The BET surface area evaluation cannot directly
distinguish small particle sizes from highly porous particles, but
the surface area measurements nevertheless provide useful
characterization of the particles. BET surface area measurements
are an established approach in the field, and for silicon particles
the BET surface area can be determined with an N.sub.2 gas
absorbate. The BET surface area can be measured with commercial
instruments, such as a Micromeritics Tristar 3000.TM. instrument.
The silicon particles described herein can have BET surface areas
ranging from about 100 m.sup.2/g to about 1500 m.sup.2/g and in
further embodiments, from about 200 m.sup.2/g to about 1250
m.sup.2/g. A person of ordinary skill in the art will recognize
that additional ranges within the explicit ranges above are
contemplated and are within the present disclosure. The particle
diameters can be estimated from the BET surface areas based on the
assumption that the particles are non-porous, non-agglomerated
spheres.
[0165] X-ray diffraction can be use to evaluate the crystallinity
of the particles. Furthermore, crystalline nanoparticles produced
by laser pyrolysis can have a high degree of crystallinity.
However, x-ray diffraction can also be used to evaluate the
crystallite size. In particular, for submicron particles, the
diffraction peaks are broadened due to truncation of the crystal
lattice at the particle surface. The degree of broadening of the
x-ray diffraction peaks can be used to evaluate an estimate of the
average crystallite size. While strain in the particles and
instrument effects can also contribute to broadening of the
diffraction peaks, if the particles are assumed to be essentially
spherical, the Scherrer equation can be used to provide a lower
limit on the average particle size. Meaningful broadening is only
observed for crystallite sizes less than about 100 nm.
[0166] If the particle sizes from TEM evaluation of primary
particle diameters, particle size estimates from the BET surface
areas and the particle sizes from the Scherrer equation are roughly
equal, this determination provides significant evidence that the
fusing of the particles is not excessive, that the primary
particles are effectively single crystals and that the particles
have a high degree of uniformity. It is generally observed that
silicon particle collections in which the three measurements of
particle sizes are in rough agreement exhibit good dispersion in
appropriate solvents. Thus, the various particle size measurements
can be used as an indirect measure of particle quality.
[0167] In addition, the submicron particles may have a very high
purity level. It has been found that the silicon particles can be
produced with very low levels of metal impurities using laser
pyrolysis with appropriate particle handling procedures. Low metal
impurity levels are very desirable from the perspective of
semiconductor processing. As described further below, the particles
can be placed into dispersions. In the dispersions, processing such
as centrifugation can be performed to reduce impurities. In the
resulting dispersions, the contamination by metal elements can be
very low based on desired handling of the particles. The
contaminant levels can be evaluated by ICP-MS analysis (inductively
coupled plasma-mass spectrometry).
[0168] In particular, the submicron silicon particles can be found
to have no more than about 1 parts per million by weight (ppm) of
metal contaminants, in further embodiments no more than about 900
parts per billion by weight (ppb) and in additional embodiments no
more than about 700 ppb of total metal contaminants. For
semiconductor applications, iron can be a contaminant of particular
concern. With improved particle synthesis, handling and contaminant
removal procedures, particles can be dispersed with no more than
about 200 ppb of iron, in further embodiments, no more than about
100 ppb and in additional embodiments from about 15 ppb to about 75
ppb of iron contaminants with respect to the particle weight. A
person of ordinary skill in the art will recognize that additional
ranges of contaminant levels within the explicit ranges above are
contemplated and are within the present disclosure. The low
contaminant levels allows for the production of particles with low
dopant levels of dopants, such as boron or phosphorous, in which
the low dopant levels can be effective of tuning the electronic
properties of particles in a meaningful way that cannot be achieved
at higher contaminant levels.
[0169] To achieve the very low contaminant levels, the particles
are synthesized in a laser pyrolysis apparatus sealed from the
ambient atmosphere and appropriate cleaned and purged prior to the
synthesis. Highly pure gaseous reactants are used for the silicon
precursors as well as for the dopant precursors. The particles are
collected and handled in a glove box to keep the particles free
from contaminants from the ambient atmosphere. Very clean polymer
containers, such as polyfluoroethylene containers, can be used for
placement of the particles. The particles are dispersed in very
pure solvents within clean vessels within a glove box or clean
room. With meticulous attention to all aspects of the process, the
high purity levels described herein have been and generally can be
achieved.
[0170] The size of the dispersed particles in a liquid can be
referred to as the secondary particle size. The primary particle
size is roughly the lower limit of the secondary particle size for
a particular collection of particles, so that the average secondary
particle size can be approximately the average primary particle
size if the primary particles are substantially unfused and if the
particles are effectively completely dispersed in the liquid, which
involves solvation forces that successfully overcome the
inter-particle forces.
[0171] The secondary particle size may depend on the subsequent
processing of the particles following their initial formation and
the composition and structure of the particles. In particular, the
particle surface chemistry, properties of the dispersant, the
application of disruptive forces, such as shear or sonic forces,
and the like can influence the efficiency of fully dispersing the
particles. Ranges of values of average secondary particle sizes are
presented below with respect to the description of dispersions.
Secondary particles sizes within a liquid dispersion can be
measured by established approaches, such as dynamic light
scattering. Suitable particle size analyzers include, for example,
a Microtrac UPA instrument from Honeywell based on dynamic light
scattering, a Horiba Particle Size Analyzer from Horiba, Japan and
ZetaSizer Series of instruments from Malvern based on Photon
Correlation Spectroscopy. The principles of dynamic light
scattering for particle size measurements in liquids are well
established.
[0172] Dopants can be introduced to vary properties of the
resulting particles. In general, any reasonable element can be
introduced as a dopant to achieve desired properties. For example,
dopants can be introduced to change the electrical properties of
the particles. In particular, As, Sb and/or P dopants can be
introduced into the elemental silicon particles to form n-type
semiconducting materials in which the dopant provide excess
electrons to populate the conduction bands, and B, Al, Ga and/or In
can be introduced to form p-type semiconducting materials in which
the dopants supply holes. P and B are used as dopants in the
Examples below.
[0173] In some embodiments, one or more dopants can be introduced
into the elemental silicon particles in concentrations from about
1.0.times.10.sup.-7 to about 15 atomic percent relative to the
silicon atoms, in further embodiments from about
1.0.times.10.sup.-5 to about 5.0 atomic percent and in further
embodiments from about 1.times.10.sup.4 to about 1.0 atomic percent
relative to the silicon atoms. Both the low dopant levels and the
high dopant levels are of interest in appropriate contexts. For the
low dopant levels to be of particular usefulness, the particle
should be pure. For small particles, the low dopant levels
essentially can correspond with less than one dopant atom per
particle on average. In combination with the high purity that has
been achieved for the particles, low dopant levels from about
1.0.times.10.sup.-7 to about 5.0.times.10.sup.-3 correspond with
difficult to achieve yet potentially useful materials. In some
embodiments, high dopant levels are of particular interest, and the
highly doped particles can have a dopant concentration from about
0.25 atomic percent to about 15 atomic percent, in other
embodiments from about 0.5 atomic percent to about 12 atomic
percent, and in further embodiments from about 1 atomic percent to
about 10 atomic percent. A person of ordinary skill in the art will
recognize that additional ranges within the explicit dopant level
ranges are contemplated and are within the present disclosure.
Dispersions and Properties of the Dispersions
[0174] Dispersions of particular interest comprise a dispersing
liquid or solvent and silicon nanoparticles dispersed within the
liquid along with optional additives. Generally, the product
silicon particles from laser pyrolysis are collected as a powder,
which need to be dispersed as a step in forming the ink. The
dispersion can be stable with respect to avoidance of settling over
a reasonable period of time, generally at least an hour, without
further mixing. A dispersion can be used as a coating material or
as an ink, i.e., the dispersion can be printed. The properties of
the ink can be adjusted based on the particular printing method.
For example, in some embodiments, the viscosity of the ink is
adjusted for the particular use, such as inkjet printing, gravure
printing or screen printing, and particle concentrations and
additives provide some additional parameters to adjust the
viscosity and other properties. In some embodiments, the particles
can be formed with concentrated dispersions with desirable fluid
properties without surface modifying the particles with organic
compounds. As noted above, the lack of surface modification with
organic compounds excludes references to solvent-based
interactions. In general, the solvents may interact with the
particle surfaces with varying degrees of interactions that are
distinct from the inclusion of distinct surface modifying agents
that form strong and effectively durable chemical modification of
the particle surfaces. The availability to form stable dispersions
with small secondary particle sizes provides the ability to form
certain inks that are not otherwise possible.
[0175] Furthermore, it is desirable for the silicon particles to be
uniform with respect to particle size and other properties.
Specifically, it is desirable for the particles to have a uniform
primary particle size and for the primary particles to be
sufficiently unfused based on the primary particle size. Then, the
particles generally can be dispersed to yield a smaller more
uniform secondary particle size in the dispersion. Secondary
particle size refers to measurements of particle size within a
dispersion. The formation of a good dispersion with a small
secondary particle size can be facilitated through the matching of
the surface chemistry of the particles with the properties of the
dispersing liquid. The surface chemistry of particles can be
influenced during synthesis of the particles as well as following
collection of the particles. For example, the formation of
dispersions with polar solvents is facilitated if the particles
have polar groups on the particle surface.
[0176] As described herein, suitable approaches have been found to
disperse dry silicon nanoparticle powders produced by laser
pyrolysis and to form inks and the like for deposition. In some
embodiments, the particle can be surface modified with an organic
compound to change the surface properties of the particles in a
dispersion, but in some embodiments of particular interest, the
particles are not surface modified with an organic compound to
provide advantages with respect to properties for certain
applications and to simply processing. Thus, for some embodiments,
significant advantages are obtained by forming dispersions of
particles without surface modification. Using one or more of the
processing approaches described herein, inks can be formed that can
be deposited using convenient coating and printing approaches based
on established commercial parameters. Thus, the advantages of
vapor-based particle synthesis can be combined with desirable
solution based processing approaches with highly dispersed
particles to obtain desirable dispersions and inks, which can be
formed with doped particles.
