U.S. patent application number 11/046610 was filed with the patent office on 2005-06-23 for aluminum oxide particles.
This patent application is currently assigned to NanoGram Corporation. Invention is credited to Bi, Xiangxin, Kambe, Nobuyuki, Kumar, Sujeet, Reitz, Hariklia Dris.
Application Number | 20050132659 11/046610 |
Document ID | / |
Family ID | 22473049 |
Filed Date | 2005-06-23 |
United States Patent
Application |
20050132659 |
Kind Code |
A1 |
Kumar, Sujeet ; et
al. |
June 23, 2005 |
Aluminum oxide particles
Abstract
A collection of nanoparticles of aluminum oxide have been
produced by laser pyrolysis have a very narrow distribution of
particle diameters. Preferably, the distribution of particle
diameters effectively does not have a tail such that almost no
particles have a diameter greater than about 4 times the average
diameter. The pyrolysis preferably is performed by generating a
molecular stream containing an aluminum precursor, an oxidizing
agent and an infrared absorber. The pyrolysis can be performed with
an infrared laser such as a CO.sub.2 laser.
Inventors: |
Kumar, Sujeet; (Fremont,
CA) ; Reitz, Hariklia Dris; (Santa Clara, CA)
; Bi, Xiangxin; (San Ramon, CA) ; Kambe,
Nobuyuki; (Menlo Park, CA) |
Correspondence
Address: |
PATTERSON, THUENTE, SKAAR & CHRISTENSEN, P.A.
4800 IDS CENTER
80 SOUTH 8TH STREET
MINNEAPOLIS
MN
55402-2100
US
|
Assignee: |
NanoGram Corporation
|
Family ID: |
22473049 |
Appl. No.: |
11/046610 |
Filed: |
January 28, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11046610 |
Jan 28, 2005 |
|
|
|
09136483 |
Aug 19, 1998 |
|
|
|
Current U.S.
Class: |
51/309 |
Current CPC
Class: |
C01P 2004/50 20130101;
C01P 2004/64 20130101; C01P 2004/32 20130101; C01F 7/306 20130101;
C01P 2004/62 20130101; C09G 1/02 20130101; C01P 2002/72 20130101;
C01F 7/02 20130101; B82Y 30/00 20130101; C01P 2004/04 20130101;
C01P 2004/52 20130101; C01F 7/30 20130101 |
Class at
Publication: |
051/309 |
International
Class: |
B24D 003/02 |
Claims
What is claimed is:
1. A collection of particles comprising crystalline aluminum oxide
selected from the group consisting of delta-Al.sub.2O.sub.3 and
theta-Al.sub.2O.sub.3, the particles having an average diameter
less than about 95 nm.
2. The collection of particles of claim 1 wherein the crystalline
aluminum oxide comprises delta-Al.sub.2O.sub.3.
3. The collection of particles of claim 1 wherein the particles
comprise theta-Al.sub.2O.sub.3.
4. The collection of particles of claim 1 wherein the particles
have an average diameter less than about 50 nm.
5. The collection of particles of claim 1 wherein the particles
have an average diameter less than about 25 nm.
6. The collection of particles of claim 1 wherein the particles
have an average diameter from about 5 nm to about 25 nm
7. The collection of particles of claim 1 wherein effectively no
particles have a diameter greater than about four times the average
diameter of the collection of particles.
8. The collection of particles of claim 1 wherein effectively no
particles have a diameter greater than about three times the
average diameter of the collection of particles.
9. The collection of particles of claim 1 wherein effectively no
particles have a diameter greater than about two times the average
diameter of the collection of particles.
10. The collection of particles of claim 1 wherein the collection
of particles have a distribution of particle sizes such that at
least about 95 percent of the particles have a diameter greater
than about 40 percent of the average diameter and less than about
160 percent of the average diameter.
11. The collection of particles of claim 1 wherein the collection
of particles have a distribution of particle sizes such that at
least about 99 percent of the particles have a diameter greater
than about 40 percent of the average diameter and less than about
160 percent of the average diameter.
12. The collection of particles of claim 1 wherein the collection
of particles have a distribution of particle sizes such that at
least about 95 percent of the particles have a diameter greater
than about 60 percent of the average diameter and less than about
140 percent of the average diameter.
13. A polishing composition comprising a dispersion of a collection
of aluminum oxide particles of claim 1.
14. The polishing composition of claim 13 wherein the polishing
composition comprises from about 0.05 percent by weight to about 30
percent by weight aluminum oxide particles.
15. The polishing compositions of claim 13 wherein the polishing
composition comprises from about 1.0 percent by weight to about 10
percent by weight aluminum oxide particles.
16. The polishing composition of claim 13 wherein the dispersion is
an aqueous dispersion.
17. The polishing composition of claim 13 wherein the dispersion is
a non-aqueous dispersion.
18. The polishing composition of claim 13 further comprising
abrasive particles comprising a composition selected from the group
consisting of silicon carbide, metal oxides other than aluminum
oxide, metal sulfides and metal carbides.
19. The polishing composition of claim 16 further comprising
colloidal silica.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The current application is a continuation of pending U.S.
patent application filed on Aug. 19, 1998, entitled "Aluminum Oxide
Particles" having Ser. No. 09/136,483, which is incorporated herein
by reference.
FIELD OF THE INVENTION
[0002] The invention relates to aluminum oxide particles having
small particle diameters formed by laser pyrolysis. The invention
further relates to methods of producing the aluminum oxide
particles based on laser pyrolysis and polishing compositions
including the aluminum oxide particles.
BACKGROUND OF THE INVENTION
[0003] Technological advances have increased the demand for
improved material processing with strict tolerances on processing
parameters. In particular, smooth surfaces are required in a
variety of applications in electronics, tool production and many
other industries. The substrates requiring polishing can involve
hard materials such as semiconductors, ceramics, glass and metal.
As miniaturization continues even further, even more precise
polishing will be required. Current submicron technology requires
polishing accuracy on a nanometer scale. Precise polishing
technology can employ mechanochemical polishing involving a
polishing composition that acts by way of a chemical interaction of
the substrate with the polishing agents as well as an abrasive
effective for mechanical smoothing of the surface.
