U.S. patent application number 12/885371 was filed with the patent office on 2011-06-23 for molecular precursor methods for optoelectronics.
This patent application is currently assigned to PRECURSOR ENERGETICS, INC.. Invention is credited to Wayne A. Chomitz, Kyle L. Fujdala, Matthew C. Kuchta, Zhongliang Zhu.
Application Number | 20110146790 12/885371 |
Document ID | / |
Family ID | 44149267 |
Filed Date | 2011-06-23 |
United States Patent
Application |
20110146790 |
Kind Code |
A1 |
Fujdala; Kyle L. ; et
al. |
June 23, 2011 |
MOLECULAR PRECURSOR METHODS FOR OPTOELECTRONICS
Abstract
This invention relates to compounds and compositions used to
prepare semiconductor and optoelectronic materials and devices.
This invention provides a range of compounds, compositions,
materials and methods directed ultimately toward photovoltaic
applications, as well as devices and systems for energy conversion,
including solar cells. In particular, this invention relates to
molecular precursor compounds, precursor materials and methods for
preparing photovoltaic layers.
Inventors: |
Fujdala; Kyle L.; (San Jose,
CA) ; Chomitz; Wayne A.; (Oakland, CA) ; Zhu;
Zhongliang; (San Jose, CA) ; Kuchta; Matthew C.;
(San Francisco, CA) |
Assignee: |
PRECURSOR ENERGETICS, INC.
Santa Clara
CA
|
Family ID: |
44149267 |
Appl. No.: |
12/885371 |
Filed: |
September 17, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12848961 |
Aug 2, 2010 |
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12885371 |
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61287677 |
Dec 17, 2009 |
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Current U.S.
Class: |
136/258 ;
257/E31.04; 438/95 |
Current CPC
Class: |
C07F 5/00 20130101; C23C
16/305 20130101; C09D 11/03 20130101; C23C 18/1204 20130101; C23C
18/1287 20130101; C23C 18/1241 20130101 |
Class at
Publication: |
136/258 ; 438/95;
257/E31.04 |
International
Class: |
H01L 31/036 20060101
H01L031/036; H01L 31/18 20060101 H01L031/18 |
Claims
1. A method for making a photovoltaic absorber layer on a substrate
comprising, (a) providing one or more molecular precursor compounds
or inks thereof; (b) providing a substrate; (c) depositing the
compounds or inks onto the substrate; and (d) heating the substrate
at a temperature of from about 100.degree. C. to about 650.degree.
C. in an inert atmosphere, thereby producing a photovoltaic
absorber layer.
2. The method of claim 1, wherein at least one molecular precursor
compound has the formula
M.sup.A-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4, wherein
M.sup.A is a monovalent metal atom, M.sup.B is an atom of Group 13,
each E is independently S, Se, or Te, and R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 are the same or different and are
independently selected from alkyl, aryl, heteroaryl, alkenyl,
amido, silyl, and inorganic and organic ligands.
3. The method of claim 2, wherein M.sup.A is Cu or Ag, and M.sup.B
is Ga or In.
4. The method of claim 2, wherein each of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 is independently (C1-12)alkyl.
5. The method of claim 2, wherein each of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 is independently (C1-4)alkyl.
6. The method of claim 2, wherein the molecular precursor compound
is a dimer having the formula
(M.sup.A-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4).sub.2.
7. The method of claim 1, wherein the molecular precursor compound
is a CIS or CIGS precursor.
8. The method of claim 1, wherein the substrate is heated at a
temperature of from about 100.degree. C. to about 550.degree.
C.
9. The method of claim 1, further comprising one or more steps of
heating and one or more steps of annealing in any order.
10. The method of claim 1, wherein the depositing is done by
spraying, spray coating, spray deposition, spray pyrolysis,
printing, screen printing, inkjet printing, aerosol jet printing,
ink printing, jet printing, stamp printing, transfer printing, pad
printing, flexographic printing, gravure printing, contact
printing, reverse printing, thermal printing, lithography,
electrophotographic printing, electrodepositing, electroplating,
electroless plating, bath deposition, coating, dip coating, wet
coating, spin coating, knife coating, roller coating, rod coating,
slot die coating, meyerbar coating, lip direct coating, capillary
coating, liquid deposition, solution deposition, layer-by-layer
deposition, spin casting, solution casting, chemical vapor
deposition, aerosol chemical vapor deposition, metal-organic
chemical vapor deposition, organometallic chemical vapor
deposition, plasma enhanced chemical vapor deposition, and
combinations of any of the forgoing.
11. The method of claim 1, wherein the substrate is selected from
the group of a semiconductor, a doped semiconductor, silicon,
gallium arsenide, insulators, glass, molybdenum glass, silicon
dioxide, titanium dioxide, zinc oxide, silicon nitride, a metal, a
metal foil, molybdenum, aluminum, beryllium, cadmium, cerium,
chromium, cobalt, copper, gallium, gold, lead, manganese,
molybdenum, nickel, palladium, platinum, rhenium, rhodium, silver,
stainless steel, steel, iron, strontium, tin, titanium, tungsten,
zinc, zirconium, a metal alloy, a metal silicide, a metal carbide,
a polymer, a plastic, a conductive polymer, a copolymer, a polymer
blend, a polyethylene terephthalate, a polycarbonate, a polyester,
a polyester film, a mylar, a polyvinyl fluoride, polyvinylidene
fluoride, a polyethylene, a polyetherimide, a polyethersulfone, a
polyetherketone, a polyimide, a polyvinylchloride, an acrylonitrile
butadiene styrene polymer, a silicone, an epoxy, paper, coated
paper, and combinations of any of the forgoing.
12. The method of claim 1, wherein the substrate is a shaped
substrate, a tube, a cylinder, a roller, a rod, a pin, a shaft, a
plane, a plate, a blade, a vane, a curved surface or a
spheroid.
13. The method of claim 1, wherein the substrate is a layer of a
solar cell.
14. The method of claim 1, further comprising an optional step of
selenization or sulfurization, either before, during or after steps
(c) or (d).
15. The method of claim 1, wherein the photovoltaic absorber layer
is a thin film.
16. The method of claim 1, wherein the photovoltaic absorber layer
is a thin film having a thickness of from 0.001 to 100
micrometers.
17. A photovoltaic absorber layer made by the method of claim
1.
18. A photovoltaic device comprising a photovoltaic absorber layer
made by the method of claim 1.
19. A system for providing electrical power comprising a
photovoltaic absorber layer of claim 18.
20. A method for providing electrical power comprising using a
system of claim 19 to convert light into electrical energy.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of prior U.S. application
Ser. No. 12/848,961, filed Aug. 2, 2010, which claims the benefit
of U.S. Provisional Application No. 61/287,677, filed Dec. 17,
2009, each of which is hereby incorporated by reference in its
entirety.
BACKGROUND
[0002] The development of photovoltaic devices such as solar cells
is important for providing a renewable source of energy and many
other uses. The demand for power is ever-rising as the human
population increases. In many geographic areas, solar cells may be
the only way to meet the demand for power. The total energy from
solar light impinging on the earth for one hour is about
4.times.10.sup.20 joules. It has been estimated that one hour of
total solar energy is as much energy as is used worldwide for an
entire year. Thus, billions of square meters of efficient solar
cell devices will be needed.
[0003] Photovoltaic devices are made by a variety of processes in
which layers of semiconducting material are created on a substrate.
Layers of additional materials are used to protect the photovoltaic
semiconductor layers and to conduct electrical energy out of the
device. Thus, the usefulness of an optoelectronic or solar cell
product is in general limited by the nature and quality of the
photovoltaic layers.
[0004] For example, one way to produce a solar cell product
involves depositing a thin, light-absorbing, solid layer of the
material copper indium gallium diselenide, known as "CIGS," on a
substrate. A solar cell having a thin film CIGS layer can provide
low to moderate efficiency for conversion of sunlight to
electricity. The CIGS layer can be made by processing at relatively
high temperatures several elemental sources containing the atoms
needed for CIGS. In general, CIGS materials are complex, having
many possible solid phases.
[0005] The CIGS elemental sources must be formed or deposited,
either individually or as a mixture, in a thin, uniform layer on
the substrate. For example, deposition of the CIGS sources can be
done as a co-deposition, or as a multistep deposition. The
difficulties with these approaches include lack of uniformity of
the CIGS layers, such as the appearance of different solid phases,
imperfections in crystalline particles, voids, cracks, and other
defects in the layers. Another problem in some processes is the
inability to precisely control the stoichiometric ratios of the
metal atoms in the layers.
[0006] For example, some methods for solar cells are disclosed in
U.S. Pat. Nos. 5,441,897, 5,976,614, 6,518,086, 5,436,204,
5,981,868, 7,179,677, 7,259,322, U.S. Patent Publication No.
2009/0280598, and PCT International Application Publication Nos.
WO2008057119 and WO2008063190.
[0007] A further difficulty is the need to heat the substrate to
high temperatures to finish the film. This can cause unwanted
defects due to rapid chemical or physical transformation of the
layers. High temperatures may also limit the nature of the
substrate that can be used. For example, it is desirable to make
thin film photovoltaic layers on a flexible substrate such as a
polymer or plastic that can be formed into a roll for processing
and installation on a building or outdoor structure. Polymer
substrates may not be compatible with the high temperatures needed
to process the semiconductor layers. Preparing thin film
photovoltaic layers on a flexible substrate is an important goal
for providing renewable solar energy and developing new generations
of electro-optical products.
[0008] Moreover, methods for large scale manufacturing of solar
cells can be difficult because of the chemical processes involved.
In general, large scale processes for solar cells are unpredictable
because of the difficulty in controlling numerous chemical and
physical parameters involved in forming an absorber layer of
suitable quality on a substrate, as well as forming the other
layers required to make an efficient solar cell and provide
electrical conductivity.
[0009] What is needed are compounds and compositions to produce
materials for photovoltaic layers, especially thin film layers for
solar cell devices and other products.
BRIEF SUMMARY
[0010] This invention relates to compounds and compositions used to
prepare semiconductor and optoelectronic materials and devices
including thin film and band gap materials. This invention provides
a range of compounds, compositions, materials and methods directed
ultimately toward photovoltaic applications and other semiconductor
materials, as well as devices and systems for energy conversion,
including solar cells. In particular, this invention relates to
novel processes, compounds and materials for preparing
semiconductor materials.
[0011] This invention provides compounds, compositions, materials
and methods for preparing semiconductors and materials, as well as
optoelectronic devices and photovoltaic layers. Among other things,
this disclosure provides precursor molecules and compositions for
making and using semiconductors such as for photovoltaic layers,
solar cells and other uses.
[0012] In various embodiments of this invention, chemically and
physically uniform semiconductor layers can be prepared with the
molecular precursor compounds described herein.
[0013] In further embodiments, solar cells and other products can
be made in processes operating at relatively low temperatures with
the compounds and compositions of this disclosure.
[0014] The molecular precursor compounds and compositions of this
disclosure can provide enhanced processability for solar cell
production, and the ability to be processed on a variety of
substrates including polymers at relatively low temperatures.
[0015] The advantages provided by the compounds, compositions, and
materials of this invention in making photovoltaic layers and other
semiconductors and devices are generally obtained regardless of the
morphology or architecture of the semiconductors or devices.
[0016] In some embodiments, this invention provides compounds
comprising the formula
M.sup.A-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4, wherein
M.sup.A is a monovalent metal atom, M.sup.B is an atom of Group 13,
each E is independently S, Se, or Te, and R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 are the same or different and are
independently selected from alkyl, aryl, heteroaryl, alkenyl,
amido, silyl, and inorganic and organic ligands. M.sup.A may be Cu
or Ag, and M.sup.B may be Ga or In. Each of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 can be independently (C1-12)alkyl, or
(C1-4)alkyl.
[0017] In certain embodiments, a compound may be a dimer having the
formula
(M.sup.A-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4).sub.2.
[0018] In further embodiments, a compound can have the formula
(M.sup.A1-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4)(M.sup.A2-(ER.sup.-
1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4), wherein M.sup.A1 and
M.sup.A2 are different monovalent metal atoms.
[0019] In certain embodiments, M.sup.A is a divalent metal atom,
and the formula is
Z-M.sup.A-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4, wherein Z
is selected from alkyl, aryl, heteroaryl, alkenyl, amido, silyl,
and inorganic and organic ligands.
[0020] In additional embodiments, (ER.sup.1) is (ER.sup.1Z), and
the formula is
M.sup.A(ER.sup.1Z)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4, wherein Z is
attached to M.sup.A and Z is a neutral moiety selected from
--NR.sub.2, --PR.sub.2, --AsR.sub.2, -ER, --SR, --OR, and --SeR,
where R is alkyl or aryl.
[0021] In some aspects, M.sup.A is a divalent metal atom,
(ER.sup.1) is (ER.sup.1Z), and the formula is
M.sup.A(ER.sup.1Z)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4, wherein Z is
attached to M.sup.A and Z is an anionic moiety selected from
--NR.sup.-, -E.sup.-, --O.sup.-, --R.sup.-, -ERNR.sup.-,
-ERE.sup.-, and --SiR.sub.2.sup.-, where R is alkyl or aryl.
[0022] Embodiments of this invention may further provide an ink
comprising one or more compounds above and one or more carriers.
The ink can be a solution of the compounds in an organic carrier,
or a slurry or suspension. An ink may further contain one or more
components selected from the group of a surfactant, a dispersant,
an emulsifier, an anti-foaming agent, a dryer, a filler, a resin
binder, a thickener, a viscosity modifier, an anti-oxidant, a flow
agent, a plasticizer, a conductivity agent, a crystallization
promoter, an extender, a film conditioner, an adhesion promoter,
and a dye.
[0023] In some aspects, this invention provides methods for making
a molecular precursor compound having the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, comprising:
a) providing a first compound R.sup.1.sub.2M.sup.BER.sup.2; and b)
contacting the first compound with a second compound
M.sup.A(ER.sup.3) in the presence of a third compound HER.sup.4;
wherein M.sup.B is a Group 13 atom, M.sup.A is a monovalent metal
atom, each E is independently for each occurrence S, Se, or Te, and
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same or each
different and are independently selected from alkyl, aryl,
heteroaryl, alkenyl, amido, silyl, and inorganic and organic
ligands. The first, second and third compounds can be contacted in
a process of depositing, spraying, coating, or printing. The first,
second and third compounds can be contacted at a temperature of
from about -60.degree. C. to about 100.degree. C.
[0024] In some variations, this disclosure provides an article
comprising one or more compounds or inks above deposited onto a
substrate. The depositing can be done by spraying, spray coating,
spray deposition, spray pyrolysis, printing, screen printing,
inkjet printing, aerosol jet printing, ink printing, jet printing,
stamp/pad printing, transfer printing, pad printing, flexographic
printing, gravure printing, contact printing, reverse printing,
thermal printing, lithography, electrophotographic printing,
electrodepositing, electroplating, electroless plating, bath
deposition, coating, dip coating, wet coating, spin coating, knife
coating, roller coating, rod coating, slot die coating, meyerbar
coating, lip direct coating, capillary coating, liquid deposition,
solution deposition, layer-by-layer deposition, spin casting,
solution casting, and combinations of any of the forgoing.
[0025] A substrate may be selected from a semiconductor, a doped
semiconductor, silicon, gallium arsenide, insulators, glass,
molybdenum glass, silicon dioxide, titanium dioxide, zinc oxide,
silicon nitride, a metal, a metal foil, molybdenum, aluminum,
beryllium, cadmium, cerium, chromium, cobalt, copper, gallium,
gold, lead, manganese, molybdenum, nickel, palladium, platinum,
rhenium, rhodium, silver, stainless steel, steel, iron, strontium,
tin, titanium, tungsten, zinc, zirconium, a metal alloy, a metal
silicide, a metal carbide, a polymer, a plastic, a conductive
polymer, a copolymer, a polymer blend, a polyethylene
terephthalate, a polycarbonate, a polyester, a polyester film, a
mylar, a polyvinyl fluoride, polyvinylidene fluoride, a
polyethylene, a polyetherimide, a polyethersulfone, a
polyetherketone, a polyimide, a polyvinylchloride, an acrylonitrile
butadiene styrene polymer, a silicone, an epoxy, paper, coated
paper, and combinations of any of the forgoing. A substrate may be
a shaped substrate including a tube, a cylinder, a roller, a rod, a
pin, a shaft, a plane, a plate, a blade, a vane, a curved surface
or a spheroid.
[0026] This invention further includes methods for making an
article, the method comprising: (a) providing one or more compounds
or inks; (b) providing a substrate; and (c) depositing the
compounds or inks onto the substrate. Step (c) can be repeated. The
method can include heating the substrate at a temperature of from
about 100.degree. C. to about 400.degree. C. to convert the
compounds or inks to a material. The method can include heating the
substrate at a temperature of from about 100.degree. C. to about
400.degree. C. to convert the compounds or inks to a material,
followed by repeating step (c). The method can include annealing
the material by heating the substrate at a temperature of from
about 300.degree. C. to about 650.degree. C. The method may include
heating the substrate at a temperature of from about 100.degree. C.
to about 400.degree. C. to convert the compounds or inks to a
material, and annealing the material by heating the substrate at a
temperature of from about 300.degree. C. to about 650.degree.
C.
[0027] In certain variations, the method can include heating the
substrate at a temperature of from about 100.degree. C. to about
400.degree. C. to convert the compounds or inks to a material,
depositing the compounds or inks onto the substrate, and annealing
the material by heating the substrate at a temperature of from
about 300.degree. C. to about 650.degree. C. The method may include
(d) heating the substrate at a temperature of from about
100.degree. C. to about 400.degree. C. to convert the compounds or
inks to a material; (e) depositing the compounds or inks onto the
substrate; (f) repeating steps (d) and (e); and (g) annealing the
material by heating the substrate at a temperature of from about
300.degree. C. to about 650.degree. C. In certain embodiments, the
method includes (d) heating the substrate at a temperature of from
about 100.degree. C. to about 400.degree. C. to convert the
compounds or inks to a material; (e) annealing the material by
heating the substrate at a temperature of from about 300.degree. C.
to about 650.degree. C.; and (f) repeating steps (c), (d) and (e).
In further embodiments, the method can include an optional step of
selenization or sulfurization, either before, during or after any
step of heating or annealing.
[0028] Embodiments of this disclosure include methods for making a
material comprising, (a) providing one or more compounds or inks
above; (b) providing a substrate; (c) depositing the compounds or
inks onto the substrate; and (d) heating the substrate at a
temperature of from about 20.degree. C. to about 650.degree. C. in
an inert atmosphere, thereby producing a material.
[0029] This invention includes a thin film material made by a
process comprising,
[0030] (a) providing one or more compounds or inks above;
[0031] (b) providing a substrate;
[0032] (c) depositing the compounds or inks onto the substrate;
and
[0033] (d) heating the substrate at a temperature of from about
20.degree. C. to about 650.degree. C. in an inert atmosphere,
thereby producing a thin film material having a thickness of from
0.05 to 10 micrometers.
[0034] In some aspects, this invention includes methods for making
a photovoltaic absorber layer on a substrate comprising,
[0035] (a) providing one or more compounds or inks above;
[0036] (b) providing a substrate;
[0037] (c) depositing the compounds or inks onto the substrate;
and
[0038] (d) heating the substrate at a temperature of from about
100.degree. C. to about 650.degree. C. in an inert atmosphere,
thereby producing a photovoltaic absorber layer having a thickness
of from 0.001 to 100 micrometers.
[0039] Embodiments of this invention further include a photovoltaic
device comprising precursor or material above, and a photovoltaic
system for providing electrical power comprising a photovoltaic
device, as well as methods for providing electrical power
comprising using a photovoltaic system to convert light into
electrical energy.
[0040] This brief summary, taken along with the detailed
description of the invention, as well as the figures, the appended
examples and claims, as a whole, encompass the disclosure of the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0041] FIG. 1 shows an embodiment of a family of molecular
precursor compounds MP1. As shown in FIG. 1, the structure of these
molecular precursor compounds can be represented by the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, where E is a
chalcogen, M.sup.A is a monovalent metal atom and M.sup.B is an
atom of Group 13. The molecular structure of the family of
compounds is of a dimer, represented by the formula
(M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1).sub.2.
M.sup.A is stabilized by interactions with one or more chalcogen
atoms of the ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4).
M.sup.B is stabilized by having four ligands attached.
[0042] FIG. 2 shows an embodiment of a family of molecular
precursor compounds MP2. As shown in FIG. 2, the structure of these
molecular precursor compounds is represented by the formula
(R.sup.1M.sup.B1(ER.sup.2)(ER.sup.3)(ER.sup.4)-M.sup.A1)(M.sup.A2-(ER.sup-
.5)(ER.sup.6)(ER.sup.7)M.sup.B2R.sup.8), where E is a chalcogen,
M.sup.A1 and M.sup.A2 are the same or different monovalent metal
atoms, and M.sup.B1 and M.sup.B2 are different atoms of Group 13.
M.sup.A1 and M.sup.A2 are stabilized by interactions with chalcogen
atoms of three of the ligands (ER.sup.n). M.sup.B1 and M.sup.B2 are
stabilized by having four ligands attached.
[0043] FIG. 3 shows an embodiment of a family of molecular
precursor compounds MP3. As shown in FIG. 3, the structure of these
molecular precursor compounds is represented by the formula
(R.sup.4E)M.sup.A(ER.sup.3)(ER.sup.5)(ER.sup.2)M.sup.BR.sup.1,
where E is a chalcogen, M.sup.A is a divalent metal atom, and
M.sup.B is an atom of Group 13. M.sup.A is stabilized by having
chalcogen-containing ligands attached. M.sup.B is stabilized by
having four ligands attached.
[0044] FIG. 4 shows an embodiment of a family of molecular
precursor compounds MP3. As shown in FIG. 4, the structure of these
molecular precursor compounds is represented by the formula
R.sup.5M.sup.A(ER.sup.4)(ER.sup.3)(ER.sup.2)M.sup.BR.sup.1, where E
is a chalcogen, M.sup.A is a divalent metal atom, and M.sup.B is an
atom of Group 13. M.sup.A is stabilized by having ligands attached.
M.sup.B is stabilized by having ligands attached.