[0177] With respect to silicon dispersions, the dispersions can
have concentrations from low concentrations to about 30 weight
percent. In general, the secondary particles size can be expressed
as a cumulant mean, or Z-average particle size as measured with
dynamic light scattering (DLS). The Z-average particle size is an
intensity average based on the scattered light measurements, and
the scattering intensity based particle size distribution can be
converted to volume distributions that can be used to evaluate a
volume-average size. Generally, the Z-average particle size is no
more than about 2 microns and in some embodiments, no more than
about 250 nm. Additionally, in some embodiments it is desirable for
the secondary particle size distribution to be narrow.
[0178] In general, the surface chemistry of the particles
influences the process of forming the dispersion. In particular, it
is easier to disperse the particles to form smaller secondary
particle sizes if the dispersing liquid and the particle surfaces
are compatible chemically, although other parameters such as
density, particle surface charge, solvent molecular structure and
the like also directly influence dispersability. In some
embodiments, the liquid may be selected to be appropriate for the
particular use of the dispersion, such as for a printing process.
For silicon synthesized using silanes, the resulting silicon
generally is partially hydrogenated, i.e., the silicon includes
some small amount of hydrogen in the material. It is generally
unclear if this hydrogen or a portion of the hydrogen is at the
surface as Si--H bonds. However, the presence of a small amount of
hydrogen does not presently seem particularly significant. However,
it is found that silicon particles formed by laser pyrolysis are
suitable for forming good dispersions in appropriately selected
solvents without modifying the particles with chemically bonded
organic compounds.
[0179] In general, the surface chemistry of the particles can be
influenced by the synthesis approach, as well as subsequent
handling of the particles. The surface by its nature represents a
termination of the underlying solid state structure of the
particle. This termination of the surface of the silicon particles
can involve truncation of the silicon lattice. The termination of
particular particles influences the surface chemistry of the
particles. The nature of the reactants, reaction conditions, and
by-products during particle synthesis influences the surface
chemistry of the particles collected as a powder during flow
reactions. The silicon can be terminated, for example, with bonds
to hydrogen, as noted above. In some embodiments, the silicon
particles can become surface oxidized, for example through exposure
to air. For these embodiments, the surface can have bridging oxygen
atoms in Si--O--Si structures or Si--O--H groups if hydrogen is
available during the oxidation process.
[0180] In some embodiments, the surface properties of the particles
can be modified through surface modification of the particles with
a surface modifying composition chemically bonded to the particle
surfaces. However, in some embodiments of particular interest, the
particles are not surface modified so that unmodified particles are
deposited for further processing. In appropriate embodiments,
surface modification of the particles can influence the dispersion
properties of the particles as well as the solvents that are
suitable for dispersing the particles. Some surface active agents,
such as many surfactants, act through non-bonding interactions with
the particle surfaces, and these processing agents are described
further below. In some embodiments, desirable properties,
especially dispersability in otherwise unavailable solvents, can be
obtained through the use of surface modification agents that
chemically bond to the particle surface. The surface chemistry of
the particles influences the selection of surface modification
agents. The use of surface modifying agents to alter the silicon
particle surface properties is described further in published U.S.
patent application 2008/0160265 to Hieslmair et al., entitled
"Silicon/Germanium Particle Inks, Doped Particles, Printing, and
Processes for Semiconductor Applications," incorporated herein by
reference. While surface modified particles can be designed for use
with particular solvents, it has been found that desirable inks can
be formed without surface modification at high particle
concentrations and with good deliverability. The ability to form
desired inks without surface modification can be useful for the
formation of desired devices, especially semiconductor based
devices, with a lower level of contamination.
[0181] When processing a dry, as-synthesized powder, it has been
found that forming a good dispersion of the particles prior to
further processing facilitates the subsequent processing steps. The
dispersion of the as-synthesized particles generally comprises the
selection of a solvent that is relatively compatible with the
particles based on the surface chemistry of the particles. Shear,
stirring, sonication or other appropriate mixing conditions can be
applied to facilitate the formation of the dispersion. In general,
it is desirable for the particles to be well dispersed, although
the particles do not need to be stably dispersed initially if the
particles are subsequently transferred to another liquid.
[0182] For particular applications, there may be fairly specific
target properties of the inks as well as the corresponding liquids
used in formulating the inks. Furthermore, it can be desirable to
increase the particle concentration of a dispersion/ink relative to
an initial concentration used to form a good dispersion. Specific
formulations for inkjet printing, gravure printing and for screen
printing are discussed in detail below.
[0183] One approach for changing solvents involves the addition of
a liquid that destabilizes the dispersion. The liquid blend then
can be substantially separated from the particles through decanting
or the like. The particles are then re-dispersed in the newly
selected liquid. This approach for changing solvents is discussed
in published U.S. patent application 2008/0160265 to Hieslmair et
al., entitled "Silicon/Germanium Particle Inks, Doped Particles,
Printing and Processes for Semiconductor Applications,"
incorporated herein by reference.
[0184] However, for most inks, it is desirable to use solvent
blends, and the design of the blends can be based on the ability to
maintain a good dispersion after the initial formation of the
dispersion. Thus, a desirable approach for the formation of inks
with desired properties is to form a good dispersion of the
particles and to maintain the good dispersion of the particles
through the blending of solvents. The blend of solvents is selected
such that the different liquids combine to form a single phase
through the miscibility or solubility of the liquids with respect
to each other.
[0185] With respect to the increase of particle concentration,
solvent can be removed through evaporation to increase the
concentration. This solvent removal generally can be done
appropriately without destabilizing the dispersion. A lower boiling
solvent component can be removed preferentially through
evaporation. If the solvent blend forms an azeotrope, a combination
of evaporation and further solvent addition can be used to obtain a
target solvent blend. Solvent blends can be particularly useful for
the formation of ink compositions since the blends can have liquid
that contribute desirable properties to the ink. A low boiling
temperature solvent component can evaporate relatively quickly
after printing to stabilize the printed ink prior to further
processing and curing. A higher temperature solvent component can
be used to adjust the viscosity to limit spreading after printing.
Thus, for many printing applications, solvent blends are desirable.
The overall solvent composition can be adjusted to yield desired
ink properties and particle concentrations.
[0186] At appropriate stages of the dispersion process, the
dispersion can be processed to remove contaminants and/or any stray
unusually large particles. Generally, a filter can be selected to
exclude particulates that are much larger than the average
secondary particle size so that the filtration process can be
performed in a reasonable way. In general, the filtration processes
have not been suitable for overall improvement of the dispersion
quality. Suitable commercial filters are available, and can be
selected based on the dispersion qualities and volumes.
[0187] Alternatively or additionally, the dispersion can be
centrifuged. The centrifugation parameters can be selected such
that at least a reasonable fraction of the silicon nanoparticles
remain dispersed, but contaminants settle to the bottom of the
centrifuge container. The dispersion can be decanted or similarly
separated from the settled contaminants. The use of centrifugation
can avoid the introduction of contaminants from a filtration
material. It has been found that centrifugation of silicon particle
dispersions can be useful for the formation of the highly pure
dispersions with very low metal contamination described herein.
[0188] The dispersions can be formulated for a selected
application. The dispersions can be characterized with respect to
composition as well as the characterization of the particles within
the dispersions. In general, the term ink is used to describe a
dispersion that is subsequently deposited using a printing
technique, and an ink may or may not include additional additives
to modify the ink properties.
[0189] Better dispersions generally are more stable and/or have a
smaller secondary particle size indicating less agglomeration. As
used herein, stable dispersions have no settling without continuing
mixing after one hour. In some embodiments, the dispersions exhibit
no settling of particles without additional mixing after one day
and in further embodiments after one week, and in additional
embodiments after one month. In general, dispersions with well
dispersed particles can be formed at concentrations of at least up
to 30 weight percent inorganic particles. Generally, for some
embodiments it is desirable to have dispersions with a particle
concentration of at least about 0.05 weight percent, in other
embodiments at least about 0.25 weight percent, in additional
embodiments from about 0.5 weight percent to about 25 weight
percent and in further embodiments from about 1 weight percent to
about 20 weight percent. A person of ordinary skill in the art will
recognize that additional ranges of stability times and
concentrations within the explicit ranges above are contemplated
and are within the present disclosure.
[0190] The dispersions can include additional compositions besides
the silicon particles and the dispersing liquid or liquid blend to
modify the properties of the dispersion to facilitate the
particular application. For example, property modifiers can be
added to the dispersion to facilitate the deposition process.
Surfactants can be effectively added to the dispersion to influence
the properties of the dispersion.
[0191] In general, cationic, anionic, zwitter-ionic and nonionic
surfactants can be helpful in particular applications. In some
applications, the surfactant further stabilizes the particle
dispersions. For these applications, the selection of the
surfactant can be influenced by the particular dispersing liquid as
well as the properties of the particle surfaces. In general,
surfactants are known in the art. Furthermore, the surfactants can
be selected to influence the wetting or beading of the
dispersion/ink onto the substrate surface following deposition of
the dispersion. In some applications, it may be desirable for the
dispersion to wet the surface, while in other applications it may
be desirable for the dispersion to bead on the surface. The surface
tension on the particular surface is influenced by the surfactant.
Also, blends of surfactants can be helpful to combine the desired
features of different surfactants, such as improve the dispersion
stability and obtaining desired wetting properties following
deposition. In some embodiments, the dispersions can have
surfactant concentrations from about 0.01 to about 5 weight
percent, and in further embodiments from about 0.02 to about 3
weight percent.
[0192] The use of non-ionic surfactants in printer inks is
described further in U.S. Pat. No. 6,821,329 to Choy, entitled "Ink
Compositions and Methods of Ink-Jet Printing on Hydrophobic Media,"
incorporated herein by reference. Suitable non-ionic surfactants
described in this reference include, for example, organo-silicone
surfactants, such as SILWET.TM. surfactants from Crompton Corp.,
polyethylene oxides, alkyl polyethylene oxides, other polyethylene
oxide derivatives, some of which are sold under the trade names,
TERGITOL.TM., BRIJ.TM., TRITON.TM., PLURONIC.TM., PLURAFAC.TM.,
IGEPALE.TM., and SULFYNOL.TM. from commercial manufacturers Union
Carbide Corp., ICI Group, Rhone-Poulenc Co., Rhom & Haas Co.,
BASF Group and Air Products Inc. Other nonionic surfactants include
MACKAM.TM. octylamine chloroacetic adducts from McIntyre Group and
FLUORAD.TM. fluorosurfactants from 3M. The use of cationic
surfactants and anionic surfactants for printing inks is described
in U.S. Pat. No. 6,793,724 to Satoh et al., entitled "Ink for
Ink-Jet Recording and Color Ink Set," incorporated herein by
reference. This patent describes examples of anionic surfactants
such as polyoxyethylene alkyl ether sulfate salt and polyoxyalkyl
ether phosphate salt, and examples of cationic surfactants, such as
quaternary ammonium salts.