SUMMARY OF THE INVENTION
[0004] In a first aspect, the invention pertains to a collection of
particles comprising aluminum oxide. The collection of particle
have an average diameter from about 5 nm to about 500 nm. Also,
effectively no particles have a diameter greater than about four
times the average diameter of the collection of particles. A
polishing composition can be formed from a dispersion of these
aluminum oxide particles.
[0005] In another aspect, the invention pertains to a polishing
composition including a dispersion of nanoscale aluminum oxide
particles having an average diameter from about 5 nm to about 500
nm. The nanoparticles in the polishing composition preferably have
effectively no particles with a diameter greater than about four
times the average diameter of the particles.
[0006] In another aspect, the invention pertains to a method for
producing a collection of aluminum oxide particles having an
average diameter from about 5 nm to about 500 nm. The method
includes pyrolyzing a molecular stream in a reaction chamber. The
molecular stream includes an aluminum precursor, an oxidizing
agent, and an infrared absorber. The pyrolysis is driven by heat
absorbed from a laser beam.
[0007] In another aspect, the invention pertains to a collection of
particles comprising aluminum oxide, the collection of particle
having an average diameter from about 5 nm to about 500 nm. The
collection of aluminum oxide particles have a distribution of
particle sizes such that at least about 95 percent of the particles
have a diameter greater than about 40 percent of the average
diameter and less than about 160 percent of the average
diameter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a schematic sectional view of a solid precursor
delivery system taken through the center of the system.
[0009] FIG. 2 is a schematic, sectional view of an embodiment of a
laser pyrolysis apparatus taken through the middle of the laser
radiation path. The upper insert is a bottom view of the injection
nozzle, and the lower insert is a top view of the collection
nozzle.
[0010] FIG. 3 is a schematic, perspective view of a reaction
chamber of an alternative embodiment of the laser pyrolysis
apparatus, where the materials of the chamber are depicted as
transparent to reveal the interior of the apparatus.
[0011] FIG. 4 is a sectional view of the reaction chamber of FIG. 2
taken along line 3-3.
[0012] FIG. 5 is a schematic, sectional view of an oven for heating
nanoparticle, in which the section is taken through the center of
the quartz tube.
[0013] FIG. 6 is an x-ray diffractogram of aluminum oxide
nanoparticles produced by laser pyrolysis.
[0014] FIG. 7 is a TEM micrograph of nanoparticles whose x-ray
diffractogram is shown of FIG. 6.
[0015] FIG. 8 is a plot of the distribution of primary particle
diameters for the nanoparticles shown in the TEM micrograph of FIG.
7.
[0016] FIG. 9 is an x-ray diffractogram of nanoparticles of
aluminum oxide following heating in an oven.
[0017] FIG. 10 is a TEM micrograph of aluminum oxide nanoparticles
following heat treatment in an oven.
[0018] FIG. 11 is a plot of the distribution of primary particle
diameters for the nanoparticles shown in the TEM micrograph of FIG.
10.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Aluminum oxide (Al.sub.2O.sub.3) particles have been
produced having primary particles with extremely small average
diameters and a very narrow particle size distribution.
Furthermore, the particle size distribution effectively does not
have a tail so that there are no primary particles with diameters
significantly larger than the average. The particles have a roughly
spherical morphology, although the particles generally are
crystalline and can have a more specific shape reflecting the
underlying crystal lattice.
[0020] Due to their extremely high uniformity in size and shape,
these nanoscale aluminum oxide particles can be used to form
improved abrasive compositions. Also, the aluminum oxide particles
are highly pure and, in particular, lack metal contaminants.
Abrasive compositions incorporating these particles are useful for
polishing surfaces that have restrictive tolerance requirements
with respect to smoothness. The small diameter of the particles
along with the extremely high degree of uniformity of the particles
make them particularly desirable for formulating abrasive or
polishing compositions for planarization such as
chemical-mechanical polishing.
[0021] To generate the desired nanoparticles, laser pyrolysis is
used either alone or in combination with additional processing.
Specifically, laser pyrolysis is an excellent process for
efficiently producing suitable aluminum oxide particles with a
narrow distribution of average particle diameters. In addition,
nanoscale aluminum oxide particles produced by laser pyrolysis can
be subjected to heating in an oxygen environment or an inert
environment to alter and/or improve the properties of the
particles.
[0022] A basic feature of successful application of laser pyrolysis
for the production of aluminum oxide nanoparticles is the
generation of a molecular stream containing an aluminum precursor
compound, a radiation absorber and a reactant serving as an oxygen
source. The molecular stream is pyrolyzed by an intense laser beam.
As the molecular stream leaves the laser beam, the particles are
rapidly quenched.
[0023] A. Particle Production
[0024] Laser pyrolysis has been discovered to be a valuable tool
for the production of nanoscale aluminum oxide particles. In
addition, the particles produced by laser pyrolysis are a
convenient material for further processing to expand the pathways
for the production of desirable aluminum oxide particles. Thus,
using laser pyrolysis alone or in combination with additional
processes, a wide variety of aluminum oxide particles can be
produced.
[0025] The reaction conditions determiine 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. 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 aluminum oxide particles in a particular apparatus are
described below in the Examples. Furthermore, some general
observations on the relationship between reaction conditions and
the resulting particles can be made.
[0026] Increasing the laser power results in increased reaction
temperatures in the reaction region as well as a faster quenching
rate. A rapid quenching rate tends to favor production of high
energy phases, which may not be obtained with processes near
thermal equilibriun. Similarly, increasing the chamber pressure
also tends to favor the production of higher energy structures.
Also, increasing the concentration of the reactant serving as the
oxygen source in the reactant stream favors the production of
particles with increased amounts of oxygen.
[0027] Reactant gas flow rate and velocity of the reactant gas
stream are inversely related to particle size so that increasing
the reactant gas flow rate or velocity tends to result in smaller
particle size. Also, the growth dynamics of the particles have a
significant influence on the size of the resulting particles. In
other words, different forms of a product compound have a tendency
to form different size particles from other phases under relatively
similar conditions. Laser power also influences particle size with
increased laser power favoring larger particle formation for lower
melting materials and smaller particle formation for higher melting
materials.