[0045] FIG. 5 shows an embodiment of a family of molecular
precursor compounds MP4. As shown in FIG. 5, the structure of these
molecular precursor compounds is represented by the formula
M.sup.A(ER.sup.2Z)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, where E is a
chalcogen, M.sup.A is a metal atom, and M.sup.B is an atom of Group
13. M.sup.A is stabilized by having ligands attached, including Z
which is a neutral or anionic moiety attached to M.sup.A. M.sup.B
is stabilized by having four ligands attached.
[0046] FIG. 6 Schematic representation of embodiments of this
invention in which molecular precursors and ink compositions are
deposited onto particular substrates by methods including spraying,
coating, and printing, and are used to make semiconductor and
optoelectronic materials and devices, as well as energy conversion
systems.
[0047] FIG. 7 Schematic representation of a solar cell embodiment
of this invention.
[0048] FIG. 8 shows the structure of an embodiment of a molecular
precursor compound (MP1) as determined by single crystal X-ray
diffraction. As shown in FIG. 8, the molecular structure of this
compound is represented by the formula
(Cu--(S.sup.tBu).sub.3In.sup.nBu).sub.2.
[0049] FIG. 9 shows the transition of a molecular precursor
embodiment (MP1) of this invention into a material as determined by
thermogravimetric analysis. As shown in FIG. 9, the molecular
structure of the precursor compound is represented by the formula
(Cu--(S.sup.tBu).sub.3In.sup.tBu).sub.2. The transition of the
precursor compound into the material CuInS.sub.2 takes place
sharply and is completed at a temperature of about 240.degree.
C.
[0050] FIG. 10 shows the transition of a molecular precursor
embodiment (MP1) of this invention into a material as determined by
thermogravimetric analysis. As shown in FIG. 10, the molecular
structure of the precursor compound is represented by the formula
(Cu--(Se.sup.tBu).sub.3Ga.sup.tBu).sub.2. The transition of the
precursor compound into the material CuGaSe.sub.2 takes place
sharply and is completed at a temperature of about 210.degree.
C.
[0051] FIG. 11 shows the transition of a molecular precursor
embodiment (MP1) of this invention into a material as determined by
thermogravimetric analysis. As shown in FIG. 11, the molecular
structure of the precursor compound is represented by the formula
(Cu--(S.sup.tBu).sub.3Ga.sup.tBu).sub.2. The transition of the
precursor compound into the material CuGaS.sub.2 takes place
sharply and is completed at a temperature of about 225.degree.
C.
[0052] FIG. 12 shows the transition of a molecular precursor
embodiment (MP1) of this invention into a material as determined by
thermogravimetric analysis. As shown in FIG. 12, the molecular
structure of the precursor compound is represented by the formula
(Cu--(Se.sup.tBu).sub.3In.sup.tBu).sub.2. The transition of the
precursor compound into the material CuInSe.sub.2 takes place
sharply and is completed at a temperature of about 192.degree.
C.
[0053] FIG. 13 shows the transition of a mixture of molecular
precursor embodiments (MP1) of this invention into a material as
determined by thermogravimetric analysis. As shown in FIG. 13, the
molecular structures of the precursor compounds are represented by
the formulas (Cu--(Se.sup.tBu).sub.3In.sup.tBu).sub.2 and
(Cu--(Se.sup.tBu).sub.3Ga.sup.tBu).sub.2. The transition of the
precursor compounds into the material
CuIn.sub.0.75Ga.sub.0.25Se.sub.2 takes place sharply and is
completed at a temperature of about 195.degree. C.
[0054] FIG. 14 shows the transition of a molecular precursor
embodiment (MP1-Ag) of this invention into a material as determined
by thermogravimetric analysis. As shown in FIG. 14, the molecular
structure of the precursor compound is represented by the formula
(Ag--(Se.sup.tBu).sub.3In.sup.nBu).sub.2. The transition of the
precursor compound into the material AgInSe.sub.2 is completed at a
temperature of about 205.degree. C.
[0055] FIG. 15 shows the transition of a molecular precursor
embodiment (MP1-Ag) of this invention into a material as determined
by thermogravimetric analysis. As shown in FIG. 15, the molecular
structure of the precursor compound is represented by the formula
(Ag--(Se.sup.tBu).sub.3Ga.sup.nBu).sub.2. The transition of the
precursor compound into the material AgGaSe.sub.2 is completed at a
temperature of about 210.degree. C.
[0056] FIG. 16 shows the transition of a molecular precursor
embodiment (MP1-Ag) of this invention into a material as determined
by thermogravimetric analysis. As shown in FIG. 16, the molecular
structure of the precursor compound is represented by the formula
(Ag--(Se.sup.tBu).sub.3In.sup.sBu).sub.2. The transition of the
precursor compound into the material AgInSe.sub.2 is completed at a
temperature of about 195.degree. C.
[0057] FIG. 17 shows the transition of a molecular precursor
embodiment (MP1-Ag) of this invention into a material as determined
by thermogravimetric analysis. As shown in FIG. 17, the molecular
structure of the precursor compound is represented by the formula
(Ag--(Se.sup.tBu).sub.3Ga.sup.sBu).sub.2. The transition of the
precursor compound into the material AgGaSe.sub.2 is completed at a
temperature of about 195.degree. C.
[0058] FIG. 18 shows the transition of a molecular precursor
embodiment (MP1-Ag) of this invention into a material as determined
by thermogravimetric analysis. As shown in FIG. 18, the molecular
structure of the precursor compound is represented by the formula
(Ag--(Se.sup.tBu).sub.3In.sup.iPr).sub.2. The transition of the
precursor compound into the material AgInSe.sub.2 is completed at a
temperature of about 205.degree. C.
DETAILED DESCRIPTION
[0059] This disclosure provides a range of novel compounds,
compositions, materials and methods for semiconductor and
optoelectronic materials and devices including thin film
photovoltaics and various semiconductor band gap materials.
[0060] This invention provides compounds and compositions for
photovoltaic applications, as well as for devices and systems for
energy conversion, including solar cells.
[0061] The compounds and compositions of this disclosure include
molecular precursor compounds and precursors for materials for
preparing novel semiconductor and photovoltaic materials, films,
and products. Among other advantages, this disclosure provides
stable molecular precursor compounds for making and using layered
materials and photovoltaics, such as for solar cells and other
uses.
[0062] In general, the structure and properties of the compounds,
compositions, and materials of this invention provide advantages in
making photovoltaic layers, semiconductors, and devices regardless
of the morphology, architecture, or manner of fabrication of the
semiconductors or devices.
[0063] The molecular precursor compounds of this invention are
desirable for preparing semiconductor materials and compositions. A
molecular precursor has a structure containing two or more
different metal atoms which may be bound to each other through
interactions or bridges with one or more chalcogen atoms of
chalcogen-containing moieties.
[0064] With this structure, when a molecular precursor is used in a
process such as deposition, coating or printing on a substrate or
surface, as well as processes involving annealing, sintering,
thermal pyrolysis, and other semiconductor manufacturing processes,
use of the molecular precursors can enhance the formation of a
semiconductor and its properties.
[0065] For example, the use of a molecular precursor in
semiconductor manufacturing processes can enhance the formation of
M-E-M' bonding, such as is required for chalcogen-containing
semiconductor compounds and materials, where M is an atom of one of
Groups 3 to 12, M' is an atom of Group 13, and E is a
chalcogen.
[0066] In aspects of this invention, chemically and physically
uniform semiconductor layers can be prepared with molecular
precursor compounds.
[0067] In further embodiments, solar cells and other products can
be made in processes operating at relatively low temperatures using
the precursor compounds and compositions of this disclosure.
[0068] The molecular precursors of this disclosure are useful to
prepare inks that can be used in various methods to prepare
semiconductor materials.
[0069] The molecular precursor compounds and compositions of this
disclosure can provide enhanced processability for solar cell
production.
[0070] Certain molecular precursor compounds and compositions of
this disclosure provide the ability to be processed at relatively
low temperatures, as well as the ability to use a variety of
substrates including flexible polymers in solar cells.
Empirical Formulas of Molecular Precursors
[0071] This disclosure provides a range of molecular precursor
compounds having two or more different metal atoms and one or more
chalcogen atoms.
[0072] In certain aspects, a molecular precursor compound may
contain one or more metal atoms, and one or more atoms of Group 13,
as well as combinations thereof. Any of these atoms may be bonded
to one or more atoms selected from atoms of Group 15, S, Se, and
Te, as well as one or more ligands. A molecular precursor compound
may be a neutral compound, or an ionic form, or have a charged
complex or counterion.
[0073] A molecular precursor compound may contain one or more atoms
selected from the transition metals of Group 3 through Group 12, B,
Al, Ga, In, Tl, Si, Ge, Sn, Pb, and Bi. Any of these atoms may be
bonded to one or more atoms selected from atoms of Group 15, S, Se,
and Te, as well as one or more ligands.
[0074] A molecular precursor compound may contain one or more atoms
selected from Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In,
Tl, Si, Ge, Sn, Pb, and Bi. Any of these atoms may be bonded to one
or more atoms selected from atoms of Group 15, S, Se, and Te, as
well as one or more ligands.
[0075] In some embodiments, a molecular precursor compound may
contain one or more atoms selected from Cu, Ag, Zn, Ga, In, Tl, Si,
Ge, Sn, and Pb. Any of these atoms may be bonded to one or more
atoms selected from atoms of Group 15, S, Se, and Te, as well as
one or more ligands.
[0076] In some embodiments, a molecular precursor compound may
contain one or more atoms selected from Cu, Ag, Zn, Ga, In, Tl, Si,
Ge, Sn, and Pb. Any of these atoms may be bonded to one or more
chalcogen atoms, as well as one or more ligands.
[0077] In some variations, a molecular precursor compound may
contain one or more atoms selected from Cu, Ag, Ga, and In. Any of
these atoms may be bonded to one or more atoms selected from S, Se,
and Te, as well as one or more ligands.
Precursor Molecular Structure and Properties
[0078] A molecular precursor compound of this disclosure is stable
at ambient temperatures. Molecular precursors can be used for
making layered materials, optoelectronic materials, and devices.
Using molecular precursors advantageously allows control of the
stoichiometry, structure, and ratios of various atoms in a
material, layer, or semiconductor.
[0079] Molecular precursor compounds of this invention may be
solids, solids with low melting temperatures, oily substances, or
liquids at ambient temperatures. Embodiments of this disclosure
that are fluids at ambient temperatures can provide superior
processability for production of solar cells and other products, as
well as the enhanced ability to be processed on a variety of
substrates including flexible substrates.
[0080] In general, a molecular precursor compound can be processed
through the application of heat, light, kinetic, mechanical or
other energy to be converted to a material, including a
semiconductor material. In these processes, a molecular precursor
compound undergoes a transition to become a material. The
conversion of a molecular precursor compound to a material can be
done in processes known in the art, as well as the novel processes
of this disclosure.
[0081] Embodiments of this invention may further provide processes
for making optoelectronic materials. Following the synthesis of a
molecular precursor compound, the compound can be deposited,
sprayed, or printed onto a substrate by various means. Conversion
of the molecular precursor compound to a material can be done
during or after the process of depositing, spraying, or printing
the compound onto the substrate.
[0082] A molecular precursor compound of this disclosure may have a
transition temperature below about 400.degree. C., or below about
300.degree. C., or below about 280.degree. C., or below about
260.degree. C., or below about 240.degree. C., or below about
220.degree. C., or below about 200.degree. C.
[0083] In some aspects, molecular precursors of this disclosure
include molecules that are fluid or liquid at relatively low
temperatures and can be processed as a neat liquid. In certain
embodiments, a molecular precursor has a liquid state at a
temperature below about 200.degree. C., or below about 180.degree.
C., or below about 160.degree. C., or below about 140.degree. C.,
or below about 120.degree. C., or below about 100.degree. C., or
below about 80.degree. C., or below about 60.degree. C., or below
about 40.degree. C.
[0084] A molecular precursor compound of this invention can be
crystalline or amorphous, and can be soluble in various non-aqueous
solvents.
[0085] A molecular precursor compound may contain ligands, or
ligand fragments, or portions of ligands that can be removed under
mild conditions, at relatively low temperatures, and therefore
provide a facile route to convert the molecular precursor to a
material or semiconductor. The ligands, or some atoms of the
ligands, may be removable in various processes, including certain
methods for depositing, spraying, and printing, as well as by
application of energy.
[0086] These advantageous features allow enhanced control over the
structure of a semiconductor material made with the molecular
precursor compounds of this invention.
Molecular Precursors (MP1) for Semiconductors and
Optoelectronics
[0087] In some embodiments, a molecular precursor compound of the
family MP1 contains an atom M.sup.B of Group 13 selected from Al,
Ga, and In, which is stabilized by having ligands attached. These
molecular precursor compounds further contain a monovalent metal
atom M.sup.A selected from Cu, Au, Ag, and Hg, which is stabilized
by interactions with one or more chalcogen atoms. The atom M.sup.A
may further be stabilized by interacting with another M.sup.A atom.
Aside from interactions with chalcogen atoms, the atom M.sup.A has
no other ligands attached.
[0088] The structure of a family of MP1 precursor molecules
represented by the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1 is shown in
FIG. 1.
[0089] The molecular structure of the family of compounds is of a
dimer, represented by the formula
(M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1).sub.2.
[0090] The local structure surrounding the atom M.sup.B in a
molecule of the MP1 family is a tetrahedral arrangement of four
atoms. At one apex of the M.sup.B tetrahedron is an atom of R.sup.1
through which it is attached to M.sup.B. The remainder of the
tetrahedron is formed by the chalcogen atoms of three of the
ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4), each of which is
attached through a chalcogen atom to M.sup.B.
[0091] The local structure surrounding the atom M.sup.A includes
bonding interactions with three chalcogen atoms that belong to
three of the ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4). The
three ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4), are chalcogen
bridging ligands that are each shared through bonding of their
chalcogen atom to an M.sup.A atom and an M.sup.B atom. The atom
M.sup.A may further be stabilized by interacting with another
M.sup.A atom. Aside from interactions with chalcogen atoms, the
atom M.sup.A has no other ligands attached.
[0092] The portion R.sup.n, where n is 1, 2, 3, or 4, of each of
the ligands attached to the atoms M.sup.A and M.sup.B may be a good
leaving group in relation to a transition of the molecular
precursor compound at elevated temperatures or upon application of
energy.
[0093] The arrangement of atoms in a molecular precursor compound
of the MP1 family may be described by the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, wherein E is
chalcogen, and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are the same
or different and are groups attached through a carbon or non-carbon
atom, including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and
inorganic and organic ligands. In some embodiments, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are the same or different and are
alkyl groups attached through a carbon atom.
[0094] In some embodiments, molecular precursor compounds of the
MP1 family advantageously do not contain a phosphine ligand, or a
ligand or attached compound containing phosphorus, arsenic, or
antimony, or a halogen ligand.
[0095] Embodiments of this invention further provide a family MP1
of molecular precursor compounds in which the arrangement of atoms
may be described by the formula
Cu-(ER.sup.2)(ER.sup.3)(ER.sup.4)(In,Ga)R.sup.1, wherein E is
chalcogen, and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are the same
or different and are groups attached through a carbon or non-carbon
atom, including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and
inorganic and organic ligands. In some embodiments, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are the same or different and are
alkyl groups attached through a carbon atom.
[0096] In certain variations, a molecular precursor compound of the
MP1 family contains an atom M.sup.B, being In or Ga, which is
stabilized by attached ligands. These molecular precursor compounds
further contain an atom M.sup.A, being Cu, which is stabilized by
interactions with one or more chalcogen atoms. The atom M.sup.A may
further be stabilized by interacting with another M.sup.A atom.
Aside from interactions with chalcogen atoms, the atom M.sup.A has
no other ligands attached.
[0097] In additional aspects, a molecular precursor compound may
have the formula
(M.sup.A1-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4)(M.sup.A2--
(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4), wherein M.sup.A1 and
M.sup.A2 are different atoms defined as for M.sup.A.
[0098] In further embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 may independently be (C1-22)alkyl groups. In
these embodiments, the alkyl group may be a (C1)alkyl (methyl), or
a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a
(C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a
(C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl, or a
(C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a (C16)alkyl, or a
(C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a (C20)alkyl, or a
(C21)alkyl, or a (C22)alkyl.
[0099] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 may independently be (C1-12)alkyl groups. In
these embodiments, the alkyl group may be a (C1)alkyl (methyl), or
a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a
(C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a
(C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl.
[0100] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 may independently be (C1-6)alkyl groups. In
these embodiments, the alkyl group may be a (C1)alkyl (methyl), or
a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a
(C5)alkyl, or a (C6)alkyl.
[0101] In further variations, R.sup.1 is (C8)alkyl and R.sup.2,
R.sup.3, and R.sup.4 are the same and are (C3-4)alkyl.
[0102] In other forms, R.sup.1 is (C6)alkyl and R.sup.2, R.sup.3,
and R.sup.4 are the same and are (C3-4)alkyl.
[0103] In some aspects, a molecular precursor compound can be
represented by the formula
(M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1).sub.2,
referred to as a dimer, wherein M.sup.A is a monovalent atom
selected from Cu, Au, Ag, and Hg, which is stabilized by
interactions with one or more chalcogen atoms. The atom M.sup.A may
further be stabilized by interacting with another M.sup.A atom.
Aside from interactions with chalcogen atoms, the atom M.sup.A has
no other ligands attached. M.sup.B is an atom of Ga or In, each E
is independently S or Se, and R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 are as defined above. In certain variations, M.sup.A is an
atom of Group 11, or M.sup.A is Cu.
[0104] A molecular precursor compound of the MP1 family may be
crystalline, or non-crystalline.
[0105] Examples of molecular precursor compounds of the MP1 family
of this disclosure include compounds having any one of the
formulas: Cu--(S.sup.tBu).sub.3In.sup.iPr;
Cu--(S.sup.tBu).sub.3In.sup.nBu; Cu--(Se.sup.tBu).sub.3In.sup.nBu;
Cu--(S.sup.tBu).sub.3In.sup.tBu; Cu--(Se.sup.tBu).sub.3Ga.sup.tBu;
Cu--(S.sup.tBu).sub.3Ga.sup.tBu; Cu--(Se.sup.tBu).sub.3In.sup.tBu;
Cu--(Se.sup.tBu).sub.3In.sup.iPr; Cu--(Se.sup.tBu).sub.3In.sup.sBu;
Cu--(Se.sup.tBu).sub.3Ga.sup.iPr; Cu--(S.sup.tBu).sub.3Ga.sup.iPr;
and a dimer of any of the foregoing.
[0106] Examples of molecular precursor compounds of the MP1 family
of this disclosure include compounds having any one of the
formulas: Cu--(S.sup.tBu).sub.3In(NEt.sub.2);
Cu--(S.sup.tBu).sub.3In(N.sup.iPr.sub.2);
Cu--(Se.sup.tBu).sub.3In(NEt.sub.2);
Cu--(S.sup.tBu).sub.3In(NMe.sub.2);
Cu--(Se.sup.tBu).sub.3Ga(NEt.sub.2);
Cu--(S.sup.tBu).sub.3Ga(N.sup.nBu.sub.2);
Cu--(Se.sup.tBu).sub.3In(NEt.sub.2);
Cu--(Se.sup.tBu).sub.3In(N.sup.iPr.sub.2);
Cu--(Se.sup.tBu).sub.3In(N.sup.iPr.sub.2);
Cu--(Se.sup.tBu).sub.3Ga(N.sup.iPr.sub.2);
Cu--(S.sup.tBu).sub.3Ga(N.sup.sBu.sub.2); and a dimer of any of the
foregoing.
[0107] Examples of molecular precursor compounds of the MP1 family
of this disclosure include compounds having any one of the
formulas: Cu--(S.sup.tBu).sub.3Tl.sup.iPr;
Cu--(S.sup.tBu).sub.3Tl.sup.nBu; Cu--(Se.sup.tBu).sub.3Tl.sup.nBu;
Cu--(S.sup.tBu).sub.3Tl.sup.tBu; Cu--(Se.sup.tBu).sub.3Tl.sup.tBu;
Cu--(Se.sup.tBu).sub.3Tl.sup.iPr; and a dimer of any of the
foregoing.
[0108] Examples of molecular precursor compounds of the MP1 family
of this disclosure include compounds having any one of the
formulas: Au--(S.sup.tBu).sub.3In.sup.iPr;
Ag--(S.sup.tBu).sub.3In.sup.nBu; Hg--(Se.sup.tBu).sub.3Ga.sup.tBu;
and a dimer of any of the foregoing.
[0109] Examples of molecular precursor compounds of the MP1 family
of this disclosure include compounds having any one of the
formulas: Cu--(S.sup.tBu).sub.2(S.sup.tBu)In.sup.tBu;
Cu--(S.sup.tBu).sub.2(S.sup.nBu)In.sup.iPr;
Cu--(S.sup.tBu).sub.2(S.sup.iPr)In.sup.nBu;
Cu--(S.sup.tBu).sub.2(Se.sup.iPr)In.sup.iPr;
Cu--(Te.sup.tBu).sub.2(Se.sup.iPr)In.sup.nBu;
Cu--(Se.sup.tBu).sub.2(Te.sup.iPr)In.sup.nBu;
Cu--(S.sup.tBu).sub.2(Te.sup.iPr)In.sup.tBu; and a dimer of any of
the foregoing.
[0110] Examples of molecular precursor compounds of the MP1 family
of this disclosure include compounds having any one of the
formulas: Cu--(S.sup.tBu)(S.sup.iPr)(S.sup.nBu)In.sup.iPr;
Cu--(Se.sup.tBu)(S.sup.iPr)(S.sup.nBu)In.sup.nBu;
Cu--(Se.sup.tBu)(S.sup.iPr)(Te.sup.nBu)In.sup.tBu;
Cu--(Se.sup.tBu)(Se.sup.iPr)(Se.sup.nBu)In.sup.iPr; and a dimer of
any of the foregoing.
[0111] Examples of molecular precursor compounds of the MP1 family
of this disclosure include compounds having any one of the
formulas: Cu--(S.sup.tBu).sub.3In(n-octyl);
Cu--(S.sup.tBu).sub.3In(n-dodecyl);
Cu--(Se.sup.tBu).sub.3In(branched-C18);
Cu--(S.sup.tBu).sub.3In(branched-C22);
Cu--(Se(n-hexyl)).sub.3Ga.sup.tBu;
Cu--(S(n-octyl)).sub.3Ga.sup.tBu; and a dimer of any of the
foregoing.