[0193] Viscosity modifiers can be added to alter the viscosity of
the dispersions. Suitable viscosity modifiers include, for example
soluble polymers, such as polyacrylic acid, polyvinyl pyrrolidone
and polyvinyl alcohol. Other potential additives include, for
example, pH adjusting agents, antioxidants, UV absorbers,
antiseptic agents and the like. These additional additives are
generally present in amounts of no more than about 5 weight
percent. A person of ordinary skill in the art will recognize that
additional ranges of surfactant and additive concentrations within
the explicit ranges herein are contemplated and are within the
present disclosure.
[0194] For electronic applications, it can be desirable to remove
organic components to the ink prior to or during certain processing
steps such that the product materials are effectively free from
carbon. In general, organic liquids can be evaporated to remove
them from the deposited material. However, surfactants, surface
modifying agents and other property modifiers may not be removable
through evaporation, although they can be removed through heating
at moderate temperature in an oxygen atmosphere to combust the
organic materials.
[0195] The use and removal of surfactants for forming metal oxide
powders is described in U.S. Pat. No. 6,752,979 to Talbot et al.,
entitled "Production of Metal Oxide Particles with Nano-Sized
Grains," incorporated herein by reference. The '979 patent teaches
suitable non-ionic surfactants, cationic surfactants, anionic
surfactants and zwitter-ionic surfactants. The removal of the
surfactants involves heating of the surfactants to moderate
temperatures, such as to 200.degree. C. in an oxygen atmosphere to
combust the surfactant. Other organic additives generally can be
combusted for removal analogously with the surfactants. If the
substrate surface is sensitive to oxidation during the combustion
process, a reducing step can be used following the combustion to
return the surface to its original state.
[0196] The Z-average particle sizes can be measured using dynamic
light scattering. The Z-average particle size is based on a
scattering intensity weighted distribution as a function of
particle size. The scattering intensity is a function of the
particle size to the 6th power so that larger particle scatter much
more intensely and are correspondingly weighted much more in the
measurements. Evaluation of this distribution is prescribed in ISO
International Standard 13321, Methods for Determination of Particle
Size Distribution Part 8: Photon Correlation Spectroscopy, 1996.
The Z-average distributions are based on a single exponential fit
to time correlation functions. However, small particles scatter
light with less intensity relative to their volume contribution to
the dispersion. The intensity weighted distribution can be
converted to a volume-weighted distribution that is perhaps more
conceptually relevant for evaluating the properties of a
dispersion. For nanoscale particles, the volume-based distribution
can be evaluated from the intensity distribution using Mie Theory.
The volume-average particle size can be evaluated from the
volume-based particle size distribution. Further description of the
manipulation of the secondary particle size distributions can be
found in Malvern Instruments--DLS Technical Note MRK656-01,
incorporated herein by reference. As a general matter, due to the
scaling of volume average particle sizes by the cube of the
particle diameter and the scattering intensity average (Z-average)
by the sixth power of the average particle size, these measurements
significantly weight larger particles over smaller particles.
[0197] In general, if processed appropriately, for dispersions with
well dispersed particles and little fusing of the primary
particles, the Z-average secondary particle size can be no more
than a factor of four times the average primary particle size, in
further embodiments no more than about 3 times the average primary
particle size and in additional embodiments no more than about 2
times the average primary particle size. For primary particles that
exhibit some fusing, the absolute value of the Z-average dispersed
particle size is still very significant for the processing
properties of the silicon particle distributions. In some
embodiments, the Z-average particle size is no more than about 1
micron, in further embodiments no more than about 250 nm, in
additional embodiments no more than about 200 nm, in some
embodiments from about 5 nm to about 150 nm, in other embodiments
from about 5 nm to about 100 nm, in further embodiments from about
5 nm to about 75 nm and in some embodiments from about 5 nm to
about 50 nm. In particular, for some printing applications, it is
observed that good printing properties are generally correlated
with Z-average particle sizes of no more than about 200 nm. With
respect to the particle size distribution, in some embodiment,
essentially all of the secondary particles can have a size
distribution from scattering results with effectively no intensity
corresponding to more than 5 times the Z-average secondary particle
size, in further embodiments no more than about 4 times the
Z-average particle size and in other embodiments no more than about
3 times the Z-average particle size. Furthermore, the DLS particle
size distribution can have in some embodiments a full width at
half-height of no more than about 50 percent of the Z-average
particle size. Also, the secondary particles can have a
distribution in sizes such that at least about 95 percent of the
particles have a diameter greater than about 40 percent of the
Z-average particle size and less than about 250 percent of the
Z-average particle size. In further embodiments, the secondary
particles can have a distribution of particle sizes such that at
least about 95 percent of the particles have a particle size
greater than about 60 percent of the Z-average particle size and
less than about 200 percent of the Z-average particle size. A
person of ordinary skill in the art will recognize that additional
ranges of particle sizes and distributions within the explicit
ranges above are contemplated and are within the present
disclosure.
[0198] The viscosity of the dispersion/ink is dependent on the
silicon particle concentration, the nature of the liquids as well
as the presence of any other additives. Thus, there are several
parameters that provide for adjustment of the viscosity. In
general, a selected coating or printing approach has an appropriate
range of viscosity. Surface tension may also be a significant
parameter for certain printing applications. In general, for most
ink formulations, the use of a solvent blend can provide for the
rapid evaporation of a low boiling temperature solvent (boiling
point approximately no more than about 160.degree. C.) while using
a higher boiling solvent (boiling point at least about 175.degree.
C.) to control the viscosity. The high boiling solvent generally
can be removed more slowly without excessive blurring of the
printed image. After removal of the higher boiling temperature
solvent, the printed silicon particles can be cured, or further
processed into the desired device. The properties for inkjet
printing, gravure printing and screen printing for silicon
nanoparticle inks are described in more detail in the following.
These printing techniques represent a significant range of desired
viscosities from relatively low viscosity for inkjet inks, to
moderate viscosities for gravure printing inks and high viscosities
for screen print pastes.
[0199] For some inkjet embodiments, the viscosity can be from 0.1
cP (mPas) to about 100 cP, in other embodiments from about 0.5 cP
to about 50 cP and in further embodiments from about 1 cP to about
30 cP. Surface tension can be a significant parameter for inkjet
inks. For some inkjet embodiments, the dispersions/inks can have a
surface tension from about 20 to about 100 dynes/cm and in further
embodiments from about 25 to about 80 dynes/cm and in additional
embodiments form about 30 to about 55 dynes/cm. A person of
ordinary skill in the art will recognize that additional ranges of
viscosity and surface tension within the explicit ranges above are
contemplated and are within the present disclosure.
[0200] To achieve the target fluid properties, the compositions of
the fluids can be correspondingly adjusted. For inkjet inks, the
silicon particle concentrations are generally at least about 1
weight percent, in further embodiments at least about 2.5 weight
percent and in additional embodiments from about 5 weight percent
to about 15 weight percent. In some embodiments, the inkjet inks
can comprise an alcohol and a polar aprotic solvent. The alcohol
can be a relatively low boiling point solvent, such as isopropanol,
ethylene glycol, propylene glycol, ethanol, methanol or
combinations thereof. In some embodiments, suitable aprotic
solvents include, for example, N-methylpyrrolidone,
dimethylformamide, dimethylsulfoxide, methylethylketone,
acetonitrile, ethylacetate and combinations thereof. In general,
the ink can comprise from about 10 weight percent to about 70
weight percent alcohol and in further embodiments from about 20
weight percent to about 50 weight percent alcohol. Similarly, the
ink can comprise from about 30 weight percent to about 80 weight
percent polar aprotic solvent and in additional embodiments form
about 40 weight percent to about 70 weight percent polar aprotic
solvent. A person of ordinary skill in the art will recognize that
additional concentration and property ranges within the explicit
ranges above are contemplated and are within the present
disclosure.
[0201] For screen printing, the formulations are prepared as a
paste that can be delivered through the screen. The screens
generally are reused repeatedly. The solvent systems for the paste
should be selected to both provide desired printing properties and
to be compatible with the screens so that the screens are not
damaged by the paste. Suitable lower boiling point solvents
include, for example, isopropyl alcohol, cyclohexanone,
dimethylformamide, acetone or combinations thereof. Suitable higher
boiling point solvents include, for examples, ethylene glycol,
propylene glycol, N-methylpyrrolidone, terpineols, such as
.alpha.-terpineol, Carbitol, butyl Cellosolve, or combinations
thereof. The screen printing paste can further include a surfactant
and/or a viscosity modifier. In general, the screen printable ink
or paste are very viscous and can be desired to have a viscosity
from about 10 Pas (Poise) to about 300 Pas, and in further
embodiments from about 50 Pa-s to about 250 Pas. The screen
printable inks can have a silicon particle concentration from about
5 weight percent to about 25 weight percent silicon particles.
Also, the screen printable inks can have from 0.25 to about 10
weight percent lower boiling solvent, in further embodiments from
about 0.5 to about 8 and in other embodiments from about 1 to about
7 weight percent lower boiling solvent. The description of screen
printable pastes for the formation of electrical components is
described further in U.S. Pat. No. 5,801,108 to Huang et al.,
entitled "Low Temperature Curable Dielectric Paste," incorporated
herein by reference, although the dielectric paste comprises
additives that are not suitable for the semiconductor pastes/inks
described herein. A person of ordinary skill in the art will
recognize that additional ranges of composition and properties for
silicon pastes within the explicit ranges above are contemplated
and are within the present disclosure.