[0028] Appropriate aluminum precursor compounds generally include
aluminum compounds with reasonable vapor pressures, i.e., vapor
pressures sufficient to get desired amounts of precursor vapor in
the reactant stream. The vessel holding the precursor compounds can
be heated to increase the vapor pressure of the aluminum precursor,
if desired. Suitable liquid, aluminum precursors include, for
example, aluminum s-butoxide (Al(OC.sub.4H.sub.9).sub.3).
[0029] A number of suitable solid, aluminum precursor compounds are
available including, for example, aluminum chloride (AlCl.sub.3),
aluminum ethoxide (Al(OC.sub.2H.sub.5).sub.3), and aluminum
isopropoxide (Al[OCH(CH.sub.3).sub.2].sub.3). Solid precursors
generally are heated to produce a sufficient vapor pressure. A
suitable container for heating and delivering of a solid precursor
to a laser pyrolysis apparatus is shown in FIG. 1.
[0030] Referring to FIG. 1, the solid precursor delivery system 50
includes a container 52 and a lid 54. A gasket 56 is located
between container 52 and lid 54. In one preferred embodiment,
container 52 and lid 54 are made from stainless steel and gasket 56
is made from copper. In this embodiment, lid 54 and gasket 56 are
bolted to container 52. Other inert materials, such as Pyrex.RTM.,
suitable for the temperatures and pressures applied to the solid
precursor system can be used. Container 52 is surrounded with a
band heater 58, which is used to set the temperature of the
delivery system 50 at desired values. Suitable band heaters are
available from Omega Engineering Inc. Stamford, Conn. The
temperature of the band heater can be adjusted to yield a desired
vapor pressure of the precursor compound. Additional portions of
the precursor delivery system can be heated to maintain the
precursor in a vapor state after it has left container 52.
[0031] Preferably, a thermocouple 60 is inserted into container 52
through lid 54. Thermocouple 60 can be inserted by way of a
Swagelok.RTM. fitting 62 or other suitable connection. Tubing 64
provides a flow input for a carrier gas into container 52. Tubing
64 preferably includes a shut off valve 66 and can be inserted
through lid 54 by way of a Swagelok.RTM. fitting 68 or other
suitable connection. Output tube 70 also preferably includes a shut
off valve 72. Output tube 70 preferably enters into container 52
through lid 54 at a sealed connection 74. Tubes 64 and 70 can be
made of any suitable inert material such as stainless steel. A
solid precursor can be placed directly within container 52 or it
can be placed within a smaller, open container within container
52.
[0032] Preferred reactants serving as oxygen source include, for
example, O.sub.2, CO, CO.sub.2, O.sub.3 and mixtures thereof. The
reactant compound from the oxygen source should not react
significantly with the aluminum precursor prior to entering the
reaction zone since this generally would result in the formation of
large particles.
[0033] Laser pyrolysis can be performed with a variety of optical
laser frequencies. Preferred lasers operate in the infrared portion
of the electromagnetic spectrum. CO.sub.2 lasers are particularly
preferred sources of laser light. Infrared absorbers for inclusion
in the molecular stream include, for example, C.sub.2H.sub.4,
NH.sub.3, SF.sub.6, SiH.sub.4 and O.sub.3. O.sub.3 can act as both
an infrared absorber and as an oxygen source. The radiation
absorber, such as the infrared absorber, absorbs energy from the
radiation beam and distributes the energy to the other reactants to
drive the pyrolysis.
[0034] Preferably, the energy absorbed from the radiation beam
increases the temperature at a tremendous rate, many times the rate
that energy generally would be produced even by strongly exothermic
reactions under controlled condition. While the process generally
involves nonequilibrium conditions, the temperature can be
described approximately based on the energy in the absorbing
region. The laser pyrolysis process is qualitatively different from
the process in a combustion reactor where an energy source
initiates a reaction, but the reaction is driven by energy given
off by an exothermic reaction.
[0035] An inert shielding gas can be used to reduce the amount of
reactant and product molecules contacting the reactant chamber
components. Appropriate shielding gases include, for example, Ar,
He and N.sub.2.
[0036] An appropriate laser pyrolysis apparatus generally includes
a reaction chamber isolated from the ambient environment. A
reactant inlet connected to a reactant supply system produces a
molecular stream through the reaction chamber. A laser beam path
intersects the molecular stream at a reaction zone. The molecular
stream continues after the reaction zone to an outlet, where the
molecular stream exits the reaction chamber and passes into a
collection system. Generally, the laser is located external to the
reaction chamber, and the laser beam enters the reaction chamber
through an appropriate window.
[0037] Referring to FIG. 2, a particular embodiment 100 of a
pyrolysis apparatus involves a reactant supply system 102, reaction
chamber 104, collection system 106 and laser 108. Reactant supply
system 102 includes a source 120 of precursor compound. For liquid
or solid precursors, a carrier gas from carrier gas source 122 can
be introduced into precursor source 120, containing the precursor
to facilitate delivery of the precursor. Precursor source 120 can
be a solid precursor delivery system 50, as shown in FIG. 1. The
carrier gas from source 122 preferably is either an infrared
absorber or an inert gas and is preferably bubbled through a
liquid, precursor compound or delivered into a solid precursor
delivery system. The quantity of precursor vapor in the reaction
zone is roughly proportional to the flow rate of the carrier
gas.
[0038] Alternatively, carrier gas can be supplied directly from
infrared absorber source 124 or inert gas source 126, as
appropriate. The reactant providing the oxygen is supplied from
reactant source 128, which can be a gas cylinder or other suitable
container. The gases from the precursor source 120 are mixed with
gases from reactant source 128, infrared absorber source 124 and
inert gas source 126 by combining the gases in a single portion of
tubing 130. The gases are combined a sufficient distance from
reaction chamber 104 such that the gases become well mixed prior to
their entrance into reaction chamber 104. The combined gas in tube
130 passes through a duct 132 into rectangular channel 134, which
forms part of an injection nozzle for directing reactants into the
reaction chamber. Portions of reactant supply system 102 can be
heated to inhibit the deposition of precursor compound on the walls
of the delivery system. In particular, the entire chamber
preferably is heated to about 140.degree. C. when aluminum chloride
precursor is used. Similarly, the argon shielding gas preferably is
heated to about 150.degree. C. when aluminum chloride precursor is
used.