[0112] As used herein, the term dimer refers to a molecule composed
of two moieties having the same empirical formula. For example,
(Cu--(S.sup.tBu).sub.3In.sup.iPr).sub.2 is a dimer of
Cu--(S.sup.tBu).sub.3In.sup.iPr.
Preparation of Molecular Precursors (MP1)
[0113] Embodiments of this invention provide a family MP1 of
precursor molecules which can be synthesized from a compound
containing an atom M.sup.B of Group 13 selected from Al, Ga, In,
and Tl, and a compound containing a monovalent atom M.sup.A
selected from Cu, Au, Ag, and Hg.
[0114] Advantageously facile routes for the synthesis and isolation
of molecular precursor compounds of this invention have been
discovered, as described below.
[0115] In some aspects, synthesis of a molecular precursor of the
MP1 family begins with providing a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2.
[0116] A compound having the formula R.sup.1.sub.2M.sup.BER.sup.2
containing a Group 13 atom M.sup.B can be prepared by reacting
M.sup.BR.sup.1.sub.3 with HER.sup.2, where R.sup.1, R.sup.2, and E
are as defined above.
[0117] In other variations, a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2 containing a Group 13 atom M.sup.B can
be prepared by reacting R.sup.1.sub.2M.sup.BX with M.sup.CER.sup.2,
where R.sup.1, R.sup.2 and E are as defined above, X is halogen,
and M.sup.C is an alkali metal.
[0118] In additional variations, a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2 containing a Group 13 atom M.sup.B can
be prepared by reacting R.sup.1.sub.2M.sup.BX with
R.sup.2ESi(CH.sub.3).sub.3, where R.sup.1, R.sup.2 and E are as
defined above, and X is halogen.
[0119] To prepare a molecular precursor of the MP1 family, the
compound R.sup.1.sub.2M.sup.BER.sup.2 may be reacted with a
compound containing a monovalent atom M.sup.A defined above.
[0120] In some embodiments, a compound R.sup.1.sub.2M.sup.BER.sup.2
can be contacted with a chalcogen-containing compound
M.sup.A(ER.sup.3) in the presence of one equivalent of HER.sup.4,
where M.sup.A, M.sup.B, E, R.sup.1, R.sup.2, R.sup.3, and R.sup.4
are as defined above. As shown in Reaction Scheme 1a,
M.sup.BR.sup.1.sub.3 can be reacted with HER.sup.2 to form
R.sup.1.sub.2M.sup.BER.sup.2. The product R can be contacted with a
compound M.sup.A(ER.sup.3) in the presence of one equivalent of
HER.sup.4 to form a molecular precursor compound having the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1.
##STR00001##
In Reaction Scheme 1a, for each occurrence, E may be S, Se, or
Te.
[0121] In certain variations, the starting compound
M.sup.BR.sup.1.sub.3 may be stabilized as an adduct, for example,
as the diethylether adduct, and the diethylether may be
removed.
[0122] Alternatively, in some embodiments, M.sup.BR.sup.1.sub.3 can
be reacted with a compound M.sup.A(ER.sup.3) in the presence of two
equivalents of HER.sup.2 to form a molecular precursor compound
having the formula
M.sup.A-(ER.sup.2).sub.2(ER.sup.3)M.sup.BR.sup.1. As shown in
Reaction Scheme 1b, M.sup.BR.sup.1.sub.3 can be reacted with
compounds M.sup.A(ER.sup.3), HER.sup.2, and HER.sup.4 to form a
molecular precursor compound having the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1.
##STR00002##
[0123] In further aspects, a compound
(NR.sup.1.sub.2)M.sup.B(R.sup.2)(ER.sup.3) may be contacted with a
chalcogen-containing compound M.sup.A(ER.sup.4) in the presence of
one equivalent of HER.sup.5, where M.sup.A, M.sup.B, E, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are as defined above, R.sup.5 is
defined the same as R.sup.1, R.sup.2, R.sup.3, and R.sup.4, and
NR.sup.1.sub.2 is amido. As shown in Reaction Scheme 1c,
(NR.sup.1.sub.2)M.sup.BR.sup.2.sub.2 may be reacted with HER.sup.3
to form (NR.sup.1.sub.2)M.sup.B(R.sup.2)(ER.sup.3). The product
(NR.sup.1.sub.2)M.sup.B(R.sup.2)(ER.sup.3) may be contacted with a
compound M.sup.A(ER.sup.4) in the presence of one equivalent of
HER.sup.5 to form a molecular precursor compound having the formula
M.sup.A-(ER.sup.3)(ER.sup.4)(ER.sup.5)M.sup.B(NR.sup.1.sub.2).
##STR00003##
In Reaction Scheme 1c, the ligand (NR.sup.1.sub.2) corresponds to
the R.sup.1 of Reaction Scheme 1a.
[0124] In additional variations, a compound
R.sup.1.sub.2M.sup.BX.sub.2 can be contacted with a
chalcogen-containing compound M.sup.A(ER.sup.2) in the presence of
one equivalent of R.sup.3ESi(CH.sub.3).sub.3 and one equivalent of
R.sup.4ESi(CH.sub.3).sub.3, where M.sup.A, M.sup.B, E, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are as defined above. As shown in
Reaction Scheme 1d, R.sup.1M.sup.BX.sub.2 can be reacted with
M.sup.A(ER.sup.2), R.sup.3ESi(CH.sub.3).sub.3, and
R.sup.4ESi(CH.sub.3).sub.3 to form a molecular precursor compound
having the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1.
##STR00004##
[0125] The reactions and manipulations of reagents can be carried
out using known techniques under controlled inert atmosphere, such
as dry nitrogen, and anaerobic conditions using a drybox and a
Schlenk line system.
[0126] In certain examples, a molecular precursor of the MP1 family
can be synthesized by the following procedure. A Schlenk tube can
be charged with R.sup.1.sub.2M.sup.B(ER.sup.2) and an equimolar
amount of M.sup.A(ER.sup.2) in a glovebox in an inert, anaerobic
atmosphere. To this mixture can be added dry solvent via cannula on
a Schlenk line. The mixture can optionally be heated to dissolve or
disperse the components. An equimolar amount of HER.sup.2 can be
added by use of a syringe and the Schlenk tube sealed under
N.sub.2. The mixture can be heated, optionally for about 12 hours
at a temperature from about 30.degree. C. to about 120.degree. C.
The solution can then be cooled, optionally for several hours at a
temperature from about -80.degree. C. to about 15.degree. C. A
solid or crystalline product can be isolated.
[0127] Among other things, in some embodiments, certain starting
compounds were made in order to synthesize molecular precursor
molecules of this disclosure. The starting compounds include
certain compounds having one of the formulas M.sup.AER and
R.sup.1.sub.2M.sup.BER.sup.2, where M.sup.B is Ga or In, E is S or
Se, and R.sup.1 and R.sup.2 are alkyl. Examples of the starting
compounds that were prepared include CuSe.sup.tBu,
.sup.nBu.sub.2In(Se.sup.tBu), .sup.tBu.sub.2Ga(Se.sup.tBu),
.sup.tBu.sub.2In(Se.sup.tBu), and .sup.iPr.sub.2In(Se.sup.tBu).
[0128] Methods for making compounds comprising the formula
M.sup.AER include reacting M.sup.ACl with LiER, and reacting
M.sup.A.sub.2O with 2 equivalents of HER. In another method,
M.sup.ACl can be reacted with RESi(CH.sub.3).sub.3. In one example,
CuCl was reacted with .sup.tBuSeSi(CH.sub.3).sub.3 in THF, and
filtered. A red precipitate was obtained which was washed with
pentane and dried under vacuum. A red solid was isolated at a yield
of 90%.
Molecular Precursors (MP2) for Semiconductors and
Optoelectronics
[0129] In some embodiments, a molecular precursor compound of the
family MP2 contains two different atoms M.sup.B1 and M.sup.B2 of
Group 13 selected from Al, Ga, In, and Tl, which are stabilized by
having ligands attached. These molecular precursor compounds
further contain two monovalent atoms M.sup.A1 and M.sup.A2 which
are the same or different and are selected from Cu, Au, Ag, and Hg.
M.sup.A1 and M.sup.A2 are each stabilized by interactions with one
or more chalcogen atoms. The atoms M.sup.A1 and M.sup.A2 may
further be stabilized by interacting with each other. Aside from
interactions with chalcogen atoms, the atoms M.sup.A1 and M.sup.A2
have no other ligands attached.
[0130] The general structure of a family of MP2 precursor molecules
can be represented by the formula
(R.sup.1M.sup.B1(ER.sup.2)(ER.sup.3)(ER.sup.4)-M.sup.A1)(M.sup.A2-(ER.sup-
.5)(ER.sup.6)(ER.sup.7)M.sup.B2R.sup.8), as shown in FIG. 2.
[0131] As shown in FIG. 2, the local structure surrounding the atom
M.sup.B1 in a molecule of the MP2 family is a tetrahedral
arrangement of four atoms. At one apex of the tetrahedron is an
atom of R.sup.1 through which it is attached to M.sup.B1. The
remainder of the tetrahedron is formed by the chalcogen atoms of
three ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4), each of which
is attached through a chalcogen atom to M.sup.B1.
[0132] As shown in FIG. 2, the local structure surrounding the atom
M.sup.B2 is a tetrahedral arrangement of four atoms. At one apex of
the tetrahedron is a carbon atom of R.sup.8 through which it is
attached to M.sup.B2. The remainder of the tetrahedron is formed by
the chalcogen atoms of three ligands (ER.sup.5), (ER.sup.6), and
(ER.sup.7), each of which is attached through a chalcogen atom to
M.sup.B2.
[0133] As shown in FIG. 2, the local structure surrounding each of
the atoms M.sup.A1 and M.sup.A2 (labels "M.sup.A" in FIG. 2)
includes bonding interactions with three chalcogen atoms. For one
of the two atoms M.sup.A1 or M.sup.A2, the three chalcogen atoms
with which it has bonding interactions belong to the three ligands
(ER.sup.2), (ER.sup.3), and (ER.sup.5). For the other of the two
atoms M.sup.A1 or M.sup.A2, the three chalcogen atoms belong to the
three ligands (ER.sup.4), (ER.sup.6), and (ER.sup.7). The ligands
(ER.sup.2), (ER.sup.3), (ER.sup.4), (ER.sup.5), (ER.sup.6), and
(ER.sup.7) are chalcogen bridging ligands that are each shared
through bonding of their chalcogen atom to an M.sup.A atom and an
M.sup.B atom. Atoms M.sup.A1 and M.sup.A2 may further be stabilized
by interacting with each other. Aside from interactions with
chalcogen atoms, the atoms M.sup.A have no other ligands
attached.
[0134] The portion R.sup.n, where n is 1, 2, 3, 4, 5, 6, 7 or 8, of
each of the ligands attached to the atoms M.sup.A and M.sup.B may
be a good leaving group in relation to a transition of the
molecular precursor compound at elevated temperatures or upon
application of energy.
[0135] The arrangement of atoms in a molecular precursor compound
of the MP2 family may be described by the formula
(R.sup.1M.sup.B1(ER.sup.2)(ER.sup.3)(ER.sup.4)-M.sup.A1)(M.sup.A2-(ER.sup-
.5)(ER.sup.6)(ER.sup.7)M.sup.B2R.sup.8), wherein E is chalcogen,
and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7,
and R.sup.8 are the same or different and are groups attached
through a carbon or non-carbon atom, including alkyl, aryl,
heteroaryl, alkenyl, amido, silyl, and inorganic and organic
ligands. In some embodiments, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are the same or different
and are alkyl groups attached through a carbon atom.
[0136] In some embodiments, molecular precursor compounds of the
MP2 family advantageously do not contain a phosphine ligand, or a
ligand or attached compound containing phosphorus, arsenic, or
antimony, or a halogen ligand.
[0137] In further embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 may
independently be (C1-22)alkyl groups. In these embodiments, the
alkyl group may be a (C1)alkyl (methyl), or a (C2)alkyl (ethyl), or
a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a
(C7)alkyl, or a (C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a
(C11)alkyl, or a (C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a
(C15)alkyl, or a (C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a
(C19)alkyl, or a (C20)alkyl, or a (C21)alkyl, or a (C22)alkyl.
[0138] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 may
independently be (C1-12)alkyl groups. In these embodiments, the
alkyl group may be a (C1)alkyl (methyl), or a (C2)alkyl (ethyl), or
a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a
(C7)alkyl, or a (C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a
(C11)alkyl, or a (C12)alkyl.
[0139] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 may
independently be (C1-6)alkyl groups. In these embodiments, the
alkyl group may be a (C1)alkyl (methyl), or a (C2)alkyl (ethyl), or
a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl.
[0140] In further variations, R.sup.1 and R.sup.8 are (C8)alkyl and
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 are the
same and are (C3-4)alkyl.
[0141] In other forms, R.sup.1 and R.sup.8 are (C6)alkyl and
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 are the
same and are (C3-4)alkyl.
[0142] A molecular precursor compound of the MP2 family may be
crystalline, or non-crystalline.
[0143] Examples of molecular precursor compounds of the MP2 family
of this disclosure include compounds having any one of the
formulas:
(.sup.iPrIn(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga.sup.iPr);
(.sup.nBuIn(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga.sup.nBu);
(.sup.nBuGa(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Tl.sup.nBu);
(.sup.tBuIn(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga.sup.tBu);
(.sup.tBuTl(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga.sup.tBu);
(.sup.tBuGa(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3In.sup.tBu);
(.sup.tBuIn(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga.sup.tBu);
and
(.sup.iPrIn(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga.sup.iPr).
[0144] Examples of molecular precursor compounds of the MP2 family
of this disclosure include compounds having any one of the
formulas:
((NEt.sub.2)In(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga(NEt.sub.2));
((NEt.sub.2)In(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga.sup.nBu);
((NEt.sub.2)Ga(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Tl.sup.nBu);
((NEt.sub.2)In(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga(NEt.sub.2));
((NEt.sub.2)Tl(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga(NEt.sub.2))-
;
((NiPr.sub.2)Ga(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3In(NiPr.sub.2)-
);
((NiPr.sub.2)In(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga(NiPr.sub-
.2)); and
((NiPr.sub.2)In(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga(N-
iPr.sub.2)).
[0145] Examples of molecular precursor compounds of the MP2 family
of this disclosure include compounds having any one of the
formulas:
(.sup.iPrIn(S.sup.tBu).sub.3-Cu)(Ag--(S.sup.tBu).sub.3Ga.sup.iPr);
(.sup.nBuIn(S.sup.tBu).sub.3-Cu)(Au--(S.sup.tBu).sub.3Ga.sup.nBu);
(.sup.nBuGa(Se.sup.tBu).sub.3-Cu)(Ag--(Se.sup.tBu).sub.3Tl.sup.nBu);
(.sup.tBuIn(S.sup.tBu).sub.3-Cu)(Au--(S.sup.tBu).sub.3Ga.sup.tBu);
(.sup.tBuTl(Se.sup.tBu).sub.3-Cu)(Ag--(Se.sup.tBu).sub.3Ga.sup.tBu);
(.sup.tBuGa(S.sup.tBu).sub.3-Cu)(Au--(S.sup.tBu).sub.3In.sup.tBu);
(.sup.tBuIn(Se.sup.tBu).sub.3-Cu)(Ag--(Se.sup.tBu).sub.3Ga.sup.tBu);
and
(.sup.iPrIn(Se.sup.tBu).sub.3-Cu)(Au--(Se.sup.tBu).sub.3Ga.sup.iPr).
[0146] Examples of molecular precursor compounds of the MP2 family
of this disclosure include compounds having any one of the
formulas:
(.sup.iPrGa(S.sup.tBu).sub.3-Au)(Au--(S.sup.tBu).sub.3In.sup.iPr);
(.sup.nBuGa(S.sup.tBu).sub.3-Ag)(Ag--(S.sup.tBu).sub.3In.sup.nBu);
and
(.sup.tBuTl(Se.sup.tBu).sub.3-Hg)(Hg--(Se.sup.tBu).sub.3In.sup.tBu).
[0147] Examples of molecular precursor compounds of the MP2 family
of this disclosure include compounds having any one of the
formulas:
(.sup.iPrIn(S.sup.nBu)(S.sup.tBu).sub.2-Cu)(Cu--(S.sup.tBu).sub.2(S.sup.n-
Bu)Ga.sup.iPr);
(.sup.nBuIn(S.sup.iPr)(S.sup.tBu).sub.2-Cu)(Cu--(S.sup.tBu).sub.2(S.sup.i-
Pr)Ga.sup.nBu);
(.sup.iPrTl(Se.sup.iPr)(S.sup.tBu).sub.2-Cu)(Cu--(S.sup.tBu).sub.2(Se.sup-
.iPr)Ga.sup.iPr);
(.sup.nBuGa(Se.sup.iPr)(Te.sup.tBu).sub.2-Cu)(Cu--(Te.sup.tBu).sub.2(Se.s-
up.iPr)In.sup.nBu);
(.sup.nBuTl(Te.sup.iPr)(Se.sup.tBu).sub.2-Cu)(Cu--(Se.sup.tBu).sub.2(Te.s-
up.iPr)In.sup.nBu); and
(.sup.tBuGa(Te.sup.iPr)(S.sup.tBu).sub.2-Cu)(Cu--(S.sup.tBu).sub.2(Te.sup-
.iPr)In.sup.tBu).
[0148] Examples of molecular precursor compounds of the MP2 family
of this disclosure include compounds having any one of the
formulas:
(.sup.iPrIn(S.sup.nBu)(S.sup.iPr)(S.sup.tBu)--Cu)(Cu--(S.sup.tBu)(S.sup.i-
Pr)(S.sup.nBu)Ga.sup.iPr);
(.sup.nBuIn(S.sup.nBu)(S.sup.iPr)(Se.sup.tBu)--Cu)(Cu--(Se.sup.tBu)(S.sup-
.iPr)(S.sup.nBu)Tl.sup.nBu);
(.sup.tBuGa(Te.sup.nBu)(S.sup.iPr)(Se.sup.tBu)--Cu)(Cu--(Se.sup.tBu)(S.su-
p.iPr)(Te.sup.nBu)In.sup.tBu); and
(.sup.iPrGa(Se.sup.nBu)(Se.sup.iPr)(Se.sup.nBu)--Cu)(Cu--(Se.sup.nBu)(Se.-
sup.iPr)(Se.sup.nBu)Tl.sup.iPr).
[0149] Examples of molecular precursor compounds of the MP2 family
of this disclosure include compounds having any one of the
formulas:
((n-octyl)In(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga(n-octyl));
((n-dodecyl)In(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga(n-dodecyl));
((branched-C18)Ga(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3In(branched-
-C18));
((branched-C22)In(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Tl(bra-
nched-C22));
(.sup.tBuTl(Se(n-hexyl)).sub.3-Cu)(Cu--(Se(n-hexyl)).sub.3In.sup.tBu);
and
(.sup.tBuGa(Se(n-octyl)).sub.3-Cu)(Cu--(Se(n-octyl)).sub.3Tl.sup.tBu)-
.
Preparation of Molecular Precursors (MP2)
[0150] Embodiments of this invention provide a family MP2 of
precursor molecules which can be synthesized from compounds
containing an atom M.sup.B of Group 13 selected from Al, Ga, In,
and Tl, and compounds containing a monovalent atom M.sup.A selected
from Cu, Au, Ag, and Hg.
[0151] Advantageously facile routes for the synthesis and isolation
of molecular precursor compounds of this invention are described
below.
[0152] In some aspects, synthesis of a molecular precursor of the
MP2 family begins with providing compounds having the formulas
R.sup.1.sub.2M.sup.B1ER.sup.n and R.sup.8.sub.2M.sup.B2ER.sup.n,
where M.sup.B1 and M.sup.B2 are different Group 13 atoms.
[0153] Compounds having the formulas R.sup.1.sub.2M.sup.B1ER.sup.n
and R.sup.8.sub.2M.sup.B2ER.sup.n can be prepared by reacting
M.sup.B1R.sup.1.sub.3 and M.sup.B2R.sup.8.sub.3 with HER.sup.n,
where R.sup.1, R.sup.8, and E are as defined above.
[0154] In other variations, a compound having the formula
R.sup.1.sub.2M.sup.B1ER.sup.n can be prepared by reacting
R.sup.1.sub.2M.sup.B1X with M.sup.CER.sup.n, where X is halogen and
M.sup.C is an alkali metal.
[0155] In additional variations, a compound having the formula
R.sup.1.sub.2M.sup.B1ER.sup.n containing a Group 13 atom M.sup.B
can be prepared by reacting R.sup.1.sub.2M.sup.B1X with
R.sup.3ESi(CH.sub.3).sub.3, where R.sup.1, R.sup.3 and E are as
defined above, and X is halogen.
[0156] To prepare a molecular precursor of the MP2 family, the
compounds R.sup.1.sub.2M.sup.B1ER.sup.n and
R.sup.8.sub.2M.sup.B2ER.sup.n may be reacted with a compound
containing a monovalent atom M.sup.A defined above.
[0157] In some embodiments, the compounds
R.sup.1.sub.2M.sup.B1ER.sup.n and R.sup.8.sub.2M.sup.B2ER.sup.n can
be contacted with a chalcogen-containing compound M.sup.A(ER.sup.4)
in the presence of one equivalent of HER.sup.5, where R.sup.4 and
R.sup.5 are as defined above.
[0158] As shown in Reaction Scheme 2a, in some embodiments,
M.sup.B1R.sup.1.sub.3 and M.sup.B2R.sup.8.sub.3 can be reacted with
HER.sup.n to form R.sup.1.sub.2M.sup.B1ER.sup.n and
R.sup.8.sub.2M.sup.B2ER.sup.n. The products
R.sup.1.sub.2M.sup.B1ER.sup.n and R.sup.8.sub.2M.sup.B2ER.sup.n can
be contacted with two equivalents of a compound M.sup.A(ER.sup.4)
in the presence of two equivalents of HER.sup.5 to form a molecular
precursor compound.
##STR00005##
In the foregoing description, R.sup.n represents a mixture of R
groups, so that each group R.sup.n can be independently different.