[0202] The property ranges of inks suitable for gravure printing
are intermediate between the properties of inkjet inks can screen
printing pastes. For gravure printing, the viscosity of the ink can
be from about 10 cP to about 800 cP, in further embodiments from
about 20 cP to about 750 cP and in additional embodiments from
about 30 cP to about 600 cP. To achieve the desired ink properties,
the ink can comprise silicon particle concentrations from about 1
weight percent to about 20 weight percent, in further embodiments
from about 2 weight percent to about 17 weight percent and in other
embodiments from about 5 weight percent to about 14 weight percent
silicon particles. In general, there are a range of suitable low
boiling and high boiling solvents that can be blended for gravure
printing. For example, isopropyl alcohol is suitable for use as the
lower boiling solvent, and propylene glycol, ethylene glycol,
terpineol and combinations thereof are suitable higher boiling
solvents. For these applications, the ink can comprise from about
0.5 weight percent to about 30 weight percent low boiling alcohol
and in further embodiments from about 1 to about 25 weight percent
low boiling alcohol. The ratio of solvents can be used to adjust
the viscosity to a desired value. A person of ordinary skill in the
art will recognize that additional ranges of composition and
properties for gravure printing inks within the explicit ranges
above are contemplated and are within the present disclosure.
[0203] While the inks can comprise heavily doped silicon particles,
it can be desirable to further include a liquid dopant source in
the ink. Suitable liquid dopant sources include, for example,
organophosphorus compounds (for example, phosphonates, such as
etidronic acid and dimethyl methyl phosphonate, organophosphine
oxide, organophosphanes, such as diphenylphosphine, or
organophosphates, such as trioctyl phosphate), organoboron
compounds (tetraphenylborate or triphenylboron), phosphoric acid,
boric acid, combinations thereof or the like. In general, an ink
can comprise no more than about 10 weight percent dopant
composition as well as any and all subranges within this explicit
range.
[0204] For dopant drive in applications, it can be desirable to
include further components to the ink to facilitate the dopant
drive in process. In particular, the ink can comprise a silicon
oxide precursor, such as tetraethyl orthosilicate (TEOS). TEOS can
be converted to silica in a hydrolysis reaction with water at an
appropriate pH. A silica glass can facilitate dopant drive in from
highly doped silicon particles into a silicon substrate through the
at least partial isolation of the dopants from the vapor phase
above the deposited particles. The alternative or additional use of
spin on glasses and silica sol-gels in silicon inks is described in
copending U.S. provisional, patent application 61/438,064 to Liu et
al, entitled "Silicon Substrates With Doped Surface Contacts Formed
From Doped Silicon Inks and Corresponding Processes," incorporated
herein by reference.
[0205] The dispersions/inks can be formed using the application of
appropriate mixing conditions. For example, mixers/blenders that
apply shear can be used and/or sonication can be used to mix the
dispersions. The particular additives can be added in an
appropriate order to maintain the stability of the particle
dispersion. A person of ordinary skill in the art can select the
additives and mixing conditions empirically based on the teachings
herein.
[0206] Coating and Printing Processes
[0207] The dispersions/inks can be deposited for using a selected
approach that achieves a desired distribution of the dispersion on
a substrate. For example, coating and printing techniques can be
used to apply the ink to a surface. Using selected printing
approaches, patterns can be formed with high resolution. Coating
and/or printing processes can be repeated to obtain a thicker
deposit of ink and/or to form overlapping patterns. For example,
the printing/coating can be repeated for a total of two
printing/coating steps, three printing/coating steps, four
printing/coating steps or more than four printing/coating steps.
Each printing/coating step may or may not involve a patterning. The
ink may or may not be dried or partially dried between the
respective coating and/or printing steps. Sequential patterned
printing steps generally involve the deposition onto an initially
deposited ink material. The subsequent deposits may or may not
approximately align with the initially deposited material, and
further subsequently deposited patterns of material may or may not
approximately align with the previously deposited layers. Thus,
multiple layers can be present only at a subset of the ink deposit.
Following deposition, the deposited material can be further
processed into a desired device or state.
[0208] Suitable coating approaches for the application of the
dispersions include, for example, spin coatings, dip coating, spray
coating, knife-edge coating, extrusion or the like. In general, any
suitable coating thickness can be applied, although in embodiments
of particular interest, coating thickness can range from about 50
nm to about 500 microns and in further embodiments from about 100
nm to about 250 microns. A person of ordinary skill in the art will
recognize that additional ranges of thicknesses within the
particular ranges above are contemplated and are within the present
disclosure.
[0209] Similarly, a range of printing techniques can be used to
print the dispersion/ink into a pattern on a substrate. Suitable
printing techniques include, for example, screen printing, inkjet
printing, lithographic printing, gravure printing and the like.
Suitable substrates include, for example, polymers, such as
polysiloxanes, polyamides, polyimides, polyethylenes,
polycarbonates, polyesters, combinations thereof, and the like,
ceramic substrates, such as silica glass, and semiconductor
substrates, such as silicon or germanium substrates. The
composition of the substrates influences the appropriate range of
processing options following deposition of the dispersion/ink.
[0210] While various coating and printing approaches are suitable,
inkjet printing offers desirable features for some applications
with respect to speed, resolution and versatility with respect to
real time selection of deposition patterning while maintaining
speed and resolution. Practical deposition using inkjet printing
with inorganic particles requires dispersion properties that
involve both the techniques to form high quality silicon
nanoparticle, such as with laser pyrolysis, along with the improved
ability to form high quality dispersions from these particles.
Thus, the particles produced using laser pyrolysis combined with
the improved dispersion techniques provides for the formation of
inks that are amenable to inkjet deposition.
[0211] Similarly, screen printing can offer desirable features for
printing silicon inks for some applications. In particular, screen
printing may already be tooled for a particular use. Thus, the
substitution of the silicon inks for other materials in a
production line may be performed with reduced capital expenses.
Also, the pastes for screen printing may have a greater silicon
particle concentration relative to concentrations suitable for
other deposition approaches. The silicon particles and processes
described herein are suitable for forming good quality pastes for
screen printing as demonstrated in the examples below. Similarly,
gravure printing can provide for efficient processing at high
speeds with moderate resolution and relatively low maintenance
costs for capital equipment.
[0212] A representative printed substrate is shown in FIG. 13. In
this embodiment, substrate 450 has a surface coating 452 with
windows 454, 456 through coating 452 to expose a portion of the
substrate surface. Silicon ink is printed to form deposits 458, 460
on the substrate surface. The substrate can comprise silicon,
germanium or an alloy thereof. Suitable substrates include, for
example, high purity silicon wafers and the like. In other
embodiments, suitable substrates include silicon/germanium foils,
as described in published U.S. Patent application 2007/0212510A to
Hieslmair et al., entitled "Thin Silicon or Germanium Sheets and
Photovoltaics Formed From Thin Sheets," incorporated herein by
reference. A silicon dispersion/ink can be applied over the surface
using the coating or printing techniques described above.
[0213] In general, following deposition, the liquid evaporates to
leave the particles and any other non-volatile components of the
inks remaining. For some embodiments with suitable substrates that
tolerates suitable temperatures and with organic ink additives, if
the additives have been properly selected, the additives can be
removed through the addition of heat in an appropriate oxygen
atmosphere to remove the additives, as described above. Once the
solvent and optional additives are removed, the silicon particles
can then be processed further to achieve desired structures from
the particles.
[0214] For example, the deposited silicon nanoparticles can be
melted to form a cohesive mass of the silicon deposited at the
selected locations. If a heat treatment is performed with
reasonable control over the conditions, the deposited mass does not
migrate significantly from the deposition location, and the fused
mass can be further processed into a desired device. The approach
used to sinter the silicon particles can be selected to be
consistent with the substrate structure to avoid significant damage
to the substrate during silicon particle processing. For example,
laser sintering or oven based thermal heating can be used in some
embodiments. Laser sintering and thermal sintering of silicon
nanoparticles is described further in copending U.S. patent
application Ser. No. 12/887,262, now published Application
2011/0120537, to Liu et al., entitled "Silicon Inks for Thin Film
Solar Cell Formation, Corresponding Methods and Solar Cell
Structures," incorporated herein by reference. The use of highly
doped silicon nanoparticles for dopant drive in applications is
described further below.
Semiconductor Applications
[0215] For solar cell, thin film transistor and other semiconductor
applications, silicon particles can be used to form structures,
such as doped contacts, that can form a portion of a particular
device. In some embodiments, the inks can be used to form layers or
the like of doped or intrinsic silicon. The formation of silicon
layers can be useful for formation or thin film semiconductor
elements, such as on a polymer film for display, layers for thin
film solar cells or other applications, or patterned elements,
which can be highly doped for the introduction of desired
functionality for thin film transistors, solar cell contacts or the
like.
[0216] The formation of a solar cell junction can be performed
using the screen printing of a silicon ink with thermal
densification in which the processing steps are folded into an
overall processing scheme. In some embodiments, doped silicon
particles can be used as a dopant source that provides a dopant
that is subsequently driven into the underlying substrate to for a
doped region extending into the silicon material. Following dopant
drive-in, the silicon particles may or may not be removed. Thus,
the doped silicon particles can be used to form doped contacts for
solar cells. The use of doped silicon particles for dopant drive-in
is described further in copending provisional patent application
61/438,064 to Liu et al, entitled "Silicon Substrates With Doped
Surface Contacts Formed From Doped Silicon Inks and Corresponding
Processes," incorporated herein by reference.
[0217] Some specific embodiments of photovoltaic cells using thin
semiconductor foils and back surface contact processing is
described further in published U.S. patent application 2008/0202576
to Hieslmair, entitled "Solar Cell Structures, Photovoltaic Panels,
and Corresponding Processes," incorporated herein by reference. In
some embodiments, the silicon ink is applied through
pre-established windows to the substrate surface. The doped ink is
printed within the substrate windows. Other patterning or no
patterning can be used as desired for a particular application.
[0218] The silicon inks can also be used for the formation of
integrated circuits for certain applications. Thin film transistors
(TFTs) can be used to gate new display structures including, for
example, active matrix liquid crystal displays, electrophoretic
displays, and organic light emitting diode displays (OLED).
Appropriate elements of the transistors can be printed with silicon
inks using conventional photolithographic approaches or for
moderate resolution using inkjet printing or other suitable
printing techniques. The substrates can be selected to be
compatible with the processing temperatures for the ink.
[0219] The TFTs comprise doped semiconductor elements and
corresponding interfaces. Thin film transistors used as electronic
gates for a range of active matrix displays are described further
in Published U.S. Patent Application number 2003/0222315A to
Amundson et al., entitled "Backplanes for Display Applications, and
Components for use Therein," incorporated herein by reference. An
n-type doped polycrystalline or amorphous silicon TFT active
element with an anode common structure with an organic LED element
is described further in U.S. Pat. No. 6,727,645 to Tsjimura et al.,
entitled "Organic LED Device," incorporated herein by reference.