[0039] Flow from sources 122, 124, 126 and 128 are preferably
independently controlled by mass flow controllers 136. Mass flow
controllers 136 preferably provide a controlled flow rate from each
respective source. Suitable mass flow controllers include, for
example, Edwards Mass Flow Controller, Model 825 series, from
Edwards High Vacuum International, Wilmington, Mass.
[0040] Inert gas source 138 is connected to an inert gas duct 140,
which flows into annular channel 142. A mass flow controller 144
regulates the flow of inert gas into inert gas duct 140. Inert gas
source 126 can also function as the inert gas source for duct 140,
if desired.
[0041] The reaction chamber 104 includes a main chamber 200.
Reactant supply system 102 connects to the main chamber 200 at
injection nozzle 202. The end of injection nozzle 202 has an
annular opening 204 for the passage of inert shielding gas, and a
rectangular slit 206 for the passage of reactant gases to form a
molecular stream in the reaction chamber. Annular opening 204 has,
for example, a diameter of about 1.5 inches and a width along the
radial direction from about 1/8 in to about {fraction (1/16)} in.
The flow of shielding gas through annular opening 204 helps to
prevent the spread of the reactant gases and product particles
throughout reaction chamber 104. Injection nozzle 202 can be heated
to keep the precursor compound in the vapor state.
[0042] Tubular sections 208, 210 are located on either side of
injection nozzle 202. Tubular sections 208, 210 include ZnSe
windows 212, 214, respectively. Windows 212, 214 are about 1 inch
in diameter. Windows 212, 214 are preferably cylindrical lenses
with a focal length equal to the distance between the center of the
chamber to the surface of the lens to focus the beam to a point
just below the center of the nozzle opening. Windows 212, 214
preferably have an antireflective coating. Appropriate ZnSe lenses
are available from Janos Technology, Townshend, Vt. Tubular
sections 208, 210 provide for the displacement of windows 212, 214
away from main chamber 200 such that windows 212, 214 are less
likely to be contaminated by reactants or products. Window 212, 214
are displaced, for example, about 3 cm from the edge of the main
chamber 200.
[0043] Windows 212, 214 are sealed with a rubber o-ring to tubular
sections 208, 210 to prevent the flow of ambient air into reaction
chamber 104. Tubular inlets 216, 218 provide for the flow of
shielding gas into tubular sections 208, 210 to reduce the
contamination of windows 212, 214. Tubular inlets 216, 218 are
connected to inert gas source 138 or to a separate inert gas
source. In either case, flow to inlets 216, 218 preferably is
controlled by a mass flow controller 220.
[0044] Laser 108 is aligned to generate a laser beam 222 that
enters window 212 and exits window 214. Windows 212, 214 define a
laser light path through main chamber 200 intersecting the flow of
reactants at reaction zone 224. After exiting window 214, laser
beam 222 strikes power meter 226, which also acts as a beam dump.
An appropriate power meter is available from Coherent Inc., Santa
Clara, Calif. Laser 108 can be replaced with an intense
conventional light source such as an arc lamp. Preferably, laser
108 is an infrared laser, especially a CW CO.sub.2 laser such as an
1800 watt maximum power output laser available from PRC Corp.,
Landing, N.J.
[0045] Reactants passing through slit 206 in injection nozzle 202
initiate a molecular stream. The molecular stream passes through
reaction zone 224, where reaction involving the aluminum precursor
compound takes place. Heating of the gases in reaction zone 224 is
extremely rapid, roughly on the order of 10.sup.5 degree C./sec
depending on the specific conditions. The reaction is rapidly
quenched upon leaving reaction zone 224, and particles 228 are
formed in the molecular stream. The nonequilibrium nature of the
process allows for the production of nanoparticles with a highly
uniform size distribution and structural homogeneity.
[0046] The path of the molecular stream continues to collection
nozzle 230. Collection nozzle 230 is spaced about 2 cm from
injection nozzle 202. The small spacing between injection nozzle
202 and collection nozzle 230 helps reduce the contamination of
reaction chamber 104 with reactants and products. Collection nozzle
230 has a circular opening 232. Circular opening 232 feeds into
collection system 106.
[0047] The chamber pressure is monitored with a pressure gauge
attached to the main chamber. The preferred chamber pressure for
the production of the desired oxides generally ranges from about 80
Torr to about 500 Torr.
[0048] Reaction chamber 104 has two additional tubular sections not
shown. One of the additional tubular sections projects into the
plane of the sectional view in FIG. 2, and the second additional
tubular section projects out of the plane of the sectional view in
FIG. 2. When viewed from above, the four tubular sections are
distributed roughly, symmetrically around the center of the
chamber. These additional tubular sections have windows for
observing the inside of the chamber. In this configuration of the
apparatus, the two additional tubular sections are not used to
facilitate production of particles.
[0049] Collection system 106 can include a curved channel 250
leading from collection nozzle 230. Because of the small size of
the particles, the product particles follow the flow of the gas
around curves. Collection system 106 includes a filter 252 within
the gas flow to collect the product particles. A variety of
materials such as Teflon, glass fibers and the like can be used for
the filter as long as the material is inert and has a fine enough
mesh to trap the particles. Preferred materials for the filter
include, for example, a glass fiber filter from ACE Glass Inc.,
Vineland, N.J. and cylindrical polypropylene filters from
Cole-Parmer Instrument Co., Vernon Hills, Ill.
[0050] Pump 254 is used to maintain collection system 106 at a
selected pressure. A variety of different pumps can be used.