The groups R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, and R.sup.8 are as defined above.
[0159] Reaction Scheme 2a may afford a mixture of compounds which
can include compounds having one atom of M.sup.B1 and one atom of
M.sup.B2, compounds having two atoms of M.sup.B1 and zero atoms of
M.sup.B2, and compounds having zero atoms of M.sup.B1 and two atoms
of M.sup.B2. These compounds have the formulas
(R.sup.1M.sup.B1(ER.sup.2)(ER.sup.3)(ER.sup.4)-M.sup.A1)(M.sup.A2-(ER.sup-
.5)(ER.sup.6)(ER.sup.7)M.sup.B2R.sup.8),
(R.sup.1M.sup.B1(ER.sup.2)(ER.sup.3)(ER.sup.4)-M.sup.A1)(M.sup.A2-(ER.sup-
.5)(ER.sup.6)(ER.sup.7)M.sup.B1R.sup.8), and
(R.sup.1M.sup.B2(ER.sup.2)(ER.sup.3)(ER.sup.4)-M.sup.A1)(M.sup.A2-(ER.sup-
.5)(ER.sup.6)(ER.sup.7)M.sup.B2R.sup.8), respectively, wherein
M.sup.A1 and M.sup.A2 are the same or different.
[0160] Compounds having the formula
(R.sup.1M.sup.B1(ER.sup.2)(ER.sup.3)(ER.sup.4)-M.sup.A1)(M.sup.A2-(ER.sup-
.5)(ER.sup.6)(ER.sup.7)M.sup.B2R.sup.8) are MP2 molecular precursor
compounds.
[0161] In certain variations, the starting compound M.sup.BR.sub.3
may be stabilized by a ligand such as diethylether.
[0162] Alternatively, as shown in Reaction Scheme 2b, in some
embodiments, M.sup.B1R.sup.1.sub.3 and M.sup.B2R.sup.2.sub.3 can be
reacted with two equivalents of a compound M.sup.AER.sup.n in the
presence of four equivalents of HER.sup.4 to form a molecular
precursor compound.
##STR00006##
[0163] The product of Reaction Scheme 2b affords a mixture of
compounds as described above for Reaction Scheme 2a. The mixture of
compounds that is the product of Reaction Scheme 2a and 2b can be
used directly to make molecular precursor compositions, as well as
semiconductors and other materials.
[0164] In Reaction Schemes 2a and 2b, the atom M.sup.A of
M.sup.AER.sup.n may represent a mixture of atoms M.sup.A1 and
M.sup.A2.
[0165] In further aspects, compounds
(NR.sup.1.sub.2)M.sup.B1(R.sup.n)(ER.sup.n) and
(NR.sup.8.sub.2)M.sup.B1(R.sup.n)(ER.sup.n) can be contacted with
two equivalents of a chalcogen-containing compound
M.sup.A(ER.sup.n) in the presence of four equivalents of HER.sup.n,
where M.sup.A, M.sup.B1, M.sup.B2, E, R.sup.1, R.sup.8, and R.sup.n
are as defined above, and NR.sup.1.sub.2 is amido.
[0166] As shown in Reaction Scheme 2c,
(NR.sup.1.sub.2)M.sup.B1R.sup.1.sub.2 and
(NR.sup.8.sub.2)M.sup.B2R.sup.8.sub.2 can be reacted with
M.sup.A(ER.sup.n) in the presence of HER.sup.n to form a molecular
precursor compound.
##STR00007##
[0167] The reactions and manipulations of reagents can be carried
out using known techniques under controlled inert atmosphere, such
as dry nitrogen, and anaerobic conditions using a drybox and a
Schlenk line system.
Molecular Precursors (MP3) for Semiconductors and
Optoelectronics
[0168] In some embodiments, a molecular precursor compound of the
family MP3 contains an atom M.sup.B of Group 13 selected from Al,
Ga, In, and Tl, which is stabilized by having ligands attached.
These molecular precursor compounds further contain a divalent
metal atom M.sup.A which is stabilized by having
chalcogen-containing ligands attached. Divalent metal atoms M.sup.A
include Cu, Zn, Cd, Pt, Pd, Mo, W, Cr, Ni, Mn, Fe, Co, V, and Hg.
Aside from interactions with chalcogen-containing ligands, the atom
M.sup.A has no other ligands attached.
[0169] The general structure of a precursor molecule of the MP3
family can be represented by the formula
(R.sup.4E)M.sup.A(ER.sup.3)(ER.sup.5)(ER.sup.2)M.sup.BR.sup.1, as
shown in FIG. 3.
[0170] The molecular structure of a precursor compound of the MP3
family is of a monomer.
[0171] As shown in FIG. 3, the local structure surrounding the atom
M.sup.B is a tetrahedral arrangement of four atoms. At one apex of
the M.sup.B tetrahedron is an atom of R.sup.1 through which it is
attached to M.sup.B. The remainder of the tetrahedron is formed by
the chalcogen atoms of three ligands (ER.sup.2), (ER.sup.3), and
(ER.sup.5), each of which is attached through a chalcogen atom to
M.sup.B.
[0172] As shown in FIG. 3, the local structure surrounding the atom
M.sup.A is a tetrahedral arrangement of four atoms. At one apex of
the M.sup.A tetrahedron is a chalcogen atom of the ligand
(ER.sup.4) through which it is attached to M.sup.A. The remainder
of the tetrahedron is formed by the chalcogen atoms of three
ligands (ER.sup.2), (ER.sup.3), and (ER.sup.5), each attached
through a chalcogen atom to M.sup.A. The three ligands (ER.sup.2),
(ER.sup.3), and (ER.sup.5) are chalcogen bridging ligands that are
each shared through bonding of their chalcogen atom to M.sup.A and
M.sup.B. Aside from interactions with chalcogen atoms, the atom
M.sup.A has no other ligands attached.
[0173] The portion R.sup.n, where n is 1, 2, 3, 4, or 5, of each of
the ligands attached to the atoms M.sup.A and M.sup.B may be a good
leaving group in relation to a transition of the molecular
precursor compound at elevated temperatures or upon application of
energy.
[0174] The arrangement of atoms in a molecular precursor compound
of the MP3 family may be described by the formula
(R.sup.4E)M.sup.A(ER.sup.3)(ER.sup.5)(ER.sup.2)M.sup.BR.sup.1,
wherein E is chalcogen, and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 are the same or different and are groups attached through a
carbon or non-carbon atom, including alkyl, aryl, heteroaryl,
alkenyl, amido, silyl, and inorganic and organic ligands. In some
embodiments, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are the
same or different and are alkyl groups attached through a carbon
atom.
[0175] In some embodiments, molecular precursor compounds of the
MP3 family advantageously do not contain a phosphine ligand, or a
ligand or attached compound containing phosphorus, arsenic, or
antimony, or a halogen ligand.
[0176] Embodiments of this invention further provide a family MP3
of molecular precursor compounds in which the arrangement of atoms
may be described by the formula
(R.sup.4E)Cu(ER.sup.3)(ER.sup.5)(ER.sup.2)(In,Ga)R.sup.1, wherein E
is chalcogen, and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5
are the same or different and are groups attached through a carbon
or non-carbon atom, including alkyl, aryl, heteroaryl, alkenyl,
amido, silyl, and inorganic and organic ligands. In some
embodiments, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are the
same or different and are alkyl groups attached through a carbon
atom.
[0177] In certain variations, a molecular precursor compound of the
MP3 family contains an atom M.sup.B, being In or Ga, which is
stabilized by attached ligands. These molecular precursor compounds
further contain an atom M.sup.A, being Cu, which is stabilized by
interactions with one or more chalcogen atoms.
[0178] In further embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may independently be (C1-22)alkyl
groups. In these embodiments, the alkyl group may be a (C1)alkyl
(methyl), or a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl,
or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or
a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl, or
a (C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a (C16)alkyl, or
a (C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a (C20)alkyl, or
a (C21)alkyl, or a (C22)alkyl.
[0179] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may independently be (C1-12)alkyl
groups. In these embodiments, the alkyl group may be a (C1)alkyl
(methyl), or a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl,
or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or
a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl.
[0180] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may independently be (C1-6)alkyl
groups. In these embodiments, the alkyl group may be a (C1)alkyl
(methyl), or a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl,
or a (C5)alkyl, or a (C6)alkyl.
[0181] In further variations, R.sup.1 is (C8)alkyl and R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 are the same and are (C3-4)alkyl.
[0182] In other forms, R.sup.1 is (C6)alkyl and R.sup.2, R.sup.3,
R.sup.4 and R.sup.5 are the same and are (C3-4)alkyl.
[0183] In further embodiments, a molecular precursor compound of
the family MP3 may have the general structure represented by the
formula R.sup.5M.sup.A(ER.sup.4)(ER.sup.3)(ER.sup.2)M.sup.BR.sup.1,
as shown in FIG. 4. In these embodiments, a molecular precursor
compound of the family MP3 contains an atom M.sup.B of Group 13
selected from Al, Ga, In, and Tl, which is stabilized by having
ligands attached. These molecular precursor compounds further
contain a divalent metal atom M.sup.A which is stabilized by having
ligands attached. Divalent metal atoms M.sup.A include Cu, Zn, Cd,
Pt, Pd, Mo, W, Cr, Ni, Mn, Fe, Co, V, and Hg.
[0184] The molecular structure of a precursor compound of the MP3
family having the general structure represented by the formula
R.sup.5M.sup.A(ER.sup.4)(ER.sup.3)(ER.sup.2)M.sup.BR.sup.1 is of a
monomer.
[0185] As shown in FIG. 4, the local structure surrounding the atom
M.sup.B is a tetrahedral arrangement of four atoms. At one apex of
the M.sup.B tetrahedron is a carbon atom of R.sup.1 through which
it is attached to M.sup.B. The remainder of the tetrahedron is
formed by the chalcogen atoms of three ligands (ER.sup.2),
(ER.sup.3), and (ER.sup.4), each of which is attached through a
chalcogen atom to M.sup.B.
[0186] As shown in FIG. 4, the local structure surrounding the atom
M.sup.A is a tetrahedral arrangement of four atoms. At one apex of
the M.sup.A tetrahedron is a carbon atom of R.sup.5 through which
it is attached to M.sup.A. The remainder of the tetrahedron is
formed by the chalcogen atoms of three ligands (ER.sup.2),
(ER.sup.3), and (ER.sup.4), each of which is attached through a
chalcogen atom to M.sup.A.
[0187] The arrangement of atoms in a molecular precursor compound
of the MP3 family can be represented by the formula
R.sup.5M.sup.A(ER.sup.4)(ER.sup.3)(ER.sup.2)M.sup.BR.sup.1, wherein
E is chalcogen, and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5
are the same or different and are groups attached through a carbon
or non-carbon atom, including alkyl, aryl, heteroaryl, alkenyl,
amido, silyl, and inorganic and organic ligands. In some
embodiments, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are the
same or different and are alkyl groups attached through a carbon
atom.
[0188] In some embodiments, molecular precursor compounds of the
MP3 family advantageously do not contain a phosphine ligand, or a
ligand or attached compound containing phosphorus, arsenic, or
antimony, or a halogen ligand.
[0189] Embodiments of this invention further provide a family MP3
of molecular precursor compounds in which the arrangement of atoms
may be described by the formula
R.sup.5Zn(ER.sup.4)(ER.sup.3)(ER.sup.2)(In,Ga)R.sup.1, wherein E is
chalcogen, and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are
the same or different and are groups attached through a carbon or
non-carbon atom, including alkyl, aryl, heteroaryl, alkenyl, amido,
silyl, and inorganic and organic ligands. In some embodiments,
R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are the same or
different and are alkyl groups attached through a carbon atom.
[0190] A molecular precursor compound of the MP3 family may be
crystalline, or non-crystalline.
[0191] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.tBuS)Cu(S.sup.tBu).sub.3In.sup.iPr;
(.sup.tBuS)Cu(S.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuS)Cu(S.sup.tBu).sub.3In.sup.tBu;
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Ga.sup.tBu;
(.sup.tBuS)Cu(S.sup.tBu).sub.3Ga.sup.tBu;
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In.sup.tBu; and
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In.sup.iPr.
[0192] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.tBuS)Cu(S.sup.tBu).sub.3Ga.sup.iPr;
(.sup.tBuS)Cu(S.sup.tBu).sub.3Tl.sup.nBu;
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Ga.sup.nBu;
(.sup.tBuS)Cu(S.sup.tBu).sub.3Ga.sup.tBu;
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Tl.sup.tBu; and
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Ga.sup.iPr.
[0193] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.tBuS)Cu(S.sup.tBu).sub.3Ga(NEt.sub.2);
(.sup.tBuS)Cu(S.sup.tBu).sub.3Tl.sup.n(NEt.sub.2);
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Ga(NEt.sub.2);
(.sup.tBuS)Cu(S.sup.tBu).sub.3Ga(NEt.sub.2);
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Tl.sup.t(NEt.sub.2); and
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Ga(NEt.sub.2).
[0194] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.tBuS)Cu(S.sup.tBu).sub.3In(NEt.sub.2);
(.sup.tBuS)Cu(S.sup.tBu).sub.3In(NEt.sub.2);
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In(N.sup.iPr.sub.2);
(.sup.tBuS)Cu(S.sup.tBu).sub.3In(N.sup.iPr.sub.2);
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Ga(N.sup.iPr.sub.2);
(.sup.tBuS)Cu(S.sup.tBu).sub.3Ga(N.sup.iPr.sub.2);
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In(N.sup.nBu.sub.2); and
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In(N.sup.sBu.sub.2).
[0195] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.tBuS)Zn(S.sup.tBu).sub.3In.sup.iPr;
(.sup.tBuS)Pt(S.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuSe)Pd(Se.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuS)Mo(S.sup.tBu).sub.3In.sup.tBu;
(.sup.tBuSe)W(Se.sup.tBu).sub.3Ga.sup.tBu;
(.sup.tBuS)Cr(S.sup.tBu).sub.3Ga.sup.tBu;
(.sup.tBuS)Ni(S.sup.tBu).sub.3In.sup.iPr;
(.sup.tBuS)Mn(S.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuSe)Fe(Se.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuS)Co(S.sup.tBu).sub.3In.sup.tBu;
(.sup.tBuSe)Hg(Se.sup.tBu).sub.3Ga.sup.tBu;
(.sup.tBuS)Cd(S.sup.tBu).sub.3In.sup.iPr;
(.sup.tBuS)V(S.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuS)Ru(S.sup.tBu).sub.3In.sup.iPr;
(.sup.tBuS)Rh(S.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuSe)Re(Se.sup.tBu).sub.3In.sup.nBu;
(.sup.tBuS)Os(S.sup.tBu).sub.3In.sup.tBu; and
(.sup.tBuSe)Ir(Se.sup.tBu).sub.3Ga.sup.tBu.
[0196] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.tBuS)Cu(S.sup.tBu).sub.2(S.sup.nBu)In.sup.iPr;
(.sup.tBuS)Cu(S.sup.tBu).sub.2(S.sup.iPr)In.sup.nBu;
(.sup.tBuS)Cu(S.sup.tBu).sub.2(Se.sup.iPr)In.sup.iPr;
(.sup.tBuTe)Cu(Te.sup.tBu).sub.2(Se.sup.iPr)In.sup.nBu;
(.sup.tBuSe)Cu(Se.sup.tBu).sub.2(Te.sup.iPr)In.sup.nBu; and
(.sup.tBuS)Cu(S.sup.tBu).sub.2(Te.sup.iPr)In.sup.tBu.
[0197] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.nBuS)Cu(S.sup.tBu)(S.sup.iPr)(S.sup.nBu)In.sup.iPr;
(.sup.nBuS)Cu(Se.sup.tBu)(S.sup.iPr)(S.sup.nBu)In.sup.nBu;
(.sup.iPrS)Cu(Se.sup.tBu)(S.sup.iPr)(Te.sup.nBu)In.sup.tBu; and
(.sup.iPrSe)Cu(Se.sup.tBu)(Se.sup.iPr)(Se.sup.nBu)In.sup.iPr.
[0198] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.tBuS)Cu(S.sup.tBu).sub.3In(n-octyl);
(.sup.tBuS)Cu(S.sup.tBu).sub.3In(n-dodecyl);
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In(branched-C18);
(.sup.tBuS)Cu(S.sup.tBu).sub.3In(branched-C22);
((n-hexyl)Se)Cu(Se(n-hexyl)).sub.3Ga.sup.tBu; and
((n-octyl)S)Cu(S(n-octyl)).sub.3Ga.sup.tBu.
[0199] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (.sup.nBuS)Cu(S.sup.tBu).sub.3In.sup.iPr;
(.sup.nBuS)Cu(S.sup.tBu).sub.3In.sup.nBu;
(.sup.iPrSe)Cu(Se.sup.tBu).sub.3In.sup.nBu;
(.sup.iPrS)Cu(S.sup.tBu).sub.3In.sup.tBu;
(.sup.nBuSe)Cu(Se.sup.tBu).sub.3Ga.sup.tBu;
(.sup.iPrS)Cu(S.sup.tBu).sub.3Ga.sup.tBu;
(.sup.nBuSe)Cu(Se.sup.tBu).sub.3In.sup.tBu; and
(.sup.iPrSe)Cu(Se.sup.tBu).sub.3In.sup.iPr.
[0200] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: .sup.tBuCu(S.sup.tBu).sub.3In.sup.iPr;
.sup.tBuZn(S.sup.tBu).sub.3In.sup.nBu;
.sup.tBuZn(Se.sup.tBu).sub.3In.sup.nBu;
.sup.tBuZn(S.sup.tBu).sub.3In.sup.tBu;
.sup.tBuZn(Se.sup.tBu).sub.3Ga.sup.tBu;
.sup.tBuZn(S.sup.tBu).sub.3Ga.sup.tBu;
.sup.tBuZn(Se.sup.tBu).sub.3In.sup.tBu; and
.sup.tBuCu(Se.sup.tBu).sub.3In.sup.iPr.
[0201] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: .sup.tBuZn(S.sup.tBu).sub.3In.sup.iPr.
[0202] Examples of molecular precursor compounds of the MP3 family
of this disclosure include compounds having any one of the
formulas: (NEt.sub.2)Cu(S.sup.tBu).sub.3In(NEt.sub.2);
(N.sup.iPr.sub.2)Cu(S.sup.tBu).sub.3In(N.sup.iPr.sub.2);
(N.sup.iPr.sub.2)Cu(Se.sup.tBu).sub.3In(NEt.sub.2);
(NEt.sub.2)Cu(S.sup.tBu).sub.3In(N.sup.iPr.sub.2);
(NEt.sub.2)Cu(Se.sup.tBu).sub.3Ga(N.sup.iPr.sub.2);
(N.sup.iPr.sub.2)Cu(S.sup.tBu).sub.3Ga(N.sup.iPr.sub.2);
(N.sup.iPr.sub.2)Cu(Se.sup.tBu).sub.3In(N.sup.nBu.sub.2); and
(N.sup.iPr.sub.2)Cu(Se.sup.tBu).sub.3In(N.sup.sBu.sub.2).
Preparation of Molecular Precursors (MP3)
[0203] Embodiments of this invention provide a family MP3 of
precursor molecules which can be synthesized from a compound
containing an atom M.sup.B of Group 13 selected from Al, Ga, In,
and Tl, and a compound containing a divalent atom M.sup.A. Divalent
metal atoms M.sup.A include Cu, Zn, Cd, Pt, Pd, Mo, W, Cr, Ni, Mn,
Fe, Co, V, and Hg.
[0204] Advantageously facile routes for the synthesis and isolation
of molecular precursor compounds of this invention are described
below.
[0205] In some aspects, synthesis of a molecular precursor of the
MP3 family begins with providing a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2.
[0206] A compound having the formula R.sup.1.sub.2M.sup.BER.sup.2
containing a Group 13 atom M.sup.B can be prepared by reacting
M.sup.BR.sup.1.sub.3 with HER.sup.2, where R.sup.1, R.sup.2, and E
are as defined above.
[0207] In other variations, a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2 containing a Group 13 atom M.sup.B can
be prepared by reacting R.sup.1.sub.2M.sup.BX with M.sup.CER.sup.2,
where R.sup.1, R.sup.2 and E are as defined above, X is halogen,
and M.sup.C is an alkali metal.
[0208] In additional variations, a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2 containing a Group 13 atom M.sup.B can
be prepared by reacting R.sup.1.sub.2M.sup.BX with
R.sup.2ESi(CH.sub.3).sub.3, where R.sup.1, R.sup.2 and E are as
defined above, and X is halogen.
[0209] To prepare a molecular precursor of the MP3 family, the
compound R.sup.1.sub.2M.sup.BER.sup.2 may be reacted with a
compound containing a divalent atom M.sup.A defined above.
[0210] In some embodiments, a compound R.sup.1.sub.2M.sup.BER.sup.2
can be contacted with a chalcogen-containing compound
M.sup.A(ER.sup.3).sub.2 or M.sup.A(ER.sup.3)(ER.sup.4) in the
presence of one equivalent of HER.sup.5, where M.sup.A, M.sup.B, E,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are as defined
above.
[0211] As shown in Reaction Scheme 3a, in some embodiments,
M.sup.BR.sup.1.sub.3 can be reacted with HER.sup.2 to form
R.sup.1.sub.2M.sup.BER.sup.2. The product
R.sup.1.sub.2M.sup.BER.sup.2 can be contacted with a compound
M.sup.A(ER.sup.3)(ER.sup.4) in the presence of one equivalent of
HER.sup.5 to form a molecular precursor compound having the formula
(R.sup.4E)M.sup.A(ER.sup.3)(ER.sup.5)(ER.sup.2)M.sup.BR.sup.1.
##STR00008##
In Reaction Scheme 3a, for each occurrence, E may be S, Se, or Te.
In certain variations, the starting compound M.sup.BR.sub.3 may be
stabilized by a ligand such as diethylether.
[0212] Alternatively, in some embodiments, M.sup.BR.sup.1.sub.3 can
be reacted with a compound M.sup.A(ER.sup.3)(ER.sup.4) in the
presence of two equivalents of HER.sup.n (HER.sup.2 and HER.sup.5
in Reaction Scheme 3b) to form a molecular precursor compound
having the formula
(R.sup.4E)M.sup.A(ER.sup.n).sub.2(ER.sup.3)M.sup.BR.sup.1.