OLED display structures are described further, for example, in
published U.S. Patent Application 2003/0190763 to Cok et al.,
entitled "Method of Manufacturing a Top-Emitting OLED Display
Device With Desiccant Structures," incorporated herein by
reference. Conventional photolithography techniques for the
formation of TFTs is described further in U.S. Pat. No. 6,759,711
to Powell, entitled "Method of Manufacturing a Transistor,"
incorporated herein by reference. These conventional
photolithography approaches can be replaced with the printing
approaches described herein. U.S. Pat. No. 6,759,711 further
describes integration of TFTs with an active matrix liquid crystal
display. The silicon nanoparticle inks described herein can be
effectively used to print elements of a TFT with selected
dopants.
[0220] Biochips are growing in use for diagnostic medical purposes.
U.S. Pat. No. 6,761,816 to Blackburn et al., entitled "Printed
Circuit Boards With Monolayers and Capture Ligands," incorporated
herein by reference. These biochip arrays have electrical circuits
integrated with biological components so that automatic evaluations
can be performed. The functional inks described herein can be used
to form electrical components for these devices while biological
liquids can be printed or otherwise deposited for the other
components.
[0221] Radio-Frequency Identification (RFID) tags are gaining
widespread use for loss prevention. These devices are desired to be
small for less obtrusiveness and low cost. The silicon inks
described herein can be used effectively to print RFIDs or
components thereof. Systems for printing RFIDs on a roll-to-roll
configuration are described further in published U.S. Patent
Application serial number 2006/0267776A to Taki et al., entitled
"RFID-Tag Fabricating Apparatus and Cartridge," incorporated herein
by reference.
[0222] To form a device component from the silicon particle
deposit, the material is heated. For example, the structure can be
placed into an oven or the like with the temperature set to soften
the particles such that fuse into a mass. The time and temperature
can be adjusted to yield a desired fusing and corresponding
electrical properties of the fused mass. Alternative approaches can
be used to heat the surface of the substrate with the deposit. A
thermal process based on taking advantage of reduced melting
temperatures for silicon nanoparticles with a particle size no more
than roughly 10 nm is described in U.S. Pat. No. 5,576,248 to
Goldstein, entitled "Group IV Semiconductor Thin Films Formed at
Low Temperature Using Nanocrystal Precursors," incorporated herein
by reference. This reference describes films that are no thicker
than about 20 nm. Higher temperatures or light based fusing can be
used to achieve thicker deposits.
[0223] However, improved control of the resulting doped substrate
as well as energy saving can be obtained through the use of light
to melt the silicon particles without generally heating the
substrate or only heating the substrate to lower temperatures.
Local high temperatures on the order of 1400.degree. C. can be
reached to melt the surface layer of the substrate as well as the
silicon particles on the substrate. Generally, any intense source
selected for absorption by the particles can be used, although
excimer lasers or other lasers are a convenient UV source for this
purpose. Excimer lasers can be pulsed at 10 to 300 nanoseconds at
high fluence to briefly melt a thin layer, such as 20 nm to 1000
nm, of the substrate. Longer wavelength light sources such as 1
micron wavelength light sources can also be used.
[0224] Thermal and light based fusing of silicon particles is
described further in published U.S. Patent Application
2005/0145163A to Matsuki et al., entitled "Composition for Forming
Silicon Film and Method for Forming Silicon Film," incorporated
herein by reference. In particular, this reference describes the
alternative use of irradiation with a laser or with a flash lamp.
Suitable lasers include, for example, a YAG laser or an excimer
laser. Noble gas based flash lamps are also described. The heating
generally can be performed in a non-oxidizing atmosphere.
[0225] Following the fusing of the silicon particles into a solid
structure, additional processing steps can be performed to
incorporate the resulting structure into the device. For
photovoltaic applications, the fused deposit can comprise a doped
silicon material that forms a p-doped or n-doped contact. The
contacts are then connected to appropriate current collectors to
provide for harvesting of the power from the photovoltaic cell.
EXAMPLES
Example 1
Synthesis of Highly Doped Si Nanoparticles Using Laser Pyrolysis
with Rectangular Nozzle and Air Knife Quenching
[0226] This example demonstrates the ability to synthesize highly
doped silicon nanoparticles with high uniformity using laser
pyrolysis.
[0227] A laser pyrolysis apparatus similar to FIG. 8 of published
U.S. patent application 2009/0020411A to Holunga et al., entitled
"Laser Pyrolysis With In-Flight Particle Manipulation for Powder
Engineering," incorporated herein by reference. The apparatus was
equipped with an air knife to provide quenching of the particles
entering the exhaust conduit.
[0228] Phosphine (PH.sub.3) was used as the phosphorous dopant
source, and the phosphine gas was mixed with inert argon at a mole
ratio of 91% Ar to 9% PH.sub.3. The silane precursor was mixed with
the blend of Ar and phosphine precursor for delivery to the nozzle.
A reactant delivery system similar to the system shown in FIG. 2
was used. The parameters for the synthesis of particles with two
dopant levels are summarized in Table 1, where slm is standard
liters per minute.
TABLE-US-00001 TABLE 1 Particle Sample 1 2 SiH.sub.4 (slm)
0.02-0.15 1-5 9% PH.sub.3 + 91% Ar (slm) 0.01-0.1 1.0-10 Pressure
(Torr) 500-650 100-300 Argon - Dilution (slm) 3-10 3-10 Argon
-Shielding (slm) 3-10 3-10 Argon -Air Knives (slm) 10-25 10-25
Laser Input (Watts) 2000 1500 Measured Dopant 2.94 7.44 (atomic
percent) Stoichiometric Dopant 4.3 27.3 Incorporation (atomic
percent)
[0229] The results were obtained under the conditions where no
visible flame is observable. The dopant levels measured with
inductively coupled plasma-mass spectroscopy (ICP-MS) are presented
in Table 1. These dopant levels can also be presented in other
units, e.g., 2.94 atomic percent=32,600 ppm by
weight=1.47.times.10.sup.21 atoms/cm.sup.3, 7.44 atomic
percent=82,400 ppm by weight=3.72.times.10.sup.21 atoms/cm.sup.3,
0.39 atomic percent=4300 ppm by weight=1.94.times.10.sup.20
atoms/cm.sup.3, and 2.5 atomic percent=28,000 ppm by
weight=1.26.times.10.sup.21 atoms/cm.sup.3. Very high dopant levels
were achieved through the laser pyrolysis synthesis process.
Example 2
Synthesis of Highly N-Doped Si Nanoparticles Using Laser Pyrolysis
with Annular Nozzle
[0230] This example demonstrates the ability to synthesize highly
doped silicon nanoparticles with high uniformity using laser
pyrolysis.
[0231] The apparatus was modified with a nozzle essentially as
shown in FIGS. 3-6. Inert shielding gas was flowed through the
inner tube and the central annular passage, and the silicon
precursor (SiH.sub.4) and dopant precursor were flowed through the
inner annular passage. Inert gas as an entrainment gas was flowed
through the outer annular passage. Experiments were performed
targeting different dopant levels.
[0232] As in example 1, phosphine (PH.sub.3) was used as the
phosphorous dopant source, and the phosphine gas was mixed with
inert argon at a mole ratio of 91% Ar to 9% PH3. The silane
precursor was mixed with the blend of Ar and phosphene precursor
for delivery to the nozzle. A reactant delivery system similar to
the system shown in FIG. 2 was used. The parameters for the
synthesis of particles with 4 selected dopant levels are summarized
in Table 2, where slm is standard liters per minute.
TABLE-US-00002 TABLE 2 Particle Sample 3 4 5 6 SiH.sub.4 (slm) 1-5
1-5 1-5 0.5-2.sup. 9% PH.sub.3 + 91% Ar (slm) 0.1-0.25 1-2.5 0.5-1
.sup. 1-2.5 Pressure (Torr) 500-700 500-700 500-700 500-700 Argon
-Inner Shielding 8-12 8-12 8-12 8-12 (slm) Argon - Dilution (slm)
5-10 5-10 5-10 5-10 Argon - Outer Shielding 25-40 25-40 25-40 25-40
(slm) Argon -Entrainment (slm) 100-200 100-200 100-200 100-200
Laser Input (Watts) 2000 2000 2000 2000 Measured Dopant 0.39 2.5 1
2.3-2.7 (atomic percent) Stoichiometric Dopant 0.46 4.3 1.5 18
Incorporation (atomic percent)
[0233] In contrast with the results in Example 1, the results in
this example were obtained under conditions in which a flame was
visible. Note that the relative incorporation of dopant in the run
under the conditions for particle sample 1 in Example 1 was similar
to the relative incorporation of dopant for particles synthesizes
under the conditions noted for particle sample 4. Sample 5 was
aimed at an intermediate dopant level relative to samples 3 and 4.
The particles in sample 6 were smaller than the particles in sample
3-5, and a significantly smaller portion of dopant was incorporated
from the flow into the particles.
[0234] TEM micrographs of the particles generated under the
conditions shown in Table 2 are shown in FIGS. 14-17. FIGS. 14 and
15 show particles produced under the conditions of particle sample
3 at two magnifications, and FIGS. 16 and 17 show particles
produced under the conditions of particle sample 4 at two
magnifications. FIGS. 18-20 show particles produced under
conditions of particle sample 6 at different magnifications. The
particles are relatively uniform with respect to particle size. The
particles produced under conditions specified for samples 3-5 had
average primary particle diameters from about 22 nm to about 25 nm,
while particles produced under the conditions of sample 6 had
average primary particle diameters of about 7 nm.
[0235] The BET surface areas were measured for sample 5 and 6, and
average particle sizes obtained from the surface area measurements
assuming unagglomerated, non-porous spherical particles were 26 nm
and 7 nm, respectively.
Example 3
Synthesis of Boron Doped Si Nanoparticles Using Laser Pyrolysis
with Annular Nozzle
[0236] This example demonstrates the ability to synthesize p-doped
silicon nanoparticles with high uniformity using laser
pyrolysis.
[0237] The laser pyrolysis was performed with an apparatus equipped
with a nozzle essentially as shown in FIGS. 3-6. Inert shielding
gas was flowed through the inner tube and the central annular
passage, and the silicon precursor (SiH.sub.4) and dopant precursor
were flowed through the inner annular passage. Inert gas as an
entrainment gas was flowed through the outer annular passage.