Appropriate pumps for use as pump 254 include, for example, Busch
Model B0024 pump from Busch, Inc., Virginia Beach, Va. with a
pumping capacity of about 25 cubic feet per minute (cfm) and
Leybold Model SV300 pump from Leybold Vacuum Products, Export, Pa.
with a pumping capacity of about 195 cfm. It may be desirable to
flow the exhaust of the pump through a scrubber 256 to remove any
remaining reactive chemicals before venting into the atmosphere.
The entire apparatus 100 can be placed in a fume hood for
ventilation purposes and for safety considerations. Generally, the
laser remains outside of the fume hood because of its large
size.
[0051] The apparatus is controlled by a computer. Generally, the
computer controls the laser and monitors the pressure in the
reaction chamber. The computer can be used to control the flow of
reactants and/or the shielding gas. The pumping rate is controlled
by either a manual needle valve or an automatic throttle valve
inserted between pump 254 and filter 252. As the chamber pressure
increases due to the accumulation of particles on filter 252, the
manual valve or the throttle valve can be adjusted to maintain the
pumping rate and the corresponding chamber pressure.
[0052] The reaction can be continued until sufficient particles are
collected on filter 252 such that the pump can no longer maintain
the desired pressure in the reaction chamber 104 against the
resistance through filter 252. When the pressure in reaction
chamber 104 can no longer be maintained at the desired value, the
reaction is stopped, and the filter 252 is removed. With this
embodiment, about 1-90 grams of particles can be collected in a
single run before the chamber pressure can no longer be maintained.
A single run generally can last up to about 6 hours depending on
the type of particle being produced and the type of filter being
used. Therefore, it is straightforward to produce a macroscopic
quantity of particles, i.e., a quantity visible with the naked
eye.
[0053] The reaction conditions can be controlled relatively
precisely. The mass flow controllers are quite accurate. The laser
generally has about 0.5 percent power stability. With either a
manual control or a throttle valve, the chamber pressure can be
controlled to within about 1 percent.
[0054] The configuration of the reactant supply system 102 and the
collection system 106 can be reversed. In this alternative
configuration, the reactants are supplied from the bottom of the
reaction chamber, and the product particles are collected from the
top of the chamber. This alternative configuration can result in a
slightly higher collection of product since aluminum oxide
particles tend to be buoyant in the surrounding gases. In this
configuration, it is preferable to include a curved section in the
collection system so that the collection filter is not mounted
directly above the reaction chamber.
[0055] An alternative design of a laser pyrolysis apparatus has
been described. See, copending and commonly assigned U.S. patent
application Ser. No. 08/808,850, now U.S. Pat. No. 5,958,348,
entitled "Efficient Production of Particles by Chemical Reaction,"
incorporated herein by reference. This alternative design is
intended to facilitate production of commercial quantities of
particles by laser pyrolysis. A variety of configurations are
described for injecting the reactant materials into the reaction
chamber.
[0056] The alternative apparatus includes a reaction chamber
designed to minimize contamination of the walls of the chamber with
particles, to increase the production capacity and to make
efficient use of resources. To accomplish these objectives, the
reaction chamber conforms generally to the shape of an elongated
reactant inlet, decreasing the dead volume outside of the molecular
stream. Gases can accumulate in the dead volume, increasing the
amount of wasted radiation through scattering or absorption by
nonreacting molecules. Also, due to reduced gas flow in the dead
volume, particles can accumulate in the dead volume causing chamber
contamination.
[0057] The design of the improved reaction chamber 300 is
schematically shown in FIGS. 3 and 4. A reactant gas channel 302 is
located within block 304. Facets 306 of block 304 form a portion of
conduits 308. Another portion of conduits 308 join at edge 310 with
an inner surface of main chamber 312. Conduits 308 terminate at
shielding gas inlets 314. Block 304 can be repositioned or
replaced, depending on the reaction and desired conditions, to vary
the relationship between the elongated reactant inlet 316 and
shielding gas inlets 314. The shielding gases from shielding gas
inlets 314 form blankets around the molecular stream originating
from reactant inlet 316.
[0058] The dimensions of elongated reactant inlet 316 preferably
are designed for high efficiency particle production. Reasonable
dimensions for the reactant inlet for the production of the
aluminum oxide particles, when used with a 1800 watt CO.sub.2
laser, are from about 5 mm to about 1 meter.
[0059] Main chamber 312 conforms generally to the shape of
elongated reactant inlet 316. Main chamber 312 includes an outlet
318 along the molecular stream for removal of particulate products,
any unreacted gases and inert gases. Tubular sections 320, 322
extend from the main chamber 312. Tubular sections 320, 322 hold
windows 324, 326 to define a laser beam path 328 through the
reaction chamber 300. Tubular sections 320, 322 can include
shielding gas inlets 330, 332 for the introduction of shielding gas
into tubular sections 320, 322.
[0060] The improved apparatus includes a collection system to
remove the particles from the molecular stream. The collection
system can be designed to collect a large quantity of particles
without terminating production or, preferably, to run in continuous
production by switching between different particle collectors
within the collection system. The collection system can include
curved components within the flow path similar to curved portion of
the collection system shown in FIG. 1. The configuration of the
reactant injection components and the collection system can be
reversed such that the particles are collected at the top of the
apparatus.
[0061] As noted above, properties of the product particles can be
modified by further processing. In particular, aluminum oxide
nanoscale particles can be heated in an oven in an oxidizing
environment or an inert environment to alter the oxygen content, to
change the crystal lattice, or to remove adsorbed compounds on the
particles to improve the quality of the particles.
[0062] The use of sufficiently mild conditions, i.e., temperatures
well below the melting point of the particles, results in
modification of the aluminum oxide particles without significantly
sintering the particles into larger particles. The processing of
metal oxide nanoscale particles in an oven is discussed in
copending and commonly assigned, U.S. patent application Ser. No.
08/897,903, filed Jul. 21, 1997, now U.S. Pat. No. 5,989,514,
entitled "Processing of Vanadium Oxide Particles With Heat,"
incorporated herein by reference.
[0063] A variety of apparatuses can be used to perform the heat
processing. An example of an apparatus 400 to perform this
processing is displayed in FIG. 5. Apparatus 400 includes a tube
402 into which the particles are placed. Tube 402 is connected to a
reactant gas source 404 and inert gas source 406. Reactant gas,
inert gas or a combination thereof are placed within tube 402 to
produce the desired atmosphere.