[0213] As shown in Reaction Scheme 3b, in some embodiments,
M.sup.BR.sup.1.sub.3 can be reacted with compounds
M.sup.A(ER.sup.3)(ER.sup.4), HER.sup.2, and HER.sup.4 to form a
molecular precursor compound having the formula (R.sup.4E)
M.sup.A(ER.sup.3)(ER.sup.5)(ER.sup.2)M.sup.BR.sup.1.
##STR00009##
[0214] In Reaction Scheme 3b, each of the reagents HER.sup.2 and
HER.sup.5 can itself be a mixture of compounds with different
groups, where n is 1, 2, 3, 4, or 5, so that each group can be
independently different. Further, some of the groups -ER.sup.n may
be exchanged with each other during the reaction. Thus, the order
of appearance of the groups in the formula
(R.sup.4E)M.sup.A(ER.sup.3) (ER.sup.5) (ER.sup.2)M.sup.BR.sup.1,
can be different.
[0215] In further aspects, a compound
(NR.sup.1.sub.2)M.sup.BR.sup.2.sub.2 can be contacted with a
chalcogen-containing compound M.sup.A(ER.sup.3)(ER.sup.4) in the
presence of two equivalents of HER.sup.5, where M.sup.A, M.sup.B,
E, R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are as defined
above, and NR.sup.1.sub.2 is amido.
[0216] As shown in Reaction Scheme 3c,
(NR.sup.1.sub.2)M.sup.BR.sup.2.sub.2 can be reacted with
M.sup.A(ER.sup.3)(ER.sup.4) in the presence of two equivalents of
HER.sup.5 to form a molecular precursor compound having the formula
(R.sup.4E)M.sup.A(ER.sup.3)(ER.sup.5).sub.2M.sup.B(NR.sup.1.sub.2).
##STR00010##
[0217] In further embodiments, to prepare a molecular precursor of
the MP3 family, the compound R.sup.1.sub.2M.sup.BER.sup.2 may be
reacted with a compound containing a divalent atom M.sup.A defined
above.
[0218] In some embodiments, a compound R.sup.1.sub.2M.sup.BER.sup.2
can be contacted with a chalcogen-containing compound
M.sup.A(R.sup.5)(ER.sup.4) in the presence of one equivalent of
HER.sup.5, where M.sup.A, M.sup.B, E, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are as defined above.
[0219] As shown in Reaction Scheme 3d, in some embodiments,
M.sup.BR.sup.1.sub.3 can be reacted with HER.sup.2 to form
R.sup.1.sub.2M.sup.BER.sup.2. The product
R.sup.1.sub.2M.sup.BER.sup.2 can be contacted with a compound
M.sup.A(R.sup.5)(ER.sup.4) in the presence of one equivalent of
HER.sup.3 to form a molecular precursor compound having the formula
(R.sup.5)M.sup.A(ER.sup.4)(ER.sup.3)(ER.sup.2)M.sup.BR.sup.1.
##STR00011##
[0220] Alternatively, in some embodiments, M.sup.BR.sup.1.sub.3 can
be reacted with a compound M.sup.A(R.sup.5)(ER.sup.4) in the
presence of two equivalents of HER.sup.n (HER.sup.2 and HER.sup.3
in Reaction Scheme 3e) to form a molecular precursor compound
having the formula
(R.sup.5)M.sup.A(ER.sup.n).sub.2(ER.sup.3)M.sup.BR.sup.1.
[0221] As shown in Reaction Scheme 3e, in some embodiments,
M.sup.BR.sup.1.sub.3 can be reacted with compounds
M.sup.A(R.sup.5)(ER.sup.4), HER.sup.2, and HER.sup.3 to form a
molecular precursor compound having the formula
(R.sup.5)M.sup.A(ER.sup.4)(ER.sup.3)(ER.sup.2)M.sup.BR.sup.1.
##STR00012##
[0222] In further aspects, a compound M.sup.BR.sup.1.sub.3 can be
contacted with a chalcogen-containing compound
M.sup.A(NR.sup.5.sub.2)(ER.sup.4) in the presence of two
equivalents of HER.sup.3, where M.sup.A, M.sup.B, E, R.sup.1,
R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are as defined above, and
NR.sup.3.sub.2 is amido.
[0223] As shown in Reaction Scheme 3f, M.sup.BR.sup.1.sub.3 can be
reacted with M.sup.A(NR.sup.5.sub.2)(ER.sup.4) in the presence of
two equivalents of HER.sup.3 to form a molecular precursor compound
having the formula
(NR.sup.5.sub.2)M.sup.A(ER.sup.4)(ER.sup.3).sub.2M.sup.BR.sup.1.sub.2.
##STR00013##
[0224] The reactions and manipulations of reagents can be carried
out using known techniques under controlled inert atmosphere, such
as dry nitrogen, and anaerobic conditions using a drybox and a
Schlenk line system.
Molecular Precursors (MP4) for Semiconductors and
Optoelectronics
[0225] In some embodiments, a molecular precursor compound of the
MP4 family contains an atom M.sup.B of Group 13 selected from Al,
Ga, In, and Tl, which is stabilized by having ligands attached.
These molecular precursor compounds further contain a monovalent or
divalent atom M.sup.A which is stabilized by having ligands
attached.
[0226] The structure of a family of precursor molecules MP4 is
shown in FIG. 5 and may be represented by the formula
M.sup.A(ER.sup.2Z)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, where E is
chalcogen, Z is a neutral or anionic moiety, or portion of a
ligand, which may be capable of binding to a metal atom, and
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same or different and
are groups attached through one or more carbon or non-carbon atoms,
including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and
inorganic and organic ligands.
[0227] The general structure of a precursor molecule of the MP4
family can be represented by the formula
M.sup.A(ER.sup.2Z)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, as shown in
FIG. 5.
[0228] As shown in FIG. 5, the local structure surrounding the atom
M.sup.B is a tetrahedral arrangement of four atoms. At one apex of
the M.sup.B tetrahedron is an atom of R.sup.1 through which it is
attached to M.sup.B. The remainder of the tetrahedron is formed by
the chalcogen atoms of three ligands (ER.sup.2Z), (ER.sup.3), and
(ER.sup.4), each of which is attached through a chalcogen atom to
an M.sup.B.
[0229] As shown in FIG. 5, the local structure surrounding the atom
M.sup.A is a tetrahedral arrangement of four atoms. At one apex of
the M.sup.A tetrahedron is an atom of the moiety Z, through which
it is attached to M.sup.A. The remainder of the tetrahedron is
formed by the chalcogen atoms of three ligands (ER.sup.2Z),
(ER.sup.3), and (ER.sup.4), each of which is attached through a
chalcogen atom to M.sup.A. The three ligands (ER.sup.2Z),
(ER.sup.3), and (ER.sup.4) are chalcogen bridging ligands that are
each shared through bonding of their chalcogen atom to M.sup.A and
M.sup.B.
[0230] As shown in FIG. 5, the ligand (ER.sup.2Z) contains the
moiety Z attached through the portion R.sup.2. Thus, the ligand
(ER.sup.2Z) is essentially a bidentate ligand that is attached to
M.sup.A through both its chalcogen atom E, and through an atom of
the moiety Z.
[0231] The portion R.sup.n, where n=1-4, of each of the ligands
attached to the atoms M.sup.A and M.sup.B may be a good leaving
group in relation to a transition of the molecular precursor
compound at elevated temperatures or upon application of
energy.
[0232] The arrangement of atoms in a molecular precursor compound
of the MP4 family may be described by the formula
M.sup.A(ER.sup.2Z)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, where E is
chalcogen, and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are the same
or different and are groups attached through a carbon or non-carbon
atom, including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and
inorganic and organic ligands. In some embodiments, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are the same or different and are
alkyl groups attached through a carbon atom.
[0233] In some embodiments, Z is a neutral moiety such as
--NR.sub.2, --PR.sub.2, --AsR.sub.2, -ER, --SR, --OR, and --SeR.
When Z is a neutral moiety, the ligand (ER.sup.2Z) is a bidentate
ligand such as ER.sup.2NR.sub.2, ER.sup.2PR.sub.2,
ER.sup.2AsR.sub.2, ER.sup.2SR, and ER.sup.2SeR, each of which can
bond to M.sup.A through the atom E and a second atom such as N, P,
As, S, Se, and oxygen. When Z is a neutral ligand, M.sup.A is a
monovalent metal atom selected from Cu, Au, Ag, and Hg.
[0234] In some variations, Z is an anionic moiety such as
--NR.sup.-, -E.sup.-, --O.sup.-, --R.sup.-, -ERNR.sup.-,
-ERE.sup.-, and --SiR.sub.2.sup.-. When Z is an anionic moiety, the
ligand (ER.sup.2Z) is a bidentate ligand such as ER.sup.2NR.sup.-,
ER.sup.2PR.sup.-, ER.sup.2AsR.sup.-, ER.sup.2S.sup.-,
ER.sup.2O.sup.-, and ER.sup.2Se.sup.-, each of which can bond to
M.sup.A through E and a second atom such as N, P, As, S, Se, and O.
When Z is an anionic moiety, M.sup.A is a divalent metal atom.
Divalent metal atoms M.sup.A include Cu, Zn, Cd, Pt, Pd, Mo, W, Cr,
Ni, Mn, Fe, Co, V, and Hg.
[0235] When Z is an anionic moiety and M.sup.A is a divalent metal
atom, examples of the ligand (ER.sup.4Z) include
--SCH.sub.2CH.sub.2NR--, --SCH.sub.2CH.sub.2S--,
--SCH.sub.2CH.sub.2Se--, --SeCH.sub.2CH.sub.2NR--,
--SeCH.sub.2CH.sub.2S--, --SeCH.sub.2CH.sub.2Se--,
--SeCH.sub.2CH.sub.2CH.sub.2NR--, and
--SeCH.sub.2CH.sub.2CH.sub.2O--.
[0236] Embodiments of this invention further provide a family MP4
of molecular precursor compounds in which the arrangement of atoms
may be described by the formula
Cu(ER.sup.2Z)(ER.sup.3)(ER.sup.4)(In,Ga)R.sup.1, wherein E is
chalcogen, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same or
different and are groups attached through one or more carbon or
non-carbon atom, including alkyl, aryl, heteroaryl, alkenyl, amido,
silyl, and inorganic and organic ligands. Z is as defined
above.
[0237] In certain variations, a molecular precursor compound of the
MP4 family has the arrangement of atoms described by the formula
Cu(ER.sup.2Z)(ER.sup.3)(ER.sup.4)(In,Ga)R.sup.1, wherein E is S or
Se, R.sup.1, R.sup.3, R.sup.4 and Z are as defined above, and
R.sup.2 is --(CH.sub.2).sub.n--. As used herein, the term alkyl
includes the term alkylene or --(CH.sub.2).sub.n--.
[0238] In certain variations, a molecular precursor compound of the
MP4 family contains an atom M.sup.B, being In or Ga, which is
stabilized by attached ligands. These molecular precursor compounds
further contain an atom M.sup.A, being Cu, which is stabilized by
interactions with one or more chalcogen atoms and the moiety Z as
defined above.
[0239] In further embodiments, the groups R.sup.1, R.sup.2, R.sup.3
and R.sup.4 may independently be (C1-22)alkyl groups. In these
embodiments, the alkyl group may be a (C1)alkyl (methyl), or a
(C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl,
or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a (C9)alkyl, or
a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl, or a (C13)alkyl, or
a (C14)alkyl, or a (C15)alkyl, or a (C16)alkyl, or a (C17)alkyl, or
a (C18)alkyl, or a (C19)alkyl, or a (C20)alkyl, or a (C21)alkyl, or
a (C22)alkyl.
[0240] In certain embodiments, the groups R.sup.1, R.sup.2, R.sup.3
and R.sup.4 may independently be (C1-12)alkyl groups. In these
embodiments, the alkyl group may be a (C1)alkyl (methyl), or a
(C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl,
or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a (C9)alkyl, or
a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl.
[0241] In certain embodiments, the groups R.sup.1, R.sup.2, R.sup.3
and R.sup.4 may independently be (C1-6)alkyl groups. In these
embodiments, the alkyl group may be a (C1)alkyl (methyl), or a
(C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl,
or a (C6)alkyl.
[0242] In further variations, R.sup.1 is (C8)alkyl and R.sup.2,
R.sup.3 and R.sup.4 are the same and are (C3-4)alkyl.
[0243] In other forms, R.sup.1 is (C6)alkyl and R.sup.2, R.sup.3
and R.sup.4 are the same and are (C3-4)alkyl.
[0244] A molecular precursor compound of the MP4 family may be
crystalline, or non-crystalline.
[0245] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas: Cu(S(CH.sub.2).sub.2Se)(S.sup.tBu)(S.sup.nBu)In.sup.iPr;
Cu(S(CH.sub.2).sub.2Se)(S.sup.tBu)(S.sup.nBu)In.sup.nBu;
Cu(Se(CH.sub.2).sub.2NEt)(Se.sup.tBu)(Se.sup.nBu)In.sup.nBu;
Cu(Se(CH.sub.2).sub.2NMe)(Se.sup.tBu)(Se.sup.tBu)In.sup.tBu;
Cu(Se(CH.sub.2).sub.2N(Phenyl))(Se.sup.tBu)(Se.sup.nBu)Ga.sup.tBu;
Cu(Se(CH.sub.2).sub.2N.sup.tBu)(Se.sup.tBu).sub.2Ga.sup.tBu;
Cu(Se(CH.sub.2).sub.2Se)(Se.sup.tBu)(Se.sup.tBu)In.sup.tBu; and
Cu(Se(CH.sub.2).sub.2Se)(Se.sup.tBu).sub.2In.sup.iPr.
[0246] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas:
Cu(S(CH.sub.2).sub.2N.sup.tBu)(S.sup.tBu)(S.sup.nBu)Ga.sup.iPr;
Cu(S(CH.sub.2).sub.2N.sup.iPr)(S.sup.tBu)(S.sup.nBu)Tl.sup.nBu;
Cu(Se(CH.sub.2).sub.2).sub.2N.sup.tBu)(S.sup.tBu)(S.sup.nBu)Ga.sup.nBu;
Cu(S(CH.sub.2).sub.2N.sup.iPr(S.sup.tBu) (S.sup.nBu)Tl.sup.tBu;
Cu(Se(CH.sub.2).sub.2N.sup.tBu)(S.sup.tBu)(S.sup.nBu)Tl.sup.tBu;
and
Cu(Se(CH.sub.2).sub.2N.sup.iPr)(S.sup.tBu)(S.sup.nBu)Ga.sup.iPr.
[0247] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas: Cu(Se(CH.sub.2).sub.3.sup.-)(S.sup.tBu).sub.2In.sup.tBu
and Cu(Se.sup.iPr.sup.-)(S.sup.tBu).sub.2In.sup.tBu.
[0248] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas:
Zn(S(CH.sub.2).sub.2N.sup.tBu)(S.sup.tBu)(S.sup.nBu)In.sup.iPr;
Cd(S(CH.sub.2).sub.2S)(S.sup.tBu)(S.sup.nBu)In.sup.nBu; and
Hg(S(CH.sub.2).sub.2N.sup.iPr)(S.sup.tBu)(S.sup.nBu)Ga.sup.tBu.
[0249] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas:
Cu(S(CH.sub.2).sub.2N.sup.tBu.sub.2).sub.2(S.sup.nBu)In.sup.iPr;
Cu(S(CH.sub.2).sub.2N.sup.tBu.sub.2).sub.2(S.sup.iPr)In.sup.nBu;
Cu(S(CH.sub.2).sub.2SR).sub.2(Se.sup.iPr)In.sup.iPr;
Cu(Te(CH.sub.2).sub.2SeR).sub.2(Se.sup.iPr)In.sup.nBu;
Cu(Se(CH.sub.2).sub.2SeR).sub.2(Te.sup.iPr)In.sup.nBu; and
Cu(S(CH.sub.2).sub.2SeR).sub.2(Te.sup.iPr)In.sup.tBu.
[0250] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas:
Au(S(CH.sub.2).sub.2N.sup.iPr.sub.2).sub.2(S.sup.nBu)In.sup.iPr;
Ag(S(CH.sub.2).sub.2N.sup.tBu.sub.2).sub.2(S.sup.iPr)In.sup.nBu;
Hg(S(CH.sub.2).sub.2SR).sub.2(Se.sup.iPr)In.sup.iPr;
Au(Te(CH.sub.2).sub.2SeR).sub.2(Se.sup.iPr)In.sup.nBu;
Cu(Se(CH.sub.2).sub.2SeR).sub.2(Te.sup.iPr)In.sup.nBu; and
Cu(S(CH.sub.2).sub.2SeR).sub.2(Te.sup.iPr)In.sup.tBu.
[0251] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas:
Cu(S(CH.sub.2).sub.2N.sup.tBu.sub.2)(S.sup.iPr)(S.sup.nBu)In.sup.iPr;
Cu(Se(CH.sub.2).sub.2SeR)(S.sup.iPr)(S.sup.nBu)In.sup.nBu;
Cu(Se(CH.sub.2).sub.2SR)(S.sup.iPr)(Te.sup.nBu)In.sup.tBu; and
Cu(Se(CH.sub.2).sub.2N.sup.iPr.sub.2)(Se.sup.iPr)(Se.sup.nBu)In.sup.iPr.
[0252] Examples of molecular precursor compounds of the MP4 family
of this disclosure include compounds having any one of the
formulas: Cu(S(CH.sub.2).sub.2N.sup.tBu.sub.2).sub.3In(n-octyl);
Cu(S(CH.sub.2).sub.2SeR).sub.3In(n-dodecyl);
Cu(Se(CH.sub.2).sub.2SeR).sub.3In(branched-C18); and
Cu(S(CH.sub.2).sub.2N.sup.tBu.sub.2).sub.3In(branched-C22).
Preparation of Molecular Precursors (MP4)
[0253] Embodiments of this invention provide a family of MP4
precursor molecules which can be synthesized from a compound
containing an atom M.sup.B of Group 13 selected from Al, Ga, In,
and Tl, and a compound containing a monovalent or divalent atom
M.sup.A. Monovalent atoms M.sup.A include Cu, Au, Ag, and Hg.
Divalent atoms M.sup.A include Cu, Zn, Cd, Pt, Pd, Mo, W, Cr, Ni,
Mn, Fe, Co, V, and Hg.
[0254] Advantageously facile routes for the synthesis and isolation
of molecular precursor compounds of this invention are described
below.
[0255] In some aspects, synthesis of a molecular precursor of the
MP4 family begins with providing a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2Z.
[0256] A compound having the formula R.sup.1.sub.2M.sup.BER.sup.2Z
containing a Group 13 atom M.sup.B can be prepared by reacting
M.sup.BR.sup.1.sub.3 with HER.sup.2Z, where R.sup.1, R.sup.2,
R.sup.3, E, and Z are as defined above.
[0257] In other variations, a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2Z containing a Group 13 atom M.sup.B
can be prepared by reacting R.sup.1.sub.2M.sup.BX with
M.sup.CER.sup.2Z, where R.sup.1, R.sup.2 and E are as defined
above, X is halogen, and M.sup.C is an alkali metal.
[0258] To prepare a molecular precursor of the MP4 family with a
monovalent atom M.sup.A, the compound R.sup.1.sub.2M.sup.BER.sup.2Z
may be reacted with a compound containing a monovalent atom M.sup.A
defined above.
[0259] In some embodiments, a compound
R.sup.1.sub.2M.sup.BER.sup.2Z can be contacted with a
chalcogen-containing compound M.sup.A(ER.sup.3) in the presence of
HER.sup.4, where M.sup.A, M.sup.B, E, R.sup.1, R.sup.2, R.sup.3,
and R.sup.4 are as defined above.
[0260] As shown in Reaction Scheme 4a, in some embodiments,
M.sup.BR.sup.1.sub.3 can be reacted with HER.sup.2Z to form
R.sup.1.sub.2M.sup.BER.sup.2Z. The product
R.sup.1.sub.2M.sup.BER.sup.2Z can be contacted with a compound
M.sup.A(ER.sup.3) in the presence of HER.sup.4 to form a molecular
precursor compound having the formula
M.sup.A(ER.sup.2Z)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1. Z is a
neutral moiety in Reaction Scheme 4a.
##STR00014##
[0261] Alternatively, in some embodiments, as shown in Reaction
Scheme 4b, M.sup.BR.sup.1.sub.3 can be reacted with compounds
M.sup.A(ER.sup.3), HER.sup.2Z, and HER.sup.4 to form a molecular
precursor compound having the formula
M.sup.A(ER.sup.2Z)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1. Z is a
neutral moiety in Reaction Scheme 4b.
##STR00015##
[0262] To prepare a molecular precursor of the MP4 family with a
divalent atom M.sup.A, the compound M.sup.AER.sup.3Z may be reacted
with a compound containing an atom M.sup.B defined above.
[0263] In some embodiments, a compound R.sup.1.sub.2M.sup.BER.sup.2
can be contacted with a chalcogen-containing compound
M.sup.AER.sup.3Z in the presence of one equivalent of HER.sup.4,
where M.sup.A, M.sup.B, E, R.sup.1, R.sup.2, R.sup.3, and R.sup.4
are as defined above.
[0264] As shown in Reaction Scheme 4c, in some embodiments,
M.sup.BR.sup.1.sub.3 can be reacted with HER.sup.2 to form
R.sup.1.sub.2M.sup.B ER.sup.2. The product
R.sup.1.sub.2M.sup.BER.sup.2 can be contacted with a compound
M.sup.AER.sup.3Z in the presence of HER.sup.4 to form a molecular
precursor compound having the formula
M.sup.A(ER.sup.3Z)(ER.sup.2)(ER.sup.4)M.sup.BR.sup.1. Z is a
anionic moiety in Reaction Scheme 4c.
##STR00016##
[0265] To prepare a molecular precursor of the MP4 family, in
additional embodiments, the following Reaction Schemes 4d, 4e, and
4f may be used.
##STR00017##
Z is an anionic moiety in Reaction Scheme 4d.
##STR00018##
Q is a leaving group including SiRN.sub.3, wherein R is alkyl. X in
Reaction Schemes 4e and 4f is a leaving group including
halogen.