Experiments were performed targeting different dopant levels with
one sample having a high boron dopant level and another sample
having a low boron dopant level.
[0238] Diborane (B.sub.2H.sub.6) was used as the borane dopant
source, and the diborane gas was mixed with inert argon at a
selected mole ratio as indicated in the table below. The silane
precursor was mixed with the blend of Ar and diborane precursor for
delivery to the nozzle. A reactant delivery system similar to the
system shown in FIG. 2 was used. The parameters for the synthesis
of particles are summarized in Table 3, where slm is standard
liters per minute.
TABLE-US-00003 TABLE 3 Particle Sample 1 2 SiH.sub.4 (slm) 1-5
0.5-2.5 1% B.sub.2H.sub.6 + 99% Ar (slm) 1-3 0.005% B.sub.2H.sub.6
+ 0.01-0.04 99.995% Ar (slm) Pressure (Torr) 500-700 500-700 Argon
-Inner Shielding 5-12 5-12 (slm) Argon - Dilution (slm) 5-10 5-10
Argon - Outer Shielding 20-40 20-40 (slm) Argon -Entrainment (slm)
100-200 100-200 Laser Input (Watts) 2000 2000 Measured Dopant 3
.times. 10.sup.-4 39 (atomic percent)
TEM micrographs of particles of generated under the conditions of
sample 2 in Table 3 are displayed in FIGS. 21-23 at various
magnifications. The particles produced under the conditions of
Table 3 had particle size estimates from BET surface areas of 7 nm
(sample 1) and 20 nm (sample 2).
[0239] Metal contamination results for particles generated under
the conditions of sample 1 in Table 3 are displayed in Table 4. The
presence of metals in the synthesized silicon particles was
analyzed by first forming a slurry comprising 18 g of isopropyl
alcohol and 2 g of silicon particles. In contrast with the
contamination measurements presented in Example 7 below, the slurry
was not centrifuged. The amount of metals present in the slurry was
then measured using ICP-MS. The amount of metals present in the dry
silicon particles was then estimated by multiplying the metal
concentrations obtained in the slurry by a factor of 10 (the slurry
was 10 wt % silicon nanoparticles).
TABLE-US-00004 TABLE 4 Detection Concentration Concentration Limits
in Slurry in Particles (ppb by wt) (ppb by wt) (ppb by wt) Aluminum
0.5 21 210.0 Antimony 0.5 <0.5 <5 Arsenic 1 <1 <10
Barium 0.1 0.38 3.8 Beryllium 0.5 <0.5 <5 Bismuth 0.5 <0.5
<5 Boron 1 120 1200.0 Cadmium 0.1 <0.1 <1 Calcium 1 190
1900.0 Chromium 0.5 14 140.0 Cobalt 0.1 0.14 1.4 Copper 0.5 4.4
44.0 Gallium 0.1 1.9 19.0 Germanium 0.5 <0.5 <5 Gold 1 <1
<10 Iron 1 66 660.0 Lead 0.5 <0.5 <5 Lithium 0.5 <0.5
<5 Magnesium 0.5 19 190.0 Manganese 0.5 1.5 15.3 Molybdenum 0.5
0.94 9.4 Nickel 0.5 8.5 85.0 Niobium 0.5 <0.5 <5 Potassium 1
18 180.0 Silver 0.5 <0.5 <5 Sodium 1 12 120.0 Strontium 0.1
0.19 1.9 Tantalum 0.5 <0.5 <5 Thallium 0.5 <0.5 <5 Tin
0.5 <0.5 <5 Titanium 0.5 7.7 77.0 Vanadium 0.5 <0.5 <5
Zinc 0.5 19 190.0 Zirconium 0.1 0.15 1.5
Most metals were present in only very low concentrations in the
dispersion. Of the transition metals, only iron was present in
amounts greater than 200 ppb.
Example 4
Dispersions of Si Nanoparticles
[0240] This example demonstrates the ability to form well dispersed
silicon nanoparticles at high concentrations without surface
modification of the particles.
[0241] Dispersions have been formed with silicon nanoparticles
having different average primary particle sizes. The crystalline
silicon particles were formed as described in Example 2 with high
levels of doping. Concentrated solutions were formed that are
suitable for ink applications, and the solvent is also selected for
the particular printing application. For secondary particle size
measurements, the solutions were diluted so that reasonable
measurements could be made since concentrated solutions scatter too
much light to allow secondary particle size measurements.
[0242] The particles were mixed with the solvent and sonicated to
form the dispersion. The dispersions were formed at concentrations
of 3-7 weight percent particles. The samples were diluted to 0.4
weight percent particles for the secondary particle size
measurements, and the measurements were made using differential
light scattering (DLS). Referring to FIGS. 24 and 25, the secondary
particle sizes were measured in isopropyl alcohol for particles
with average primary particle sizes of 25 nm (FIG. 24) and 9 nm
(FIG. 25). The Z-average secondary particle sizes were similar for
the two sets of Si particles with the Z-average particles sizes
being slightly larger for the particles with about 9 nm average
primary particle size. These results suggest greater agglomeration
for the particles having a 9 nm average particle diameter. A close
examination of the 9 nm particles by transmission electron
microscopy yielded a view of more agglomerated non-spherical
particles, which is consistent with the secondary particle size
measurements.
[0243] Dispersions were also formed in other solvent systems
suitable for other printing approaches. Specifically, a dispersion
was formed in ethylene glycol. The solution was formed at a
concentration of silicon particles of 3-7 weight percent. For the
measurement of the secondary particle size by DLS, the dispersion
was diluted to 0.5 weight percent Si nanoparticles. The DLS results
are shown in FIG. 26. Also, a dispersion was formed in terpineol.
Again, the dispersion was diluted to a concentration of 0.5 weight
percent particles for measurement of the secondary particle size by
DLS as shown in FIG. 27. The secondary particle size measurements
for the terpineol based solvent system were similar to the particle
size measurements in the ethylene glycol based solvent system.
[0244] As discussed further in the following examples, these
secondary particles sizes were suitable for forming inks with good
performance for inkjet printing, spin coating and screen
printing.
Example 5
Inkjet Ink and Printing
[0245] This example demonstrates the suspension of doped silicon
nanoparticles in a solvent suitable for inkjet printing as well as
the demonstration of successful inkjet printing of the resulting
ink using a commercial inkjet head.
[0246] In a set of experiments, a silicon ink was formed with
undoped Si particles formed as described in Example 1 having an
average particle size of about 26 nm. The particles had a BET
surface area corresponding to 28 nm particles. The ink was
formulated with a concentration of 12 weight percent particles in a
solvent of 1 part by weight propylene glycol and 7 parts by weight
N-methylpyrrolidone. The ink had a viscosity (.eta.) of 13.7 cP and
a surface tension (.gamma.) of about 44 D/cm. The inkjet printing
properties of the ink were evaluated with a Dimatix DMP-2800 inkjet
printer with 16 nozzles. 15 of the 16 nozzles printed successfully
after one initial purge. No clogging was observed with reasonably
stable ejection over 1.5 hours. The stability of the printed line
is shown in FIG. 28. A printed drop had a spot size of 60 microns
as printed and 65 microns after baking, as shown in FIG. 29.
Acceptable printing results were obtained, and the inkjets did not
clog.
[0247] Inkjet tests were also performed with dispersions comprising
doped Si particles formed as described in Example 2. The particles
had an average primary particle size of 35 nm. A shear test was
performed with dispersions in solvent blends of NMP with ethyl
lactate (EL) at a ratio of 9:1 by weight and of NMP with ethylene
glycol (EG) at a ratio from 9:1 to 7:3 by weight. The shear stress
as a function of shear rate is plotted in FIG. 30 for these two
dispersions. The dispersion with the NMP/EL solvent blend had a
viscosity of 7.6 cP, and the dispersion with the NMP/EG solvent
blend had a viscosity of 11.9 cP. Inkjet printing was tested for
the dispersions with the NMP/EG blend. Prior to printing, the
dispersions were filtered through a filter with a pore size of 450
nm to remove any large particulates. The drop watcher test results
are shown in FIG. 31 at the start of the test (a), after 1 hour (b)
and after 1 hour with a purge to clean the nozzle (c). Acceptable
printing results were observed.
Example 6
Viscosity Measurements on Inks
[0248] This example demonstrates concentrated suspensions of doped
silicon nanoparticles in a solvent suitable for screen
printing.
[0249] For screen printing, the dispersions are desired to have a
greater viscosity and a greater concentration. Various solvent
mixtures were tested with respect to viscosity. Dispersions of
silicon nanoparticles were formed in solvent mixtures of NPM and PG
at various particle concentrations. The undoped silicon
nanoparticles had an average primary particle diameter of about 30
nm. Ultrasound was used to facilitate the dispersion. The rheology
of the resulting dispersions was studied. Some of the dispersions
solidified so that fluid measurements could not be performed. The
results are presented in Table 5.
TABLE-US-00005 TABLE 5 Solvent Si Viscosity YS Sample ID wt % (cP)
(D/cm.sup.2) Rheology 1 1 17.0 16.88 0 N 2 2 15.4 12.99 4.3 NN 3 3
15.3 31.70 6.3 NN 4 4 15.5 -- .infin. -- 5 5 14.4 -- .infin. -- 6 6
13.2 -- .infin. -- 7 1 14.1 5.83 3.4 NN 8 2 16.1 10.03 0.0 N 9 3
14.6 10.58 0.0 N 10 4 14.1 22.89 3.3 NN 11 5 14.8 -- .infin. -- 12
6 13.1 -- .infin. -- 13 1 11.7 1.81 0.0 N 14 2 14.0 11.51 0.0 N 15
3 11.4 7.29 0.0 N 16 4 10.9 13.60 1.7 NN 17 5 12.3 15.18 2.3 NN 18
6 11.9 -- .infin. --
In Table 5, YS refers to yield stress in dynes per square
centimeter. Yield stress is proportional to a force exerted to
initiate flow of the non-Newtonian fluid in a tube. The shear
stresses as a function of the shear rates were fit to a straight
line by least squares, and the slope corresponds to the viscosity
and the y-intercept corresponds to the yield stress. By increasing
the particle concentration in a good dispersing solvent,
non-Newtonian properties can be obtained that are expected for
proper inkjet ink. From the results above, yield stress increased
with an increase in Si particle concentration and an increase in
propylene glycol concentration.