[0064] Preferably, the desired gases are flowed through tube 402.
Appropriate reactant gases to produce an oxidizing environment
include, for example, O.sub.2, O.sub.3, CO, CO.sub.2 and
combinations thereof. The reactant gas can be diluted with inert
gases such as Ar, He and N.sub.2. The gases in tube 402 can be
exclusively inert gases if an inert atmosphere is desired. The
reactant gases may not result in changes to the stoichiometry of
the particles being heated.
[0065] Tube 402 is located within oven or furnace 408. Oven 408
maintains the relevant portions of the tube at a relatively
constant temperature, although the temperature can be varied
systematically through the processing step, if desired. Temperature
in oven 408 generally is measured with a thermocouple 410. The
aluminum oxide particles can be placed in tube 402 within a vial
412. Vial 412 prevents loss of the particles due to gas flow. Vial
412 generally is oriented with the open end directed toward the
direction of the source of the gas flow.
[0066] The precise conditions including type of oxidizing gas (if
any), concentration of oxidizing gas, pressure or flow rate of gas,
temperature and processing time can be selected to produce the
desired type of product material. The temperatures generally are
mild, i.e., significantly below the melting point of the material.
The use of mild conditions avoids interparticle sintering resulting
in larger particle sizes. Some controlled sintering of the
particles can be performed in oven 408 at somewhat higher
temperatures to produce slightly larger, average particle
diameters.
[0067] For the processing of aluminum oxide, for example, the
temperatures preferably range from about 50.degree. C. to about
1200.degree. C. and more preferably from about 50.degree. C. to
about 800.degree. C. The particles preferably are heated for about
1 hour to about 100 hours. Some empirical adjustment may be
required to produce the conditions appropriate for yielding a
desired material.
[0068] B. Particle Properties
[0069] A collection of particles of interest generally has an
average diameter for the primary particles of less than about 500
nm, preferably from about 5 nm to about 100 nm, more preferably
from about 5 nm to about 25 nm. The primary particles usually have
a roughly spherical gross appearance. Upon closer examination, the
aluminum oxide particles generally have facets corresponding to the
underlying crystal lattice. Nevertheless, the primary particles
tend to exhibit growth that is roughly equal in the three physical
dimensions to give a gross spherical appearance. Generally, 95
percent of the primary particles, and preferably 99 percent, have
ratios of the dimension along the major axis to the dimension along
the minor axis less than about 2. Diameter measurements on
particles with asymmetries are based on an average of length
measurements along the principle axes of the particle.
[0070] Because of their small size, the primary particles tend to
form loose agglomerates due to van der Waals and other
electromagnetic forces between nearby particles. Nevertheless, the
nanometer scale of the primary 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. For example,
TiO.sub.2 nanoparticles generally exhibit altered absorption
properties based on their small size, as described in copending and
commonly assigned U.S. patent application Ser. No. 08/962,515, now
U.S. Pat. No. 6,099,798, entitled "Ultraviolet Light Block and
Photocatalytic Materials," incorporated herein by reference.
[0071] The primary particles preferably have a high degree of
uniformity in size. 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
preferably 99 percent, of the primary particles have a diameter
greater than about 40 percent of the average diameter and less than
about 160 percent of the average diameter. Preferably, the primary
particles have a distribution of diameters such that at least about
95 percent of the primary particles have a diameter greater than
about 60 percent of the average diameter and less than about 140
percent of the average diameter.
[0072] Furthermore, essentially no primary particles have an
average diameter greater than about 4 times the average diameter
and preferably 3 times the average diameter, and more preferably 2
times the average diameter. In other words, the 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 and corresponding rapid quench
of the particles. An effective cut off in the tail indicates that
there are less than about 1 particle in 10.sup.6 have a diameter
greater than a particular cut off value above the average diameter.
The narrow size distributions, lack of a tail in the distributions
and the roughly spherical morphology can be exploited in a variety
of applications, especially for abrasive applications.
[0073] In addition, the nanoparticles generally have a very high
purity level. The crystalline aluminum oxide nanoparticles produced
by the above described methods are expected to have a purity
greater than the reactant gases because the crystal formation
process tends to exclude contaminants from the lattice.
Furthermore, crystalline aluminum oxide particles produced by laser
pyrolysis have a high degree of crystallinity.
[0074] Aluminum oxide is known to exist in several crystalline
phases including .alpha.-Al.sub.2O.sub.3, .delta.-Al.sub.2O.sub.3,
.gamma.-Al.sub.2O.sub.3, .epsilon.-Al.sub.2O.sub.3,
.delta.-Al.sub.2O.sub.3, and .eta.-Al.sub.2O.sub.3. The delta phase
has a tetragonal crystal structure, and the gamma phase has a cubic
crystal structure. Although under certain conditions mixed phase
materials are formed, laser pyrolysis generally can be used
effectively to produce single phase crystalline particles. The
conditions of the laser pyrolysis can be varied to favor the
formation of a single, selected phase of crystalline
Al.sub.2O.sub.3.
[0075] Amorphous aluminum oxide can also be formed. Conditions
favoring the formation of amorphous particles include, for example,
high pressures, high flow rates, high laser power and combinations
thereof.
[0076] C. Polishing Compositions
[0077] A variety of polishing compositions can advantageously
incorporate nanoscale aluminum oxide particles, including
compositions for performing chemical-mechanical polishing. The
aluminum oxide particles can function as abrasive particles. In its
simplest form, the polishing composition can just involve the
abrasive, aluminum oxide particles, produced as described above.
More preferably, the abrasive particles are dispersed in an aqueous
or nonaqueous solution. The solution generally includes a solvent
such as water, alcohol, acetone or the like. A surfactant can be
added to add with dispersion, if desired. The abrasive particles
should not be significantly soluble in the solvent. The polishing
composition generally includes from about 0.05 percent to about 30
percent, and preferably from about 1.0 percent to about 10 percent
by weight aluminum oxide particles. The selected composition of the
slurry generally depends on the substrate being processed and the
eventual use for that substrate. In particular, aluminum oxide
particles are useful in slurries to polish metal materials
including, for example, copper and tungsten wires and films.