##STR00019##
[0266] The reactions and manipulations of reagents can be carried
out using known techniques under controlled inert atmosphere, such
as dry nitrogen, and anaerobic conditions using a drybox and a
Schlenk line system.
Molecular Precursors (MP1-Ag) for Semiconductors and
Optoelectronics
[0267] In some embodiments, a molecular precursor compound of the
family MP1-Ag contains an atom M.sup.B of Group 13 selected from
Al, Ga, In, and Tl, which is stabilized by having ligands attached.
These molecular precursor compounds further contain a monovalent
silver (Ag) atom M.sup.A, which is stabilized by interactions with
one or more chalcogen atoms. The atom M.sup.A may further be
stabilized by interacting with another M.sup.A atom. Aside from
interactions with chalcogen atoms, the atom M.sup.A has no other
ligands attached.
[0268] The structure of a family of MP1-Ag precursor molecules
represented by the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1 is shown in
FIG. 1.
[0269] The molecular structure of the family of compounds is of a
dimer, represented by the formula
(M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1).sub.2.
[0270] The local structure surrounding the atom M.sup.B in a
molecule of the MP1-Ag family is a tetrahedral arrangement of four
atoms. At one apex of the M.sup.B tetrahedron is an atom of R.sup.1
through which it is attached to M.sup.B. The remainder of the
tetrahedron is formed by the chalcogen atoms of three of the
ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4), each of which is
attached through a chalcogen atom to M.sup.B.
[0271] The local structure surrounding the atom M.sup.A includes
bonding interactions with three chalcogen atoms that belong to
three of the ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4). The
three ligands (ER.sup.2), (ER.sup.3), and (ER.sup.4), are chalcogen
bridging ligands that are each shared through bonding of their
chalcogen atom to an M.sup.A atom and an M.sup.B atom. The atom
M.sup.A may further be stabilized by interacting with another
M.sup.A atom. Aside from interactions with chalcogen atoms, the
atom M.sup.A has no other ligands attached.
[0272] The portion R.sup.n, where n is 1, 2, 3, or 4, of each of
the ligands attached to the atoms M.sup.A and M.sup.B may be a good
leaving group in relation to a transition of the molecular
precursor compound at elevated temperatures or upon application of
energy.
[0273] The arrangement of atoms in a molecular precursor compound
of the MP1-Ag family may be described by the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1, wherein E is
chalcogen, and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are the same
or different and are groups attached through a carbon or non-carbon
atom, including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and
inorganic and organic ligands. In some embodiments, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are the same or different and are
alkyl groups attached through a carbon atom.
[0274] In some embodiments, molecular precursor compounds of the
MP1-Ag family advantageously do not contain a phosphine ligand, and
do not contain a ligand or attached compound containing phosphorus,
arsenic, or antimony, or a halogen ligand.
[0275] Embodiments of this invention further provide a family
MP1-Ag of molecular precursor compounds in which the arrangement of
atoms may be described by the formula
Ag-(ER.sup.2)(ER.sup.3)(ER.sup.4)(In,Ga)R.sup.1, wherein E is
chalcogen, and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are the same
or different and are groups attached through a carbon or non-carbon
atom, including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and
inorganic and organic ligands. In some embodiments, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are the same or different and are
alkyl groups attached through a carbon atom.
[0276] In certain variations, a molecular precursor compound of the
MP1-Ag family contains an atom M.sup.B, being In or Ga, which is
stabilized by attached ligands. These molecular precursor compounds
further contain an atom M.sup.A, being Ag, which is stabilized by
interactions with one or more chalcogen atoms. The atom M.sup.A may
further be stabilized by interacting with another M.sup.A atom.
Aside from interactions with chalcogen atoms, the atom M.sup.A has
no other ligands attached.
[0277] In additional aspects, a molecular precursor compound may
have the formula
(M.sup.A1-(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4)(M.sup.A2--
(ER.sup.1)(ER.sup.2)(ER.sup.3)M.sup.BR.sup.4), wherein M.sup.A1 is
Ag and M.sup.A2 is Cu, Au or a mixture thereof.
[0278] In further embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 may independently be (C1-22)alkyl groups. In
these embodiments, the alkyl group may be a (C1)alkyl (methyl), or
a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a
(C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a
(C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl, or a
(C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a (C16)alkyl, or a
(C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a (C20)alkyl, or a
(C21)alkyl, or a (C22)alkyl.
[0279] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 may independently be (C1-12)alkyl groups. In
these embodiments, the alkyl group may be a (C1)alkyl (methyl), or
a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a
(C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a
(C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl.
[0280] In certain embodiments, the groups R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 may independently be (C1-6)alkyl groups. In
these embodiments, the alkyl group may be a (C1)alkyl (methyl), or
a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a
(C5)alkyl, or a (C6)alkyl.
[0281] In further variations, R.sup.1 is (C8)alkyl and R.sup.2,
R.sup.3, and R.sup.4 are the same and are (C3-4)alkyl.
[0282] In other forms, R.sup.1 is (C6)alkyl and R.sup.2, R.sup.3,
and R.sup.4 are the same and are (C3-4)alkyl.
[0283] In some aspects, a molecular precursor compound can be
represented by the formula
(M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1).sub.2,
referred to as a dimer, wherein M.sup.A is Ag, which is stabilized
by interactions with one or more chalcogen atoms. The atom M.sup.A
may further be stabilized by interacting with another M.sup.A atom.
Aside from interactions with chalcogen atoms, the atom M.sup.A has
no other ligands attached. M.sup.B is an atom of Ga or In, each E
is independently S or Se, and R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 are as defined above.
[0284] A molecular precursor compound of the MP1-Ag family may be
crystalline, or non-crystalline.
[0285] Examples of molecular precursor compounds of the MP1-Ag
family of this disclosure include compounds having any one of the
formulas: Ag--(S.sup.tBu).sub.3In.sup.iPr;
Ag--(S.sup.tBu).sub.3In.sup.nBu; Ag--(Se.sup.tBu).sub.3In.sup.nBu;
Ag--(S.sup.tBu).sub.3In.sup.tBu; Ag--(Se.sup.tBu).sub.3Ga.sup.nBu;
Ag--(Se.sup.tBu).sub.3Ga.sup.sBu; Ag--(Se.sup.tBu).sub.3Ga.sup.tBu;
Ag--(S.sup.tBu).sub.3Ga.sup.tBu; Ag--(Se.sup.tBu).sub.3In.sup.tBu;
Ag--(Se.sup.tBu).sub.3In.sup.iPr; Ag--(Se.sup.tBu).sub.3In.sup.sBu;
Ag--(Se.sup.tBu).sub.3Ga.sup.iPr; Ag--(S.sup.tBu).sub.3Ga.sup.iPr;
and a dimer of any of the foregoing.
[0286] Examples of molecular precursor compounds of the MP1-Ag
family of this disclosure include compounds having any one of the
formulas: Ag--(S.sup.tBu).sub.3Tl.sup.iPr;
Ag--(S.sup.tBu).sub.3Tl.sup.nBu; Ag--(Se.sup.tBu).sub.3Tl.sup.nBu;
Ag--(S.sup.tBu).sub.3Tl.sup.tBu; Ag--(Se.sup.tBu).sub.3Tl.sup.tBu;
Ag--(Se.sup.tBu).sub.3Tl.sup.iPr; and a dimer of any of the
foregoing.
[0287] Examples of molecular precursor compounds of the MP1-Ag
family of this disclosure include compounds having any one of the
formulas: Ag--(S.sup.nBu).sub.2(S.sup.tBu)In.sup.tBu;
Ag--(S.sup.tBu).sub.2(S.sup.nBu)In.sup.iPr;
Ag--(S.sup.tBu).sub.2(S.sup.iPr)In.sup.nBu;
Ag--(S.sup.tBu).sub.2(Se.sup.iPr)In.sup.iPr;
Ag--(Te.sup.tBu).sub.2(Se.sup.iPr)In.sup.nBu;
Ag--(Se.sup.tBu).sub.2(Te.sup.iPr)In.sup.nBu;
Ag--(S.sup.tBu).sub.2(Te.sup.iPr)In.sup.tBu; and a dimer of any of
the foregoing.
[0288] Examples of molecular precursor compounds of the MP1-Ag
family of this disclosure include compounds having any one of the
formulas: Ag--(S.sup.tBu)(S.sup.iPr)(S.sup.nBu)In.sup.iPr;
Ag--(Se.sup.tBu)(S.sup.iPr)(S.sup.nBu)In.sup.nBu;
Ag--(Se.sup.tBu)(S.sup.iPr)(Te.sup.nBu)In.sup.tBu;
Ag--(Se.sup.tBu)(Se.sup.iPr)(Se.sup.nBu)In.sup.iPr; and a dimer of
any of the foregoing.
[0289] Examples of molecular precursor compounds of the MP1-Ag
family of this disclosure include compounds having any one of the
formulas: Ag--(S.sup.tBu).sub.3In(n-octyl);
Ag--(S.sup.tBu).sub.3In(n-dodecyl);
Ag--(Se.sup.tBu).sub.3In(branched-C18);
Ag--(S.sup.tBu).sub.3In(branched-C22);
Ag--(Se(n-hexyl)).sub.3Ga.sup.tBu;
Ag--(S(n-octyl)).sub.3Ga.sup.tBu; and a dimer of any of the
foregoing.
[0290] As used herein, the term dimer refers to a molecule composed
of two moieties having the same empirical formula. For example,
(Ag--(S.sup.tBu).sub.3In.sup.iPr).sub.2 is a dimer of
Ag--(S.sup.tBu).sub.3In.sup.iPr.
Preparation of Molecular Precursors (MP1-Ag)
[0291] Embodiments of this invention provide a family MP1-Ag of
precursor molecules which can be synthesized from a compound
containing an atom M.sup.B of Group 13 selected from Al, Ga, In,
and Tl, and a compound containing a monovalent silver (Ag) atom
M.sup.A.
[0292] Advantageously facile routes for the synthesis and isolation
of molecular precursor compounds of this invention have been
discovered, as described below.
[0293] In some aspects, synthesis of a molecular precursor of the
MP1-Ag family begins with providing a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2.
[0294] A compound having the formula R.sup.1.sub.2M.sup.BER.sup.2
containing a Group 13 atom M.sup.B can be prepared by reacting
M.sup.BR.sup.1.sub.3 with HER.sup.2, where R.sup.1, R.sup.2, and E
are as defined above.
[0295] In other variations, a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2 containing a Group 13 atom M .sup.B
can be prepared by reacting R.sup.1.sub.2M.sup.BX with
M.sup.CER.sup.2, where R.sup.1, R.sup.2 and E are as defined above,
X is halogen, and M.sup.C is an alkali metal.
[0296] In additional variations, a compound having the formula
R.sup.1.sub.2M.sup.BER.sup.2 containing a Group 13 atom M.sup.B can
be prepared by reacting R.sup.1.sub.2M.sup.BX with
R.sup.2ESi(CH.sub.3).sub.3, where R.sup.1, R.sup.2 and E are as
defined above, and X is halogen.
[0297] To prepare a molecular precursor of the MP1-Ag family, the
compound R.sup.1.sub.2M.sup.BER.sup.2 may be reacted with a
compound containing a monovalent silver (Ag) atom M.sup.A.
[0298] In some embodiments, a compound R.sup.1.sub.2M.sup.BER.sup.2
can be contacted with a chalcogen-containing compound
M.sup.A(ER.sup.3) in the presence of one equivalent of HER.sup.4,
where M.sup.A, M.sup.B, E, R.sup.1, R.sup.2, R.sup.3, and R.sup.4
are as defined above. As shown in Reaction Scheme 5a,
M.sup.BR.sup.1.sub.3 can be reacted with HER.sup.2 to form
R.sup.1.sub.2M.sup.BER.sup.2. The product R can be contacted with a
compound M.sup.A(ER.sup.3) in the presence of one equivalent of
HER.sup.4 to form a molecular precursor compound having the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1.
##STR00020##
In Reaction Scheme 5a, for each occurrence, E may be S, Se, or
Te.
[0299] In certain variations, the starting compound
M.sup.BR.sup.1.sub.3 may be stabilized as an adduct, for example,
as the diethylether adduct, and the diethyl ether may be
removed.
[0300] Alternatively, in some embodiments, M.sup.BR.sup.1.sub.3 can
be reacted with a compound M.sup.A(ER.sup.3) in the presence of two
equivalents of HER.sup.2 to form a molecular precursor compound
having the formula
M.sup.A-(ER.sup.2).sub.2(ER.sup.3)M.sup.BR.sup.1. As shown in
Reaction Scheme 5b, M.sup.BR.sup.1.sub.3 can be reacted with
compounds M.sup.A(ER.sup.3), HER.sup.2, and HER.sup.4 to form a
molecular precursor compound having the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1.
##STR00021##
[0301] In further aspects, a compound
(NR.sup.1.sub.2)M.sup.B(R.sup.2)(ER.sup.3) may be contacted with a
chalcogen-containing compound M.sup.A(ER.sup.4) in the presence of
one equivalent of HER.sup.5, where M.sup.A, M.sup.B, E, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are as defined above, R.sup.5 is
defined the same as R.sup.1, R.sup.2, R.sup.3, and R.sup.4, and
NR.sup.1.sub.2 is amido. As shown in Reaction Scheme 5c,
(NR.sup.1.sub.2)M.sup.BR.sup.2.sub.2 may be reacted with HER.sup.3
to form (NR.sup.1.sub.2)M.sup.B(R.sup.2)(ER.sup.3). The product
(NR.sup.1.sub.2)M.sup.B(R.sup.2)(ER.sup.3) may be contacted with a
compound M.sup.A(ER.sup.4) in the presence of one equivalent of
HER.sup.5 to form a molecular precursor compound having the formula
M.sup.A-(ER.sup.3)(ER.sup.4)(ER.sup.5)M.sup.B(NR.sup.1.sub.2).
##STR00022##
In Reaction Scheme 5c, the ligand (NR.sup.1.sub.2) corresponds to
the R.sup.1 of Reaction Scheme 5a.
[0302] In additional variations, a compound
R.sup.1.sub.2M.sup.BX.sub.2 can be contacted with a
chalcogen-containing compound M.sup.A(ER.sup.2) in the presence of
one equivalent of R.sup.3ESi(CH.sub.3).sub.3 and one equivalent of
R.sup.4ESi(CH.sub.3).sub.3, where M.sup.A, M.sup.B, E, R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are as defined above. As shown in
Reaction Scheme 5d, R.sup.1M.sup.BX.sub.2 can be reacted with
M.sup.A(ER.sup.2), R.sup.3ESi(CH.sub.3).sub.3, and
R.sup.4ESi(CH.sub.3).sub.3 to form a molecular precursor compound
having the formula
M.sup.A-(ER.sup.2)(ER.sup.3)(ER.sup.4)M.sup.BR.sup.1.
##STR00023##
[0303] The reactions and manipulations of reagents can be carried
out using known techniques under controlled inert atmosphere, such
as dry nitrogen, and anaerobic conditions using a drybox and a
Schlenk line system.
[0304] In certain examples, a molecular precursor of the MP1-Ag
family can be synthesized by the following procedure. A Schlenk
tube can be charged with R.sup.1.sub.2M.sup.B(ER.sup.2) and an
equimolar amount of M.sup.A(ER.sup.2) in a glovebox in an inert,
anaerobic atmosphere. To this mixture can be added dry solvent via
cannula on a Schlenk line. The mixture can optionally be heated to
dissolve or disperse the components. An equimolar amount of
HER.sup.2 can be added by use of a syringe and the Schlenk tube
sealed under N.sub.2. The mixture can be heated, optionally for
about 12 hours at a temperature from about 30.degree. C. to about
120.degree. C. The solution can then be cooled, optionally for
several hours at a temperature from about -80.degree. C. to about
15.degree. C. A solid or crystalline product can be isolated.
[0305] Among other things, in some embodiments, certain starting
compounds were made in order to synthesize molecular precursor
molecules of this disclosure. The starting compounds include
certain compounds having one of the formulas M.sup.AER and
R.sup.1.sub.2M.sup.BER.sup.2, where M.sup.B is Ga or In, E is S or
Se, and R.sup.1 and R.sup.2 are alkyl. Examples of the starting
compounds that were prepared include AgSe.sup.tBu,
.sup.nBu.sub.2In(Se.sup.tBu), .sup.tBu.sub.2Ga(Se.sup.tBu), and
.sup.iPr.sub.2In(Se.sup.tBu).
[0306] In one example, .sup.tBuSeH (5.8 mmol) and Et.sub.3N (1.1
mL) were slowly added to a solution of AgNO.sub.3 (1.0 g, 5.8 mmol)
in CH.sub.3CN (20 mL) at 0.degree. C. A colorless solution with
light yellow precipitate formed rapidly. The reaction mixture was
allowed to warm to 25.degree. C. and stirred for 12 h. The excess
.sup.tBuSeH was removed under dynamic vacuum and a grey solid was
recovered. The solid was washed with CH.sub.3CN (2.times.100 mL) to
afford a grey solid, AgSe.sup.tBu (1.23 g, 87%).
Ligands
[0307] As used herein, the term ligand refers to any atom or
chemical moiety that can donate electron density in bonding or
coordination.
[0308] A ligand can be monodentate, bidentate or multidentate.
[0309] As used herein, the term ligand includes Lewis base
ligands.
[0310] As used herein, the term organic ligand refers to an organic
chemical group composed of atoms of carbon and hydrogen, having
from 1 to 22 carbon atoms, and optionally containing oxygen,
nitrogen, sulfur or other atoms, which can bind to another atom or
molecule through a carbon atom. An organic ligand can be branched
or unbranched, substituted or unsubstituted.
[0311] As used herein, the term inorganic ligand refers to an
inorganic chemical group which can bind to another atom or molecule
through a non-carbon atom.
[0312] Examples of ligands include halogens, water, alcohols,
ethers, hydroxyls, amides, carboxylates, chalcogenylates,
thiocarboxylates, selenocarboxylates, tellurocarboxylates,
carbonates, nitrates, phosphates, sulfates, perchlorates, oxalates,
and amines.
[0313] As used herein, the term chalcogenylate refers to
thiocarboxylate, selenocarboxylate, and tellurocarboxylate, having
the formula RCE.sub.2.sup.-, where E is S, Se, or Te.
[0314] As used herein, the term chalcocarbamate refers to
thiocarbamate, selenocarbamate, and tellurocarbamate, having the
formula R.sup.1R.sup.2NCE.sub.2.sup.-, where E is S, Se, or Te, and
R.sup.1 and R.sup.2 are the same or different and are hydrogen,
alkyl, aryl, or an organic ligand.
[0315] Examples of ligands include F, Cl.sup.-, H.sub.2O, ROH,
R.sub.2O, OH.sup.-, RO.sup.-, NR.sub.2.sup.-, RCO.sub.2.sup.-,
RCE.sub.2.sup.-, CO.sub.3.sup.2-, NO.sub.3.sup.-, PO.sub.4.sup.3-,
SO.sub.4.sup.2-, ClO.sub.4.sup.-, C.sub.2O.sub.4.sup.2-, NH.sub.3,
NR.sub.3, R.sub.2NH, and RNH.sub.2, where R is alkyl, and E is
chalcogen.
[0316] Examples of ligands include azides, heteroaryls,
thiocyanates, arylamines, arylalkylamines, nitrites, and
sulfites.
[0317] Examples of ligands include Br.sup.-, N.sub.3.sup.-,
pyridine, [SCN--].sup.-, ArNH.sub.2, NO.sub.2.sup.-, and
SO.sub.3.sup.2- where Ar is aryl.
[0318] Examples of ligands include cyanides or nitriles,
isocyanides or isonitriles, alkylcyanides, alkylnitriles,
alkylisocyanides, alkylisonitriles, arylcyanides, arylnitriles,
arylisocyanides, and arylisonitriles.
[0319] Examples of ligands include hydrides, carbenes, carbon
monoxide, isocyanates, isonitriles, thiolates, alkylthiolates,
dialkylthiolates, thioethers, thiocarbamates, phosphines,
alkylphosphines, arylphosphines, arylalkylphosphines, arsenines,
alkylarsenines, arylarsenines, arylalkylarsenines, stilbines,
alkylstilbines, arylstilbines, and arylalkylstilbines.
[0320] Examples of ligands include I.sup.-, H.sup.-, R.sup.-,
--CN.sup.-, --CO, RNC, RSH, R.sub.2S, RS.sup.-, --SCN.sup.-,
R.sub.3P, R.sub.3As, R.sub.3Sb, alkenes, and aryls, where each R is
independently alkyl, aryl, or heteroaryl.
[0321] Examples of ligands include trioctylphosphine,
trimethylvinylsilane and hexafluoroacetylacetonate.
[0322] Examples of ligands include nitric oxide, silyls,
alkylgermyls, arylgermyls, arylalkylgermyls, alkylstannyls,
arylstannyls, arylalkylstannyls, selenocyanates, selenolates,
alkylselenolates, dialkylselenolates, selenoethers,
selenocarbamates, tellurocyanates, tellurolates, alkyltellurolates,
dialkyltellurolates, telluroethers, and tellurocarbamates.
[0323] Examples of ligands include chalcogenates, thiothiolates,
selenothiolates, thioselenolates, selenoselenolates, alkyl
thiothiolates, alkyl selenothiolates, alkyl thioselenolates, alkyl
selenoselenolates, aryl thiothiolates, aryl selenothiolates, aryl
thioselenolates, aryl selenoselenolates, arylalkyl thiothiolates,
arylalkyl selenothiolates, arylalkyl thioselenolates, and arylalkyl
selenoselenolates.
[0324] Examples of ligands include selenoethers and
telluroethers.
[0325] Examples of ligands include NO, O.sup.2-, NH.sub.nR.sub.3-n,
PH.sub.nR.sub.3-n, SiR.sub.3.sup.-, GeR.sub.3.sup.-,
SnR.sub.3.sup.-, .sup.-SR, .sup.-SeR, .sup.-TeR, .sup.-SSR,
.sup.-SeSR, .sup.-SSeR, .sup.-SeSeR, and RCN, where n is from 1 to
3, and each R is independently alkyl or aryl.
[0326] As used herein, the term transition metals refers to atoms
of Groups 3 though 12 of the Periodic Table of the elements
recommended by the Commission on the Nomenclature of Inorganic
Chemistry and published in IUPAC Nomenclature of Inorganic
Chemistry, Recommendations 2005.