[0250] The solvents listed in Table 5 were various blends of
propylene glycol and N-methylpyrrolidone (NMP). All of the blends
had Newtonian rheology. The compositions and viscosities for these
solvent blends are summarized in TABLE 6.
TABLE-US-00006 TABLE 6 Solvent Wt % Viscosity ID PG (cP) 1 12.6
2.47 2 25.1 3.59 3 37.1 5.06 4 50.0 7.51 5 62.6 11.33 6 74.8
16.64
[0251] The dispersions that did not solidify were also diluted to
an approximate 1 weight percent concentration. Light scattering was
used to evaluate the properties of the dispersion based on the
diluted samples. The results are summarized in Table 7. No
measurements were possible for the samples that solidified. Samples
10 and 17 formed gels, but measurements were still possible for
these samples.
TABLE-US-00007 TABLE 7 Z-average Distribution Sample (nm) Peak (nm)
PDI 1 273 331 0.24 2 99 123 0.22 3 57 71 0.22 7 298 390 0.23 8 106
139 0.22 9 80 102 0.22 10 54 69 0.22 13 309 404 0.24 14 103 123
0.25 15 75 95 0.21 16 60 75 0.19 17 44 57 0.23
As seen in Table 7, the dispersion size decreased with increasing
amounts of PG in the solvent blend.
Example 7
Impurities in Si Inks
[0252] This example demonstrates the range and quantities of
impurities in Si inks.
[0253] To test the range and quantities of impurities in Si inks,
two slurries and two spin coating inks were formed, all from
phosphorous doped silicon particles formed as described in Example
2 similar to sample 4. The silicon particles had an average primary
particle diameter of about 7 nm. The slurries comprised a 5 weight
percent mixture of n++ doped silicon nanoparticles in isopropyl
alcohol. The spin coating inks were formed from a 6.3 weight
percent dispersion of phosphorous doped silicon particles in a
blend of isopropyl alcohol and ethylene glycol. The dispersion was
sonicated and centrifuged and the ink was subsequently decanted
from the processed dispersion. The composition and corresponding
amount of impurities in the slurries and the inks were measured
using ICP-MS. The results of the ICP-MS analysis are displayed in
Table 8.
TABLE-US-00008 TABLE 8 Concentration in Slurry Concentration in Ink
(ppb by wt) (ppb by wt) Sample 1 Sample 2 Sample 1 Sample 2
Aluminum 25 2.6 <0.5 0.59 Chromium 10 9.1 0.5 0.62 Copper 2.7
2.7 <0.5 0.55 Iron 62 39 1.4 2.3 Lead <0.5 <0.5 <0.5
<0.5 Manganese 1.7 2.1 <0.5 <0.5 Molybdenum 1 0.87 <0.5
<0.5 Nickel 7.8 5.7 <0.5 <0.5 Titanium 3.8 2.6 0.84
<0.5 Zinc 9.5 4.4 3 2.3 Calcium 74 10 3.2 6.3 Magnesium 11 5
<0.5 12 Potassium 23 7.3 2.4 1.9 Sodium 19 4.8 1.4 1.3
[0254] As seen from Table 8, the relative amount of metallic
impurities is generally less in the ink than it is in the slurry.
Thus, the centrifugation process is correspondingly seen to be
effective at removing impurities with metal elements.
Example 8
Laser Curing of Si Inks
[0255] This example demonstrates the laser sintering of the printed
silicon nanoparticles to obtain reasonable levels of electrical
conductivity for both junction diode type formats and solar cell
contacts.
[0256] In a first set of experiments, phosphorous-doped particles
as described in Example 2 were dispersed in isopropyl alcohol.
These were spin coated onto a p-type silicon wafer. The solvent was
dried. Then, an infrared laser was scanned to fuse the silicon at
selected locations along the substrate. Silicon inks with different
phosphorous dopant amounts were printed using notation n+ for 0.2
to 0.4 atomic %, n++ for 2 to 4 atomic % and n+++ for 7-8 atomic
percent P.
[0257] Several silicon inks were sintered using an infrared laser.
Specifically, a thicker layer 0.5-1.0 microns) was formed with
silicon particles doped at a lower of phosphorous, and thinner
layers (0.25-0.5 micron) were formed with Si particles doped at a
greater level of phosphorous. The processing had significant
tradeoffs. More intense sintering with the laser can result in
damage to the underlying substrate. The printed was done onto a
cleaned surface of a p-type silicon wafer having a 200 micro
thickness and a 1-5 ohm-cm resistance. The sintered Si ink layer
passed a tape peel test. The lowest measured sheet resistances for
the different particle doping levels were as follows: n+++6-10
.OMEGA./cm.sup.2, n++10-30 .OMEGA./cm.sup.2 and n+30-40
.OMEGA./cm.sup.2. The sintered Si ink layer had a conductivity that
is generally 1.5-3 times lower than that of bulk Si at a given
dopant level.
[0258] FIG. 32 is a plot of sheet resistance as a function of laser
fluence for an n++ Si ink layer with a 500 nm thickness for 6
different laser pulse widths. The graph in FIG. 32 shows that the
sheet resistance decreases with increasing fluence initially, and
then remains relatively constant over a range of fluence. As
fluence increases to the threshold value, sheet resistance
increases abruptly, indicating laser damage. FIG. 33 shows a linear
relationship between the fluence threshold and pulse duration.
[0259] The sheet resistance seemed consistent with surface
morphology. Optical micrograph pictures are shown for samples with
different sheet resistances in FIG. 34. Samples with lower sheet
resistances had smoother surfaces. The dopant profile was measured
using Secondary Ion Mass Spectrometry (SIMS) to evaluate the
elemental composition along with sputtering or other etching to
sample different depths from the surface. With a reasonable cutoff
based on concentration, the depth of phosphorous was essentially
0.32 microns for a sample with a sheet resistance of 33
Ohm/(square). The depth profile is shown in FIG. 35. Sheets with
lower resistance tended to have deeper penetration of P within the
layer. The minority carrier diffusion length (MCDL) increased with
a decrease in sheet resistance. A plot of MCDL as a function of
sheet resistance is found in FIG. 36.
[0260] A schematic diagram of the diodes is shown in FIG. 37.
P-type Si wafers used to fabricate p/n junctions diodes were 100 mm
in diameter, 200 microns thick and 1-5 ohm-cm in resistivity. The
wafers were etched in 25% KOH at 80.degree. C. for 15 minutes to
remove saw damage and then dipped in 2% HF for a few seconds to
remove surface oxide. Inks formed from phosphorous doped Si
particles were used to form p/n junction diodes. The particles for
these inks had BET surface area based average particle sizes of 25
nm. One set of particles had a doping of 2.times.10.sup.20 atoms of
P per cm.sup.3 and another set of particles had a doping of
1.5.times.10.sup.21 atoms of P per cm.sup.3. The particles were
dispersed at 5 weight percent in isopropyl alcohol. The inks were
applied by spin coating onto the entire surface of the wafer. The
inks layer was dried at 85.degree. C. in a glove box. The dried
layers had a thickness from 0.250 to 1 micron.
[0261] An infrared fiber laser was used to irradiate 42 1
cm.times.1 cm squares across the wafer as shown in FIG. 38 where
the numbers in each square are the sequential cell number, the
percentage of the laser power and scanning speed in mm/s. The laser
was operated at a constant repetition rate of 500 kHz and a 16 W
average power. After irradiation with the laser, the wafer was then
immersed in 1% KOH in IPA till bubbles cease, about 2-3 minutes, at
ambient temperature to removed "green" Si ink coating outside of
the illuminated squares. Sheet resistances of the irradiated
squares were in the range from 10 to .about.700 ohms/sqr. Aluminum
was deposited on the squares and the backside of the wafer to
complete the diodes. Each square was a p/n junction diode. The best
performing diode was from cell number 10, which was made from an
ink of Si particles with phosphorous at 2.times.10.sup.20
atm/cm.sup.3 and an ink layer thickness of 500 nm. The sheet
resistance of cell number 10 measured before Al deposition was 56.7
ohm/sqr. A plot of current as a function of voltage is shown in
FIG. 39.
Example 9
Printing Properties of Si Pastes
[0262] This example demonstrates the printing properties of pastes
comprising n++ doped silicon particles.
[0263] To test the printing properties of pastes, two silicon
pastes were formed with silicon particles formed as described in
Example 2. A first paste was formed with n++ doped silicon
particles and a second paste was formed with p++ doped silicon
nanoparticles. The silicon particles had an average primary
particle diameter of about 20 nm. The pastes were formulated from
dispersions comprising 17 weight percent doped silicon particles in
ethylene glycol.
[0264] The viscosity of the first paste was shear rate dependant as
well as time dependent at high shear. FIG. 40 is a plot of the time
dependent viscosity at a constant shear rate of 1000 s.sup.-1. FIG.
41 is a plot of the shear dependent viscosity over a range of shear
rates from 100 s.sup.-1-2000 s.sup.-1. The viscosities were
measured with a rheometer. Referring to FIG. 40, the viscosity
decreased as a function of time over about 100 seconds with a
minimum viscosity of about 0.600 PaS (pascal seconds) (1 PaS=1000
cP). Referring to FIG. 41, the viscosity also showed a non-linear
dependence on shear rate. In particular, the viscosity decreased
with increasing shear rate and had a minimum viscosity of about
0.544 PaS over the range of shear rates. The screen printing
properties of the first paste were tested by using a Brookfield
R/S-CPS rheometer to simulate screen printing conditions. The
simulation comprised a pre-print step, a print, step, and a
post-print step. The pre-print step comprised applying a shear rate
to the paste at a frequency of 2 s.sup.-1 in order to simulate the
pre-stressed condition of a paste as it rests on a screen, the
pre-stressed condition a result of stirring and spreading the
paste. The print step comprised applying a shear rate to the paste
at a frequency of 1000 s.sup.-1 in order to simulate the printing
step. The post-print step comprised applying a shear rate to the
paste to the paste at a frequency of 2 s.sup.-1 in order to
simulate the recovery of the paste after the printing process. A
summary of the simulation parameters in displayed in Table 9,
below.