[0078] Preferred polishing compositions have both a chemical and
mechanical effect on a substrate. Thus, they are useful in
chemical-mechanical polishing (CMP). In particular, for the
polishing of semiconducting materials, oxides of semiconductor
materials, or ceramic substrates for the production of integrated
circuits, colloidal silica can have both a chemical and/or a
mechanical effect on relevant substrates. Thus, some preferred
embodiments include in a solution both an abrasive, such as
aluminum oxide nanoparticles, and colloidal silica.
[0079] The formation of colloidal silica involves formation of an
aqueous solution of hydrated silicon oxides. The colloidal silica
solution preferably includes from about 0.05 percent to about 50
percent, and preferably from about 1.0 percent to about 20 percent
by weight silica. The use of colloidal silica for polishing hard
substrates is described in U.S. Pat. No. 5,228,886,
"Mechanochemical Polishing Abrasive," incorporated herein by
reference, and in U.S. Pat. No. 4,011,099, entitled "Preparation of
Damage-Free Surface on Alpha-Alumina," incorporated herein by
reference. Colloidal silica has been suggested to chemically react
with certain surfaces.
[0080] While conventional silica can be used to form the colloidal
silica, silica particles produced by laser pyrolysis with or
without additional heating are ideally suited for the production of
colloidal silica. The production of nanoscale silica by laser
pyrolysis is described in commonly assigned and copending U.S.
patent application Ser. No. 09/085,514 now U.S. Pat. No. 6,726,990,
entitled "Silicon Oxide Particles," incorporated herein by
reference.
[0081] The solvents used in the formation of the polishing
compositions preferably have a low level of contaminants. In
particular, water used as a solvent should be deionized and/or
distilled. The polishing composition preferably is free from any
contaminants, i.e., any composition not included for effectuating
the polishing process. In particular, the polishing composition
preferably is free of soluble metal contaminants such as potassium
and sodium salts. Preferably, the compositions contain less than
about 0.001 percent and more preferably, less than about 0.0001
percent by weight metal. Furthermore, the polishing composition
preferably is free from particulate contaminants, which are not
soluble in the solvent.
[0082] The polishing compositions can include other components to
assist with the polishing process. For example, the polishing
composition can include additional abrasive particles combined with
the aluminum oxide. Suitable abrasive particles are described, for
example, in copending and commonly assigned U.S. patent application
Ser. No. 08/961,735 now U.S. Pat. No. 6,290,735, entitled "Abrasive
Particles for Surface Polishing," incorporated herein by reference,
and in U.S. Pat. No. 5,228,886, supra. When using additional
(non-aluminum oxide) abrasive particles, the polishing composition
preferably includes from about 0.05 to about 10 percent additional
abrasive particles.
[0083] Suitable additional abrasive particles other than aluminum
oxide particles include, for example, silicon carbide, metal
oxides, metal sulfides and metal carbides with average diameters
less than about 100 nm and more preferably from about 5 nm to about
50 nm. In particular, preferred additional abrasive particles
include compounds such as SiC, TiO.sub.2, Fe.sub.2O.sub.3,
Fe.sub.3O.sub.4, Fe.sub.3C, Fe.sub.7C.sub.3, MoS.sub.2, MoO.sub.2,
WC, WO.sub.3, and WS.sub.2. Also, preferred abrasive particles have
a relatively narrow diameter distribution and an effective cut off
of particle diameters at a value that is several times larger than
the average diameter.
[0084] The particular composition of abrasive particles should be
selected such that the particles have an appropriate hardness for
the surface to be polished as well as an appropriate distribution
of diameters to obtain efficiently the desired smoothness. Aluminum
oxide is very hard. Thus, aluminum oxide is particularly suitable
for the polishing of hard substrates. Abrasive particles that are
hard can result in undesired scratches in the surface of soft
substrates.
[0085] The polishing composition can be acidic or basic to improve
the polishing characteristics. For polishing metals an acidic pH
generally is preferred, for example, in the range from about 3.0 to
about 4.0. A variety of acids can be used such as glacial acetic
acid. For polishing oxide surfaces a basic polishing composition
can be used, for example, with a pH from about 9.0 to about 11. To
form a basic polishing composition, KOH or other bases can be
added. Also, an oxidizing agent such as H.sub.2O.sub.2 can be
added, especially for polishing metals.
[0086] The composition of the abrasive particles should also
provide for removal of the polishing compositions after completion
of the polishing. One approach to cleaning polished surfaces
involves dissolving the abrasive particles with a cleaning solution
that does not damage the polished surface. The removal of an
alumina based polishing compositions using a cleaning composition
with phosphoric acid is described in U.S. Pat. No. 5,389,194,
entitled "Methods of Cleaning Semiconductor Substrates After
Polishing," incorporated herein by reference. This patent also
contains a general description of polishing with slurries
containing conventional aluminum oxides.
[0087] The polishing compositions can be used for mechanical or
chemical-mechanical polishing that is performed manually or using a
powered polishing machine. In either case, the polishing
composition is generally applied to a polishing pad or cloth to
perform the polishing. Any of a variety of mechanical polishers can
be used, for example, vibratory polishers and rotary polishers.
[0088] The polishing compositions are particularly useful for the
polishing of substrate surfaces for the production of integrated
circuits. As the density of integrated circuits on a single surface
increases, the tolerances for smoothness of the corresponding
substrates become more stringent. Therefore, it is important that
polishing process is able to remove small surface discontinuities
prior to applying circuit patterns onto the substrate. The small
size and uniformity of the abrasive particles disclosed herein are
particularly suitable in polishing compositions for these
applications. Al.sub.2O.sub.3 particles with or without colloidal
silica are suitable for the polishing of silicon based
semiconductor substrates. Similarly, layered structures involving
patterned portions of insulating layers and conducting layers can
be simultaneously planarized, as described in U.S. Pat. No.
4,956,313, incorporated herein by reference.