Photovoltaic Absorber Layer Compositions
[0327] A molecular precursor may be used to prepare a material for
use in developing semiconductor products.
[0328] A molecular precursor may be used to prepare an absorber
material for a solar cell product.
[0329] In some aspects, one or more molecular precursors may be
used to prepare a CIS or CIGS material as a photovoltaic layer.
[0330] In some variations, one or more molecular precursors may be
used to prepare a chemically and physically uniform semiconductor
CIS or CIGS layer on a variety of substrates, including flexible
substrates.
[0331] The CIS or CIGS layer may be used with various junction
partners to produce a solar cell. Examples of junction partner
layers are known in the art and include CdS, ZnS, ZnSe, and CdZnS.
See, for example, Martin Green, Solar Cells: Operating Principles,
Technology and System Applications (1986); Richard H. Bube,
Photovoltaic Materials (1998); Antonio Luque and Steven Hegedus,
Handbook of Photovoltaic Science and Engineering (2003).
[0332] In some aspects, the thickness of an absorber layer may be
from about 0.001 to about 100 micrometers, or from about 0.001 to
about 20 micrometers, or from about 0.01 to about 10 micrometers,
or from about 0.05 to about 5 micrometers, or from about 0.1 to
about 4 micrometers, or from about 0.1 to about 3.5 micrometers, or
from about 0.1 to about 3 micrometers, or from about 0.1 to about
2.5 micrometers.
Substrates
[0333] The molecular precursors of this invention can be used to
form a layer on a substrate. The substrate can be made of any
substance, and can have any shape. Substrate layers of molecular
precursors can be used to create a photovoltaic layer or
device.
[0334] Examples of substrates on which a molecular precursor of
this disclosure can be deposited or printed include semiconductors,
doped semiconductors, silicon, gallium arsenide, insulators, glass,
silicon dioxide, titanium dioxide, zinc oxide, silicon nitride, and
combinations thereof.
[0335] A substrate may be coated with molybdenum or a
molybdenum-containing compound.
[0336] In some embodiments, a substrate may be pre-treated with a
molybdenum-containing compound, or one or more compounds containing
molybdenum and selenium.
[0337] Examples of substrates on which a molecular precursor of
this disclosure can be deposited or printed include metals, metal
foils, molybdenum, aluminum, beryllium, cadmium, cerium, chromium,
cobalt, copper, gallium, gold, lead, manganese, nickel, palladium,
platinum, rhenium, rhodium, silver, stainless steel, steel, iron,
strontium, tin, titanium, tungsten, zinc, zirconium, metal alloys,
metal silicides, metal carbides, and combinations thereof.
[0338] Examples of substrates on which a molecular precursor of
this disclosure can be deposited or printed include polymers,
plastics, conductive polymers, copolymers, polymer blends,
polyethylene terephthalates, polycarbonates, polyesters, polyester
films, mylars, polyvinyl fluorides, polyvinylidene fluoride,
polyethylenes, polyetherimides, polyethersulfones,
polyetherketones, polyimides, polyvinylchlorides, acrylonitrile
butadiene styrene polymers, silicones, epoxys, and combinations
thereof.
[0339] Examples of substrates on which a molecular precursor of
this disclosure can be deposited or printed include papers and
coated papers.
[0340] A substrate of this disclosure can be of any shape. Examples
of substrates on which a precursor of this disclosure can be
deposited include a shaped substrate including a tube, a cylinder,
a roller, a rod, a pin, a shaft, a plate, a blade, a vane, or a
spheroid.
[0341] A substrate may be layered with an adhesion promoter before
the deposition, coating or printing of a layer of a molecular
precursor of this invention.
[0342] Examples of adhesion promoters include a glass layer, a
metal layer, a titanium-containing layer, a tungsten-containing
layer, a tantalum-containing layer, tungsten nitride, tantalum
nitride, titanium nitride, titanium nitride silicide, tantalum
nitride silicide, a chromium-containing layer, a
vanadium-containing layer, a nitride layer, an oxide layer, a
carbide layer, and combinations thereof.
[0343] Examples of adhesion promoters include organic adhesion
promoters such as organofunctional silane coupling agents, silanes,
hexamethyldisilazanes, glycol ether acetates, ethylene glycol
bis-thioglycolates, acrylates, acrylics, mercaptans, thiols,
selenols, tellurols, carboxylic acids, organic phosphoric acids,
triazoles, and mixtures thereof.
[0344] Substrates may be layered with a barrier layer before the
deposition of printing of a layer of a molecular precursor of this
invention.
[0345] Examples of a barrier layer include a glass layer, a metal
layer, a titanium-containing layer, a tungsten-containing layer, a
tantalum-containing layer, tungsten nitride, tantalum nitride,
titanium nitride, titanium nitride silicide, tantalum nitride
silicide, and combinations thereof.
[0346] A substrate can be of any thickness, and can be from about
20 micrometers to about 20,000 micrometers or more in
thickness.
Ink Compositions
[0347] Embodiments of this invention further provide ink
compositions which contain one or more molecular precursor
compounds. The molecular precursors of this invention may be used
to make photovoltaic materials by printing an ink onto a
substrate.
[0348] An ink of this disclosure advantageously allows precise
control of the stoichiometric ratios of certain atoms in the ink
because the ink can be composed of a mixture of molecular
precursors.
[0349] Inks of this disclosure can be made by any methods known in
the art.
[0350] In some embodiments, an ink can be made by mixing a
molecular precursor with one or more carriers. The ink may be a
suspension of the molecular precursors in an organic carrier. In
some variations, the ink is a solution of the molecular precursors
in an organic carrier. The carrier can be an organic liquid, or an
organic solvent with an aqueous component.
[0351] An ink can be made by providing one or more molecular
precursor compounds and solubilizing, dissolving, solvating, or
dispersing the compounds with one or more carriers. The compounds
dispersed in a carrier may be nanocrystalline, nanoparticles,
microparticles, amorphous, or dissolved molecules.
[0352] The concentration of the molecular precursors in an ink of
this disclosure can be from about 0.001% to about 99% (w/w), or
from about 0.001% to about 90%, or from about 0.1% to about
90%.
[0353] A molecular precursor may exist in a liquid phase under the
temperature and conditions used for deposition, coating or
printing.
[0354] In some variations of this invention, molecular precursors
that are partially soluble, or are insoluble in a particular
carrier can be dispersed in the carrier by high shear mixing.
[0355] As used herein, the term dispersing encompasses the terms
solubilizing, dissolving, and solvating.
[0356] The carrier for an ink of this disclosure may be an organic
liquid or solvent. Examples of a carrier for an ink of this
disclosure include one or more organic solvents, which may contain
an aqueous component.
[0357] Embodiments of this invention further provide molecular
precursor compounds having enhanced solubility in one or more
carriers for preparing inks. The solubility of a molecular
precursor compound can be selected by variation of the nature and
molecular size and weight of one or more organic ligands attached
to the molecule.
[0358] Ink compositions of this disclosure can be made by methods
known in the art, as well as methods disclosed herein.
[0359] Examples of a carrier for an ink of this disclosure include
water, alcohol, methanol, ethanol, isopropyl alcohol, thiols,
butanol, butanediol, glycerols, alkoxyalcohols, glycols,
1-methoxy-2-propanol, acetone, ethylene glycol, propylene glycol,
propylene glycol laurate, ethylene glycol ethers, diethylene
glycol, triethylene glycol monobutylether, propylene glycol
monomethylether, 1,2-hexanediol, ethers, diethyl ether, aliphatic
hydrocarbons, aromatic hydrocarbons, pentane, hexane, heptane,
octane, isooctane, decane, cyclohexane, p-xylene, benzene, toluene,
xylene, tetrahydrofuran, siloxanes, cyclosiloxanes, silicone
fluids, halogenated hydrocarbons, dibromomethane, dichloromethane,
dichloroethane, trichloroethane chloroform, methylene chloride,
acetonitrile, esters, acetates, ethyl acetate, butyl acetate,
acrylates, isobornyl acrylate, 1,6-hexanediol diacrylate,
polyethylene glycol diacrylate, ketones, acetone, methyl ethyl
ketone, cyclohexanone, butyl carbitol, cyclopentanone,
cyclohexanone, lactams, N-methylpyrrolidone,
N-(2-hydroxyethyl)-pyrrolidone, cyclic acetals, cyclic ketals,
aldehydes, amides, dimethylformamide, methyl lactate, oils, natural
oils, terpenes, and mixtures thereof.
[0360] An ink of this disclosure may further include components
such as a surfactant, a dispersant, an emulsifier, an anti-foaming
agent, a dryer, a filler, a resin binder, a thickener, a viscosity
modifier, an anti-oxidant, a flow agent, a plasticizer, a
conductivity agent, a crystallization promoter, an extender, a film
conditioner, an adhesion promoter, and a dye. Each of these
components may be used in an ink of this disclosure at a level of
from about 0.001% to about 10% or more of the ink composition.
[0361] Examples of surfactants include siloxanes, polyalkyleneoxide
siloxanes, polyalkyleneoxide polydimethylsiloxanes, polyester
polydimethylsiloxanes, ethoxylated nonylphenols, nonylphenoxy
polyethyleneoxyethanol, fluorocarbon esters, fluoroaliphatic
polymeric esters, fluorinated esters, alkylphenoxy alkyleneoxides,
cetyl trimethyl ammonium chloride, carboxymethylamylose,
ethoxylated acetylene glycols, betaines,
N-n-dodecyl-N,N-dimethylbetaine, dialkyl sulfosuccinate salts,
alkylnaphthalenesulfonate salts, fatty acid salts, polyoxyethylene
alkylethers, polyoxyethylene alkylallylethers,
polyoxyethylene-polyoxypropylene block copolymers, alkylamine
salts, quaternary ammonium salts, and mixtures thereof.
[0362] Examples of surfactants include anionic, cationic,
amphoteric, and nonionic surfactants. Examples of surfactants
include SURFYNOL, DYNOL, ZONYL, FLUORAD, and SILWET
surfactants.
[0363] A surfactant may be used in an ink of this disclosure at a
level of from about 0.001% to about 2% of the ink composition.
[0364] Examples of a dispersant include a polymer dispersant, a
surfactant, hydrophilic-hydrophobic block copolymers, acrylic block
copolymers, acrylate block copolymers, graft polymers, and mixtures
thereof.
[0365] Examples of an emulsifier include a fatty acid derivative,
an ethylene stearamide, an oxidized polyethylene wax, mineral oils,
a polyoxyethylene alkyl phenol ether, a polyoxyethylene glycol
ether block copolymer, a polyoxyethylene sorbitan fatty acid ester,
a sorbitan, an alkyl siloxane polyether polymer, polyoxyethylene
monostearates, polyoxyethylene monolaurates, polyoxyethylene
monooleates, and mixtures thereof.
[0366] Examples of an anti-foaming agent include polysiloxanes,
dimethylpolysiloxanes, dimethyl siloxanes, silicones, polyethers,
octyl alcohol, organic esters, ethyleneoxide propyleneoxide
copolymers, and mixtures thereof.
[0367] Examples of a dryer include aromatic sulfonic acids,
aromatic carboxylic acids, phthalic acid, hydroxyisophthalic acid,
N-phthaloylglycine, 2-Pyrrolidone 5-carboxylic acid, and mixtures
thereof.
[0368] Examples of a filler include metallic fillers, silver
powder, silver flake, metal coated glass spheres, graphite powder,
carbon black, conductive metal oxides, ethylene vinyl acetate
polymers, and mixtures thereof.
[0369] Examples of a resin binder include acrylic resins, alkyd
resins, vinyl resins, polyvinyl pyrrolidone, phenolic resins,
ketone resins, aldehyde resins, polyvinyl butyral resin, amide
resins, amino resins, acrylonitrile resins, cellulose resins,
nitrocellulose resins, rubbers, fatty acids, epoxy resins, ethylene
acrylic copolymers, fluoropolymers, gels, glycols, hydrocarbons,
maleic resins, urea resins, natural rubbers, natural gums, phenolic
resins, cresols, polyamides, polybutadienes, polyesters,
polyolefins, polyurethanes, isocynates, polyols, thermoplastics,
silicates, silicones, polystyrenes, and mixtures thereof.
[0370] Examples of thickeners and viscosity modifiers include
conducting polymers, celluloses, urethanes, polyurethanes, styrene
maleic anhydride copolymers, polyacrylates, polycarboxylic acids,
carboxymethylcelluoses, hydroxyethylcelluloses, methylcelluloses,
methyl hydroxyethyl celluloses, methyl hydroxypropyl celluloses,
silicas, gellants, aluminates, titanates, gums, clays, waxes,
polysaccharides, starches, and mixtures thereof.
[0371] Examples of anti-oxidants include phenolics, phosphites,
phosphonites, thioesters, stearic acids, ascorbic acids, catechins,
cholines, and mixtures thereof.
[0372] Examples of flow agents include waxes, celluloses,
butyrates, surfactants, polyacrylates, and silicones.
[0373] Examples of a plasticizer include alkyl benzyl phthalates,
butyl benzyl phthalates, dioctyl phthalates, diethyl phthalates,
dimethyl phthalates, di-2-ethylhexy-adipates, diisobutyl
phthalates, diisobutyl adipates, dicyclohexyl phthalates, glycerol
tribenzoates, sucrose benzoates, polypropylene glycol dibenzoates,
neopentyl glycol dibenzoates, dimethyl isophthalates, dibutyl
phthalates, dibutyl sebacates, tri-n-hexyltrimellitates, and
mixtures thereof.
[0374] Examples of a conductivity agent include lithium salts,
lithium trifluoromethanesulfonates, lithium nitrates, dimethylamine
hydrochlorides, diethylamine hydrochlorides, hydroxylamine
hydrochlorides, and mixtures thereof.
[0375] Examples of a crystallization promoter include alkali metal
salts, alkaline earth metal salts, sodium chalcogenates, cadmium
salts, cadmium sulfates, cadmium sulfides, cadmium selenides,
cadmium tellurides, indium sulfides, indium selenides, indium
tellurides, gallium sulfides, gallium selenides, gallium
tellurides, molybdenum, molybdenum sulfides, molybdenum selenides,
molybdenum tellurides, molybdenum-containing compounds, and
mixtures thereof.
[0376] An ink may contain one or more components selected from the
group of a conducting polymer, copper metal, indium metal, gallium
metal, zinc metal, alkali metals, alkali metal salts, alkaline
earth metal salts, sodium chalcogenates, calcium chalcogenates,
cadmium sulfide, cadmium selenide, cadmium telluride, indium
sulfide, indium selenide, indium telluride, gallium sulfide,
gallium selenide, gallium telluride, zinc sulfide, zinc selenide,
zinc telluride, copper sulfide, copper selenide, copper telluride,
molybdenum sulfide, molybdenum selenide, molybdenum telluride, and
mixtures of any of the foregoing.
[0377] An ink of this disclosure may contain particles of a metal,
a conductive metal, or an oxide. Examples of metal and oxide
particles include silica, alumina, titania, copper, iron, steel,
aluminum and mixtures thereof.
[0378] In certain variations, an ink may contain a biocide, a
sequestering agent, a chelator, a humectant, a coalescent, or a
viscosity modifier.
[0379] In certain aspects, an ink of this disclosure may be formed
as a solution, a suspension, a slurry, or a semisolid gel or paste.
An ink may include one or more molecular precursors solubilized in
a carrier, or may be a solution of the molecular precursors. In
certain variations, a molecular precursor may include particles or
nanoparticles that can be suspended in a carrier, and may be a
suspension or paint of the molecular precursors. In certain
embodiments, a molecular precursor can be mixed with a minimal
amount of a carrier, and may be a slurry or semisolid gel or paste
of the molecular precursor.
[0380] The viscosity of an ink of this disclosure can be from about
0.5 centipoises (cP) to about 50 cP, or from about 0.6 to about 30
cP, or from about 1 to about 15 cP, or from about 2 to about 12
cP.
[0381] The viscosity of an ink of this disclosure can be from about
20 cP to about 2.times.10.sup.6 cP, or greater. The viscosity of an
ink of this disclosure can be from about 20 cP to about
1.times.10.sup.6 cP, or from about 200 cP to about 200,000 cP, or
from about 200 cP to about 100,000 cP, or from about 200 cP to
about 40,000 cP, or from about 200 cP to about 20,000 cP.
[0382] The viscosity of an ink of this disclosure can be about 1
cP, or about 2 cP, or about 5 cP, or about 20 cP, or about 100 cP,
or about 500 cP, or about 1,000 cP, or about 5,000 cP, or about
10,000 cP, or about 20,000 cP, or about 30,000 cP, or about 40,000
cP.
[0383] An ink may be composed of one or more molecular precursor
compounds and one or more carriers. The ink may be a suspension or
solution of the compounds in an organic carrier. An ink may further
contain an additional indium-containing compound, such as
In(SeR).sub.3, wherein R is alkyl or aryl. An ink may further
contain an additional indium-containing compound, such as
In(SeR).sub.3, and an additional gallium-containing compound, such
as Ga(SeR).sub.3, wherein R is alkyl or aryl. For example, an ink
may further contain In(Se.sup.nBu).sub.3 and Ga(Se.sup.nBu).sub.3.
In some embodiments, an ink may contain one or more components from
the group of a surfactant, a dispersant, an emulsifier, an
anti-foaming agent, a dryer, a filler, a resin binder, a thickener,
a viscosity modifier, an anti-oxidant, a flow agent, a plasticizer,
a conductivity agent, a crystallization promoter, an extender, a
film conditioner, an adhesion promoter, and a dye. In certain
variations, an ink may contain one or more compounds from the group
of cadmium sulfide, cadmium selenide, cadmium telluride, zinc
sulfide, zinc selenide, zinc telluride, copper sulfide, copper
selenide, and copper telluride. In some aspects, an ink may contain
particles of a metal, a conductive metal, or an oxide.
[0384] An ink may be made by dispersing one or more molecular
precursor compounds of this disclosure in one or more carriers to
form a dispersion or solution.
[0385] A molecular precursor ink composition can be prepared by
dispersing one or more molecular precursors in a solvent, and
heating the solvent to dissolve or disperse the molecular
precursors. The molecular precursors may have a concentration of
from about 0.001% to about 99% (w/w), or from about 0.001% to about
90%, or from about 0.1% to about 90%, or from about 0.1% to about
50%, or from about 0.1% to about 40%, or from about 0.1% to about
30%, or from about 0.1% to about 20%, or from about 0.1% to about
10% in the solution or dispersion. To the solution or dispersion
can also be added sources of a Group 13 compound or a chalcogen
compound. For example, an ink may contain either one or both of
In(ER).sub.3 and Ga(ER).sub.3, where each R is the same or
different alkyl or aryl, in a total amount representing 0.1
atom-equivalents of indium plus gallium relative to the amount of
copper in the molecular precursors. To this solution or dispersion
can be added a binder, for example, polyvinyl pyrrolidone, and a
thickener, for example, methylcelluose. Other components may be
added as described above.
Processes for Films of Molecular Precursors on Substrates
[0386] The molecular precursors of this invention can be used to
make photovoltaic materials by depositing a layer onto a substrate,
where the layer contains one or more molecular precursors. The
deposited layer may be a film or a thin film. Substrates are
described above.
[0387] As used herein, the terms "deposit," "depositing," and
"deposition" refer to any method for placing a compound or
composition onto a surface or substrate, including spraying,
coating, and printing.
[0388] As used herein, the term "thin film" refers to a layer of
atoms or molecules, or a composition layer on a substrate having a
thickness of less than about 300 micrometers.
[0389] A deposited layer of this disclosure advantageously allows
precise control of the stoichiometric ratios of certain atoms in
the layer because the layer can be composed of a mixture of
molecular precursors.
[0390] The molecular precursors of this invention, and compositions
containing molecular precursors, can be deposited onto a substrate
using methods known in the art, as well as methods disclosed
herein.
[0391] Examples of methods for depositing a molecular precursor
onto a surface or substrate include all forms of spraying, coating,
and printing.
[0392] Solar cell layers can be made by depositing one or more
molecular precursors of this disclosure on a flexible substrate in
a high throughput roll process. The depositing of molecular
precursors in a high throughput roll process can be done by
spraying or coating a composition containing one or more molecular
precursors, or by printing an ink containing one or more molecular
precursors of this disclosure.
[0393] Examples of methods for depositing a molecular precursor
onto a surface or substrate include spraying, spray coating, spray
deposition, spray pyrolysis, and combinations thereof.
[0394] Examples of methods for printing using an ink of this
disclosure include screen printing, inkjet printing, aerosol jet
printing, ink printing, jet printing, stamp/pad printing, transfer
printing, pad printing, flexographic printing, gravure printing,
contact printing, reverse printing, thermal printing, lithography,
electrophotographic printing, and combinations thereof.
[0395] Examples of methods for depositing a molecular precursor
onto a surface or substrate include electrodepositing,
electroplating, electroless plating, bath deposition, coating, dip
coating, wet coating, spin coating, knife coating, roller coating,
rod coating, slot die coating, meyerbar coating, lip direct
coating, capillary coating, liquid deposition, solution deposition,
layer-by-layer deposition, spin casting, solution casting, chemical
vapor deposition, aerosol chemical vapor deposition, metal-organic
chemical vapor deposition, organometallic chemical vapor
deposition, plasma enhanced chemical vapor deposition, and
combinations thereof.
[0396] Examples of methods for depositing a molecular precursor
onto a surface or substrate include atomic layer deposition,
plasma-enhanced atomic layer deposition, vacuum chamber deposition,
sputtering, RF sputtering, DC sputtering, magnetron sputtering,
evaporation, electron beam evaporation, laser ablation, gas-source
molecular beam epitaxy, vapor phase epitaxy, liquid phase epitaxy,
and combinations thereof.
[0397] In certain embodiments, a first molecular precursor may be
deposited onto a substrate, and subsequently a second molecular
precursor may be deposited onto the substrate. In certain
embodiments, several different molecular precursors may be
deposited onto the substrate to create a layer.
[0398] In certain variations, different molecular precursors may be
deposited onto a substrate simultaneously, or sequentially, whether
by spraying, coating, printing, or by other methods. The different
molecular precursors may be contacted or mixed before the
depositing step, during the depositing step, or after the
depositing step. The molecular precursors can be contacted before,
during, or after the step of transporting the molecular precursors
to the substrate surface.