TABLE-US-00009 TABLE 9 Simulation Step Shear Rate (s.sup.-1) Time
(s) Pre-Print 2 60 Print 1000 60 Post-Print 2 180
[0265] During the screen printing simulation, the viscosity
decreased during the print step and increased during the recover
step. FIG. 42 is a plot of the time dependent viscosity during the
simulation. During the pre-print step, the viscosity increased
non-monotonically from about 200 PaS to about 240 PaS. At the
beginning the print step, the viscosity decreases to about 0.808
PaS. This result reflects the shear rate dependent viscosity
displayed in FIG. 41. At the beginning of the post-print step, the
viscosity increases to about 115 PaS and levels out at about 130
PaS after about 75. Notably, there is about a 100 PaS difference
between the pre-print viscosity and the post-print viscosity,
suggesting an irreversible change in the paste viscosity over the
time period of the measurement indicating that the paste has a high
thixotropy.
[0266] The printing properties of the first and second pastes were
tested by printing the pastes on a substrate. Lines were printed on
a substrate over 30 minutes using a manual screen printer. The
printed lines could be formed with desired printing properties with
widths ranging from about 170 .mu.m to about 310 .mu.m and the
thicknesses of the printed inks ranging from about 200 nm to about
5 .mu.m. No clogging was observed over 30 minutes of printing.
FIGS. 43-45 are optical micrograph images of printed lines. FIGS.
43 and 44 are optical micrograph images of lines printed with the
first ink. FIG. 45 is an optical micrograph image of a line printed
with the second paste.
Example 10
Impurities in Si Pastes
[0267] This example demonstrates the range and quantities of
impurities in Si pastes.
[0268] To test the range and quantity of impurities in Si pastes,
two silicon nanoparticle pastes were formed from n++ doped silicon
particles formed as described in Example 2. The silicon particles
had an average primary particle diameter of about 7 nm. Two pastes
were formulated from a 6.3 weight percent dispersion of n++ doped
silicon particles in a solvent comprising isopropyl alcohol.
Additional efforts were made in the second sample in processing to
further reduce the introduction of contaminants from the process
equipment. The dispersion was sonicated and centrifuged. The
composition and corresponding amount of impurities in the paste
were measured using ICP-MS for the two pastes. The results of the
ICP-MS analysis are displayed in Table 10.
TABLE-US-00010 TABLE 10 Detection Concentration Concentration
Limits in Sample 1 in Sample 2 (ppb) (ppb by wt) (ppb by wt)
Aluminum 0.5 12 53 Calcium 1 110 380 Chromium 0.5 8.5 6 Copper 0.5
3.3 1.3 Iron 1 140 39 Lead 0.5 <0.5 0.5 Magnesium 0.5 14 110
Molybdenum 0.5 <0.5 <0.5 Nickel 0.5 5.5 0.94 Potassium 1 61
78 Sodium 1 750 92 Titanium 0.5 4.1 3.1 Zinc 0.5 12 43
The samples exhibited very low contaminant levels, especially with
respect to transition metal contaminants. Overall the second sample
had lower transition metal contamination, although zinc
contamination was somewhat higher in the second sample.
Example 10
Viscosity of Silicon Paste
[0269] This example demonstrates dependence of silicon paste
viscosity on the concentration of silicon particles.
[0270] To demonstrate the viscosity dependence, several silicon
pastes were formed. The pastes were formed from dispersions
comprising n++ doped silicon particles with an average primary
particle size of about 20 nm, synthesized as described in Example
2, above. The as synthesized particles were added to ethylene
glycol ("EG") to form a dispersion. The resulting mixture was
sonicated to form the pastes. Each paste was formulated with a
silicon particle concentration of either 10 wt %, 11.5 wt %, 12.5
wt %, 14.5 wt %, 16 wt %, or 18 wt %. The viscosities of the
various pastes were measured at shear rates of 2 s.sup.-1 and 1000
s.sup.-1 using a Brookfield R/S-CPS rheometer.
[0271] At constant shear rate, the paste viscosity had a roughly
exponential dependence on the silicon particle concentration. FIGS.
46 and 47 are plots of particle concentration versus viscosity for
the pastes formed as described above, at shear rates of 2 s.sup.-1
(FIG. 46) or 1000 s.sup.-1 (FIG. 47). The points are measured
viscosity data and the lines are exponential fits to the data. The
viscosities measured at a shear rate of 2 s.sup.-1 were
substantially higher than the corresponding viscosities measure at
a shear rate of 1000 s.sup.-1. These results demonstrate that
viscosities of silicon pastes can be selected over a wide range
through the corresponding selection of the particle concentration
over desirable ranges.
Example 11
Dispersibility of Particles with Various Solvents
[0272] This example demonstrates the dispersibility of silicon
particles in various ink compositions as well as the effectiveness
of various degglomeration processes.
[0273] To demonstrate dispersibility, a first set of samples was
formed from silicon particles formed as described in Example 2 with
about a 7 nm average primary particle size. For each sample, a
dispersion was formed by combining an appropriate amount of silicon
particle powder to a solvent. To form the first set of samples, one
of three solvents were selected: ethylene glycol ("EG"), isopropyl
alcohol ("IPA"), or n-methylpyrrolidone ("NMP"). After combining
the particles and the solvent, the resulting mixture was sonicated
to disperse the particles. Each sample had a concentration of about
0.5 wt percent silicon particles. All of the samples exhibited some
level of sedimentation within about 30 minutes. After this initial
settling, stable dispersions were obtained. The dispersibility of
silicon particles in each sample was then evaluated by measuring
the Z-average particle size, i.e. secondary average particle size,
of particles using DLS.
[0274] FIG. 48 is a graph containing plots of relative intensity
versus particle size obtained from DLS analysis of these three
samples. Based on these results, the sample comprising IPA had
improved dispersibility relative to the samples that comprised
other solvents, and NMP provided better dispersibility of the
silicon particles than ethylene glycol. Referring to FIG. 48, the
distributions of secondary particle sizes in all samples were
multimodal, i.e. each distribution has a plurality of identifiable
distinct peaks. Keeping in mind that the scattering intensity is a
weighted distribution in which larger particles are weighted more
than smaller particles, the number of particles that gave rise to
the modes near about 20 nm was significant relative to the number
of particles that gave rise to the modes near about 105 nm.
[0275] Another set of samples were prepared with 5 different
solvents to demonstrate the respective dispersability with these
five solvents. The five solvents were ethylene glycol (EG),
diethylene glycol (DEG), propylene glycol (PG), and ethylene glycol
phenyl ether (EGPE). FIG. 49 is a graph containing plots of
relative intensity versus particle size obtained from DLS analysis
of the samples for these five solvents. Based on these results, the
sample with the PG solvent had improved dispersibility relative to
samples comprising other solvents. In particular, the
characteristics of the distribution can be examined using the
Z-average particle size and the distribution can be characterized.
Specifically, the distribution width is reported as the
polydispersity index (PDI). The PDI is a parameter that results
from the light scattering calculations. Table 11 displays the
Z-average particle size and polydispersity index for the samples,
both calculated from the intensity distributions shown in FIG. 49.
Table 11 reveals that silicon particles had the smallest Z-average
particle size when dispersed with PG and had the most uniform
distribution of secondary particles size when dispersed with DEG.
On the other hand, silicon particles had the largest Z-average
particle size and the least uniform distribution of secondary
particle size when dispersed with glycerol. Based upon the data in
FIG. 49 and Table 11, the degree of dispersibility of the silicon
particles in the various solvents, ordered starting with better
dispersability, was PG>DEG>EG>EGPE>glycerol.
TABLE-US-00011 TABLE 11 Z-Average Particle Size Sample (nm) PDI EG
111.3 0.089 DEG 89.7 0.07 PG 70.8 0.077 EGPE 82.2 0.153 Glycerol
128.9 1
[0276] To demonstrate the effectiveness of deagglomeration
processes, three additional sets of samples were prepared by
forming dispersions and subsequently processing the dispersions to
deagglomerate the silicon particles therein. In particular, a first
set of three samples were prepared at 0.5 wt percent in ethylene
glycol. One sample was deagglomerated using test bath sonication, a
second sample was processed with centrifugal planetary milling
without beads, and a third sample was processed with centrifugal
planetary milling with fused zirconia beads having a diameter
between about 100 .mu.m to about 200 .mu.m. Test bath sonication
was done for about 3 hours. Centrifugal planetary milling was done
for about 10 minutes at about 2000 rpm using a Thinky ARE-250
Planetary Mixer. The dispersibility of silicon particles in each
sample was then assessed by measuring the Z-average particle size
of particles in the various samples using DLS. FIG. 50 is a graph
containing plots of relative intensity versus particle size
obtained from DLS analysis of the three samples. The sample
prepared with centrifugal planetary milling with beads had a
Z-average particle size of 109 nm, while the sample prepared with
centrifugal planetary milling without milling beads had a Z-average
particle size of 192 nm. The sample sonicated with test bath
sonication had a Z-average particle size of 116 nm, which is close
to the value obtained with centrifugal planetary milling with
beads.
[0277] Another set of samples was processed with varying times of
probe sonication. The dispersability of silicon particles in each
sample was then measured by measuring the Z-average particle size
of particles in the various samples using DLS. The samples were
prepared with non-doped silicon particles with an average primary
particle size of about 7 nm at 2.5 wt. percent in ethylene glycol.
After performing the probe sonication, the samples were diluted to
0.5 wt. percent to perform the DLS measurements. FIG. 51 is a graph
containing plots of relative intensity versus particle size
obtained from DLS analysis of samples processed with varying
lengths of sonication times. Increased probe sonication times
increased the effectiveness of the process as a deagglomeration
process. Specifically, the Z-average particle sizes decreased with
increasing sonication times with samples processed with sonication
times of 10 minutes, 20 minutes and 30 minutes having respective
Z-average particle sizes of 98 nm, 88 nm and 77 nm. Based on these
results, probe sonication was a more effective deagglomeration
process relative to planetary milling and bath sonication since
probe sonication achieved smaller Z-average particle sizes, with
values below 100 nm.
[0278] The specific embodiments above are intended to be
illustrative and not limiting. Additional embodiments are within
the broad concepts described herein. In addition, although the
present invention has been described with reference to particular
embodiments, those skilled in the art will recognize that changes
can be made in form and detail without departing from the spirit
and scope of the invention. Any incorporation by reference of
documents above is limited such that no subject matter is
incorporated that is contrary to the explicit disclosure
herein.
* * * * *