EXAMPLES
Example 1
Laser Pyrolysis for Formation of Al.sub.2O.sub.3 Nanoparticles
[0089] The synthesis of aluminum oxide particles described in this
example was performed by laser pyrolysis. The particles were
produced using essentially the laser pyrolysis apparatus of FIG. 2,
described above, using the solid precursor delivery system shown
schematically in FIG. 1.
[0090] The aluminum chloride (Strem Chemical, Inc., Newburyport,
Mass.) precursor vapor was carried into the reaction chamber by
flowing Ar gas through the solid precursor delivery system
containing AlCl.sub.3. The precursor was heated to a temperature as
indicated in Table 1. C.sub.2H.sub.4 gas was used as a laser
absorbing gas, and Argon was used as an inert gas. The reaction gas
mixture containing AlCl.sub.3, Ar, O.sub.2 and C.sub.2 H.sub.4 was
introduced into the reactant gas nozzle for injection into the
reaction chamber. The reactant gas nozzle had an opening with
dimensions of 5/8 in..times.1/8 in. Additional parameters of the
laser pyrolysis synthesis relating to the particles of Example 1
are specified in Table 1.
1 TABLE 1 Sample 1 Crystal Structure .gamma. -Al.sub.2O.sub.3
(cubic) Pressure 120 (Torr) Argon - Win. 700 (sccm) Argon - Sld.
2.8 (slm) Ethylene 725 (sccm) Carrier Gas 705 (Ar) (sccm) Oxygen
552 (sccm) Laser Output 600 (watts) Precursor 260 Temperature
(.degree. C.) sccm = standard cubic centimeters per minute slm =
standard liters per minute Argon - Win. = argon flow through inlets
216, 218 Argon - Sld. = argon flow through annular channel 142.
[0091] The production rate of aluminum oxide particles was
typically about 4 g/hr. To evaluate the atomic arrangement, the
samples were examined by x-ray diffraction using the Cu(K.alpha.)
radiation line on a Siemens D500 x-ray diffractometer. An x-ray
diffractogram for a sample produced under the conditions specified
in Table 1 is shown in FIG. 6. Under the set of conditions
specified in Table 1, the particles had an x-ray diffractogram
corresponding to .gamma.-Al.sub.2O.sub.3 (cubic) although the
diffractogram contained a considerable amount of noise.
[0092] Transmission electron microscopy (TEM) was used to determine
particle sizes and morphology. A TEM micrograph for the particles
produced under the conditions of Table 1 is displayed in FIG. 7. An
examination of a portion of the TEM micrograph yielded an average
particle size of about 7 mn. The corresponding particle size
distribution is shown in FIG. 8. The approximate size distribution
was determined by manually measuring diameters of the particles
distinctly visible in the micrograph of FIG. 7. Only those
particles having clear particle boundaries were measured to avoid
regions distorted or out of focus in the micrograph. Measurements
so obtained should be more accurate and are not biased since a
single view cannot show a clear view of all particles. It is
significant that the particles span a rather narrow range of
sizes.
[0093] The particles produced by laser pyrolysis had a dark color,
evidently due to the presence of carbon associated with the
particles. The carbon can come from the ethylene used as the laser
absorbing gas. The dark color was removed by heating as described
in Example 2. The production of carbon coated nanoparticles is
described further in copending and commonly assigned patent
application Ser. No. 09/123,255, now U.S. Pat. No. 6,387,531,
entitled "Metal (Silicon) Oxide/Carbon Composite Particles," filed
on Jul. 22, 1998, incorporated herein by reference.
Example 2
Oven Processed
[0094] A sample of aluminum oxide nanoparticles produced by laser
pyrolysis according to the conditions specified in Table 1 were
heated in an oven under oxidizing conditions. The oven was
essentially as described above with respect to FIG. 5. The samples
were heated in the oven at about 500.degree. C. for about 2 hours.
Oxygen gas was flowed through a 1.0 in diameter quartz tube at a
flow rate of about 250 sccm. Between about 100 and about 300 mg of
nanoparticles were placed in an open 1 cc vial within the quartz
tube projecting through the oven. After heating, the particles had
a white color. The resulting particles were .gamma.-Al.sub.2O.sub.3
as determined by x-ray diffraction. The x-ray diffractogram is
shown in FIG. 9. The diffractogram in FIG. 9 has a higher
signal-to-noise ratio than the diffraction gram in FIG. 6. This
improvement in signal-to-noise may be due to an increased level of
crystallinity.
[0095] A TEM micrograph for the heat treated Al.sub.2O.sub.3
nanoparticles is shown in FIG. 10. The corresponding particle size
distribution is shown in FIG. 11. The particle size distribution
was produced following the same procedures as used to produce the
distribution in FIG. 8.
Example 3
Slurries of Aluminum Oxide Nanoparticles
[0096] This example includes a description of the preparation of a
slurry with about 1 percent by weight aluminum oxide
nanoparticles.
[0097] A 5 ml quantity of deionized water was placed in a
Waring.RTM. blender. The blender was set on a slow setting, and
0.1000 g of Al.sub.2O.sub.3 nanoparticles made by laser pyrolysis
was added to the blender. Following addition of the dry powder, 2
ml of deionized water was added as a rinse. The pH of the
concentrated slurry was adjusted by the addition of 0.2 ml of
approximately 2 percent by weight HCl. After addition of the HCl,
the blender speed setting was increased to medium-high for 30
seconds and then lowered again to the slow setting. The
concentrated slurry was diluted with enough water to form 10 ml
total liquid content. After the addition of the additional water,
the blender speed was again increased to medium-high for 30
seconds. Then, the mixer was stopped. The pH of the resulting
slurry was about 3. The resulting slurry had a color that was
either milky if heat treated samples were used, or a coffee color
if particles that were not heat treated were used. The slurries
were each placed in a sealed bottle.
[0098] The embodiments described above are intended to be
representative and not limiting. Additional embodiments of the
invention are within the claims. Although the present invention has
been described with reference to preferred embodiments, workers
skilled in the art will recognize that changes may be made in form
and detail without departing from the spirit and scope of the
invention.
* * * * *