[0399] The depositing of molecular precursors, including by
spraying, coating, and printing, can be done in a controlled or
inert atmosphere, such as in dry nitrogen and other inert gas
atmospheres, as well as in a vacuum atmosphere.
[0400] Processes for depositing, spraying, coating, or printing
molecular precursors can be done at various temperatures including
from about -20.degree. C. to about 650.degree. C., or from about
-20.degree. C. to about 600.degree. C., or from about -20.degree.
C. to about 400.degree. C., or from about 20.degree. C. to about
360.degree. C., or from about 20.degree. C. to about 300.degree.
C., or from about 20.degree. C. to about 250.degree. C.
[0401] Processes for making a solar cell involving a step of
transforming a molecular precursor compound into a material or
semiconductor can be performed at various temperatures including
from about 100.degree. C. to about 650.degree. C., or from about
150.degree. C. to about 650.degree. C., or from about 250.degree.
C. to about 650.degree. C., or from about 300.degree. C. to about
650.degree. C., or from about 400.degree. C. to about 650.degree.
C.
[0402] In certain aspects, depositing of molecular precursors on a
substrate can be done while the substrate is heated. In these
variations, a thin-film material may be deposited or formed on the
substrate.
[0403] In some embodiments, a step of converting a precursor to a
material and a step of annealing can be done simultaneously. In
general, a step of heating a precursor can be done before, during
or after any step of depositing the precursor.
[0404] In some variations, a substrate can be cooled after a step
of heating. In certain embodiments, a substrate can be cooled
before, during, or after a step of depositing a precursor. A
substrate may be cooled to return the substrate to a lower
temperature, or to room temperature, or to an operating temperature
of a deposition unit. Various coolants or cooling methods can be
applied to cool a substrate.
[0405] The depositing of molecular precursors on a substrate may be
done with various apparatuses and devices known in art, as well as
devices described herein.
[0406] In some variations, the depositing of molecular precursors
can be performed using a spray nozzle with adjustable nozzle
dimensions to provide a uniform spray composition and
distribution.
[0407] Embodiments of this disclosure further contemplate articles
made by depositing a layer onto a substrate, where the layer
contains one or more molecular precursors. The article may be a
substrate having a layer of a film, or a thin film, which is
deposited, sprayed, coated, or printed onto the substrate. In
certain variations, an article may have a substrate printed with a
molecular precursor ink, where the ink is printed in a pattern on
the substrate.
Photovoltaic Devices
[0408] The molecular precursors of this invention can be used to
make photovoltaic materials and solar cells of high efficiency.
[0409] As shown in FIG. 6, embodiments of this invention may
further provide optoelectronic devices and energy conversion
systems. Following the synthesis of molecular precursor compounds,
the compounds can be sprayed, deposited, or printed onto substrates
and formed into absorber materials and semiconductor layers.
Absorber materials can be the basis for optoelectronic devices and
energy conversion systems.
[0410] In some embodiments, the solar cell is a thin layer solar
cell having a CIS or CIGS absorber layer deposited or printed on a
substrate. Some methods for solar cells are disclosed in U.S. Pat.
Nos. 5,441,897, 5,976,614, 6,518,086, 5,436,204, 7,179,677, and PCT
International Application Publication Nos. WO2008057119 and
WO2008063190.
[0411] In some embodiments, a solar cell of this disclosure is a
heterojunction device made with a CIS or CIGS cell. The CIS or CIGS
layer may be used as a junction partner with a layer of, for
example, cadmium sulfide, cadmium selenide, cadmium telluride, zinc
sulfide, zinc selenide, or zinc telluride. The absorber layer may
be adjacent to a layer of MgS, MgSe, MgTe, HgS, HgSe, HgTe, AN,
AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, or
combinations thereof.
[0412] In certain variations, a solar cell of this disclosure is a
multijunction device made with one or more stacked solar cells.
[0413] As shown in FIG. 7, a solar cell device of this disclosure
may have a substrate 10, an electrode layer 20, an absorber layer
30, a window layer 40, and a transparent conductive layer (TCO) 50.
The substrate 10 may be metal, plastic, glass, or ceramic. The
electrode layer 20 can be a molybdenum-containing layer. The
absorber layer 30 may be a CIS or CIGS layer. The window layer 40
may be a cadmium sulfide layer. The transparent conductive layer 50
can be an indium tin oxide layer or a doped zinc oxide layer.
[0414] A solar cell device of this disclosure may have a substrate,
an electrode layer, an absorber layer, a window layer, an adhesion
promoting layer, a junction partner layer, a transparent layer, a
transparent electrode layer, a transparent conductive oxide layer,
a transparent conductive polymer layer, a doped conductive polymer
layer, an encapsulating layer, an anti-reflective layer, a
protective layer, or a protective polymer layer. In certain
variations, an absorber layer includes a plurality of absorber
layers.
[0415] In certain variations, solar cells may be made by processes
using molecular precursor compounds and compositions of this
invention that advantageously avoid additional sulfurization or
selenization steps.
[0416] In certain variations, a solar cell device may have a
molybdenum-containing layer, or an interfacial
molybdenum-containing layer.
[0417] Examples of a protective polymer include silicon rubbers,
butyryl plastics, ethylene vinyl acetates, and combinations
thereof.
[0418] Substrates can be made of a flexible material which can be
handled in a roll. The electrode layer may be a thin foil.
[0419] Absorber layers of this disclosure can be made by depositing
or printing a composition containing nanoparticles onto a
substrate, where the nanoparticles can be made with molecular
precursor compounds of this invention. In some processes,
nanoparticles can be made with molecular precursor compounds and
deposited on a substrate. Deposited nanoparticles can subsequently
be transformed by the application of heat or energy.
Sources of Metals
[0420] Sources of copper include copper metal, Cu(I), Cu(II),
copper halides, copper chlorides, copper acetates, copper
alkoxides, copper alkyls, copper diketonates, copper
2,2,6,6,-tetramethyl-3,5,-heptanedionate, copper
2,4-pentanedionate, copper hexafluoroacetylacetonate, copper
acetylacetonate, copper dimethylaminoethoxide, copper ketoesters,
and mixtures thereof.
[0421] Sources of indium include indium metal, trialkylindium,
trisdialkylamineindium, indium halides, indium chlorides,
dimethylindium chlorides, trimethylindium, indium acetylacetonates,
indium hexafluoropentanedionates, indium methoxyethoxides, indium
methyltrimethylacetylacetates, indium trifluoropentanedionates, and
mixtures thereof.
[0422] Sources of gallium include gallium metal, trialkylgallium,
trisdialkylamine gallium, gallium halides, gallium fluorides,
gallium chlorides, gallium iodides, diethylgallium chlorides,
gallium acetate, gallium 2,4-pentanedionate, gallium ethoxide,
gallium 2,2,6,6,-tetramethylheptanedionate,
trisdimethylaminogallium, and mixtures thereof.
[0423] Some sources of gallium and indium are described in
International Patent Publication No. WO2008057119.
[0424] In various processes of this disclosure, a composition or
material may optionally be subjected to a step of sulfurization or
selenization.
[0425] Sulfurization with H.sub.2S or selenization with H.sub.2Se
may be carried out by using pure H.sub.2S or H.sub.2Se,
respectively, or may be done by dilution in hydrogen or in
nitrogen. Selenization can also be carried out with Se vapor, or
other source of elemental selenium.
[0426] A sulfurization or selenization step can be done at any
temperature from about 200.degree. C. to about 600.degree. C., or
at temperatures below 200.degree. C. One or more steps of
sulfurization and selenization may be performed concurrently, or
sequentially.
[0427] Examples of sulfurizing agents include hydrogen sulfide,
hydrogen sulfide diluted with hydrogen, elemental sulfur, sulfur
powder, carbon disulfide, alkyl polysulfides, dimethyl sulfide,
dimethyl disulfide, and mixtures thereof.
[0428] A sulfurization or selenization step can also be done with
co-deposition of another metal such as copper, indium, or
gallium.
Chemical Definitions
[0429] As used herein, the term (A,B) when referring to compounds
or atoms indicates that either A or B, or a combination thereof may
be found in the formula. For example, (S,Se) indicates that atoms
of either sulfur or selenium, or a combination thereof may be
found.
[0430] The atoms S, Se, and Te of Group 16 are referred to as
chalcogens.
[0431] As used herein, the term "chalcogenide" refers to a compound
containing one or more chalcogen atoms bonded to one or more metal
atoms.
[0432] The term "alkyl" as used herein refers to a hydrocarbyl
radical of a saturated aliphatic group, which can be a branched or
unbranched, substituted or unsubstituted aliphatic group containing
from 1 to 22 carbon atoms. This definition applies to the alkyl
portion of other groups such as, for example, cycloalkyl, alkoxy,
alkanoyl, aralkyl, and other groups defined below. The term
"cycloalkyl" as used herein refers to a saturated, substituted or
unsubstituted cyclic alkyl ring containing from 3 to 12 carbon
atoms. As used herein, the term "C(1-5)alkyl" includes C(1)alkyl,
C(2)alkyl, C(3)alkyl, C(4)alkyl, and C(5)alkyl. Likewise, the term
"C(3-22)alkyl" includes C(1)alkyl, C(2)alkyl, C(3)alkyl, C(4)alkyl,
C(5)alkyl, C(6)alkyl, C(7)alkyl, C(8)alkyl, C(9)alkyl, C(10)alkyl,
C(11)alkyl, C(12)alkyl, C(13)alkyl, C(14)alkyl, C(15)alkyl,
C(16)alkyl, C(17)alkyl, C(18)alkyl, C(19)alkyl, C(20)alkyl,
C(21)alkyl, and C(22)alkyl.
[0433] The term "alkenyl" as used herein refers to an unsaturated,
branched or unbranched, substituted or unsubstituted alkyl or
cycloalkyl having 2 to 22 carbon atoms and at least one
carbon-carbon double bond. The term "alkynyl" as used herein refers
to an unsaturated, branched or unbranched, substituted or
unsubstituted alkyl or cycloalkyl having 2 to 22 carbon atoms and
at least one carbon-carbon triple bond.
[0434] The term "alkoxy" as used herein refers to an alkyl,
cycloalkyl, alkenyl, or alkynyl group covalently bonded to an
oxygen atom. The term "alkanoyl" as used herein refers to
--C(.dbd.O)-alkyl, which may alternatively be referred to as
"acyl." The term "alkanoyloxy" as used herein refers to
--O--C(.dbd.O)-alkyl groups. The term "alkylamino" as used herein
refers to the group --NRR', where R and R' are each either hydrogen
or alkyl, and at least one of R and R' is alkyl. Alkylamino
includes groups such as piperidino wherein R and R' form a ring.
The term "alkylaminoalkyl" refers to -alkyl-NRR'.
[0435] The term "aryl" as used herein refers to any stable
monocyclic, bicyclic, or polycyclic carbon ring system of from 4 to
12 atoms in each ring, wherein at least one ring is aromatic. Some
examples of an aryl include phenyl, naphthyl, tetrahydro-naphthyl,
indanyl, and biphenyl. Where an aryl substituent is bicyclic and
one ring is non-aromatic, it is understood that attachment is to
the aromatic ring. An aryl may be substituted or unsubstituted.
[0436] The term "heteroaryl" as used herein refers to any stable
monocyclic, bicyclic, or polycyclic carbon ring system of from 4 to
12 atoms in each ring, wherein at least one ring is aromatic and
contains from 1 to 4 heteroatoms selected from oxygen, nitrogen and
sulfur. Phosphorous and selenium may be a heteroatom. Some examples
of a heteroaryl include acridinyl, quinoxalinyl, pyrazolyl,
indolyl, benzotriazolyl, furanyl, thienyl, benzothienyl,
benzofuranyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl,
pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, and
tetrahydroquinolinyl. A heteroaryl includes the N-oxide derivative
of a nitrogen-containing heteroaryl.
[0437] The term "heterocycle" or "heterocyclyl" as used herein
refers to an aromatic or nonaromatic ring system of from five to
twenty-two atoms, wherein from 1 to 4 of the ring atoms are
heteroatoms selected from oxygen, nitrogen, and sulfur. Phosphorous
and selenium may be a heteroatom. Thus, a heterocycle may be a
heteroaryl or a dihydro or tetrathydro version thereof.
[0438] The term "aroyl" as used herein refers to an aryl radical
derived from an aromatic carboxylic acid, such as a substituted
benzoic acid. The term "aralkyl" as used herein refers to an aryl
group bonded to an alkyl group, for example, a benzyl group.
[0439] The term "carboxyl" as used herein represents a group of the
formula --C(.dbd.O)OH or --C(.dbd.O)O.sup.-. The terms "carbonyl"
and "acyl" as used herein refer to a group in which an oxygen atom
is double-bonded to a carbon atom >C.dbd.O. The term "hydroxyl"
as used herein refers to --OH or --O.sup.-. The term "nitrile" or
"cyano" as used herein refers to --CN. The term "halogen" or "halo"
refers to fluoro (--F), chloro (--Cl), bromo (--Br), and iodo
(--I).
[0440] The term "substituted" as used herein refers to an atom
having one or more substitutions or substituents which can be the
same or different and may include a hydrogen substituent. Thus, the
terms alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkanoyl,
alkanoyloxy, alkylamino, alkylaminoalkyl, aryl, heteroaryl,
heterocycle, aroyl, and aralkyl as used herein refer to groups
which include substituted variations. Substituted variations
include linear, branched, and cyclic variations, and groups having
a substituent or substituents replacing one or more hydrogens
attached to any carbon atom of the group. Substituents that may be
attached to a carbon atom of the group include alkyl, cycloalkyl,
alkenyl, alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino,
alkylaminoalkyl, aryl, heteroaryl, heterocycle, aroyl, aralkyl,
acyl, hydroxyl, cyano, halo, haloalkyl, amino, aminoacyl,
alkylaminoacyl, acyloxy, aryloxy, aryloxyalkyl, mercapto, nitro,
carbamyl, carbamoyl, and heterocycle. For example, the term ethyl
includes without limitation --CH.sub.2CH.sub.3, --CHFCH.sub.3,
--CF.sub.2CH.sub.3, --CHFCH.sub.2F, --CHFCHF.sub.2, --CHFCF.sub.3,
--CF.sub.2CH.sub.2F, --CF.sub.2CHF.sub.2, --CF.sub.2CF.sub.3, and
other variations as described above. In general, a substituent may
itself be further substituted with any atom or group of atoms.
[0441] Some examples of a substituent for a substituted alkyl
include halogen, hydroxyl, carbonyl, carboxyl, ester, aldehyde,
carboxylate, formyl, ketone, thiocarbonyl, thioester, thioacetate,
thioformate, selenocarbonyl, selenoester, selenoacetate,
selenoformate, alkoxyl, phosphoryl, phosphonate, phosphinate,
amino, amido, amidine, imino, cyano, nitro, azido, carbamato,
sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido,
sulfonyl, silyl, heterocyclyl, aryl, aralkyl, aromatic, and
heteroaryl.
[0442] It will be understood that "substitution" or "substituted
with" refers to such substitution that is in accordance with
permitted valence of the substituted atom and the substituent. As
used herein, the term "substituted" includes all permissible
substituents.
[0443] In general, a compound may contain one or more chiral
centers. Compounds containing one or more chiral centers may
include those described as an "isomer," a "stereoisomer," a
"diastereomer," an "enantiomer," an "optical isomer," or as a
"racemic mixture." Conventions for stereochemical nomenclature, for
example the stereoisomer naming rules of Cahn, Ingold and Prelog,
as well as methods for the determination of stereochemistry and the
separation of stereoisomers are known in the art. See, for example,
Michael B. Smith and Jerry March, March's Advanced Organic
Chemistry, 5th edition, 2001. The compounds and structures of this
disclosure are meant to encompass all possible isomers,
stereoisomers, diastereomers, enantiomers, and/or optical isomers
that would be understood to exist for the specified compound or
structure, including any mixture, racemic or otherwise,
thereof.
[0444] This invention encompasses any and all tautomeric, solvated
or unsolvated, hydrated or unhydrated forms, as well as any atom
isotope forms of the compounds and compositions disclosed
herein.
[0445] This invention encompasses any and all crystalline
polymorphs or different crystalline forms of the compounds and
compositions disclosed herein.
Additional Embodiments
[0446] All publications, references, patents, patent publications
and patent applications cited herein are each hereby specifically
incorporated by reference in their entirety for all purposes.
[0447] While this invention has been described in relation to
certain embodiments, aspects, or variations, and many details have
been set forth for purposes of illustration, it will be apparent to
those skilled in the art that this invention includes additional
embodiments, aspects, or variations, and that some of the details
described herein may be varied considerably without departing from
this invention. This invention includes such additional
embodiments, aspects, and variations, and any modifications and
equivalents thereof. In particular, this invention includes any
combination of the features, terms, or elements of the various
illustrative components and examples.
[0448] The use herein of the terms "a," "an," "the" and similar
terms in describing the invention, and in the claims, are to be
construed to include both the singular and the plural.
[0449] The terms "comprising," "having," "include," "including" and
"containing" are to be construed as open-ended terms which mean,
for example, "including, but not limited to." Thus, terms such as
"comprising," "having," "include," "including" and "containing" are
to be construed as being inclusive, not exclusive.
[0450] Recitation of a range of values herein refers individually
to each and any separate value falling within the range as if it
were individually recited herein, whether or not some of the values
within the range are expressly recited. For example, the range "4
to 12" includes without limitation any whole, integer, fractional,
or rational value greater than or equal to 4 and less than or equal
to 12, as would be understood by those skilled in the art. Specific
values employed herein will be understood as exemplary and not to
limit the scope of the invention.
[0451] Recitation of a range of a number of atoms herein refers
individually to each and any separate value falling within the
range as if it were individually recited herein, whether or not
some of the values within the range are expressly recited. For
example, the term "C1-8" includes without limitation the species
C1, C2, C3, C4, C5, C6, C7, and C8.
[0452] Definitions of technical terms provided herein should be
construed to include without recitation those meanings associated
with these terms known to those skilled in the art, and are not
intended to limit the scope of the invention. Definitions of
technical terms provided herein shall be construed to dominate over
alternative definitions in the art or definitions which become
incorporated herein by reference to the extent that the alternative
definitions conflict with the definition provided herein.
[0453] The examples given herein, and the exemplary language used
herein are solely for the purpose of illustration, and are not
intended to limit the scope of the invention. All examples and
lists of examples are understood to be non-limiting.
[0454] When a list of examples is given, such as a list of
compounds, molecules or compositions suitable for this invention,
it will be apparent to those skilled in the art that mixtures of
the listed compounds, molecules or compositions may also be
suitable.
EXAMPLES
[0455] Thermogravimetric analysis (TGA) was performed using a Q50
Thermogravimetric Analyzer (TA Instruments, New Castle, Del.). NMR
data were recorded using a Varian 400 MHz spectrometer.
Example 1
Molecular Precursor Compounds
[0456] An MP1 molecular precursor represented by the formula
Cu--(S.sup.tBu).sub.3In.sup.iPr was synthesized using the following
procedure. A 100 mL Schlenk tube was charged with
.sup.iPr.sub.2In(S.sup.tBu) (1.68 g, 6.1 mmol) and Cu(S.sup.tBu)
(0.93 g, 6.1 mmol) in an inert atmosphere glovebox. To this mixture
was added 20 mL of dry toluene via cannula transfer using a Schlenk
line. The mixture was heated until it became homogeneous. One
equivalent of HS.sup.tBu (0.7 mL, 6.1 mmol) was added via syringe
and the Schlenk tube was kept under static N.sub.2. The mixture was
heated for about 12-14 h at 60.degree. C. with stirring. The
solution was then filtered warm and crystals began to form at room
temperature. The solution was cooled at -60.degree. C. for 16
hours. Yellow crystalline solid was isolated, 1.4 g, yield 47%.
Elemental analysis: C, 36.2; H, 6.7; Cu, 13.0; In, 23.9; S, 18.0.
NMR: (1H) 1.66 (br s 34H); (13C) 23.15 (s); 26.64 (s); 37.68 (s);
47.44 (s). Solubility: pentane, nil; diethyl ether, ss, benzene, s
heat; toluene, vs heat; THF, s; CHCl.sub.3, s.
[0457] The TGA for this MP1 molecular precursor showed a single
transition having a midpoint at 220.degree. C., ending at
227.degree. C. The yield for the transition was 50.4% (w/w), as
compared to a theoretical yield for the formula CuInS.sub.2 of
49.5% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuInS.sub.2 layers and materials, and can be
used as a component to prepare other semiconductor layers,
crystals, and materials.
[0458] The structure of this crystalline MP1 precursor molecule was
determined by single crystal X-ray diffraction. The molecular
structure of the compound was of a dimer, represented by the
formula (Cu--(S.sup.tBu).sub.3In.sup.iPr).sub.2.
[0459] The local structure surrounding the indium atom was a
tetrahedral arrangement of four atoms. At one apex of the indium
tetrahedron was the methine carbon atom of the .sup.iPr group. The
remainder of the tetrahedron was formed by the sulfur atoms of
three (S.sup.tBu) ligands, each attached through a sulfur atom to
indium.
[0460] The local structure surrounding the copper atom was bonding
of the copper atom to three sulfur atoms of three S.sup.tBu
ligands. The three S.sup.tBu ligands were bridging ligands that
were each shared through bonding of their sulfur atom to a copper
atom and an indium atom.
Example 2
[0461] An MP1 molecular precursor represented by the formula
Cu--(S.sup.tBu).sub.3In.sup.nBu was synthesized using the following
procedure. A 100 mL Schlenk tube was charged with
.sup.nBu.sub.2In(S.sup.tBu) (1.8 g, 5.8 mmol) and Cu(S.sup.tBu)
(0.89 g, 5.8 mmol) in an inert atmosphere glovebox. To this mixture
was added 20 mL of dry toluene via cannula transfer using a Schlenk
line. The mixture was heated until it became homogeneous. One
equivalent of HS.sup.tBu (0.65 mL, 5.8 mmol) was added via syringe
and the Schlenk tube was kept under static N.sub.2. The mixture was
heated for about 12-14 hours at 100.degree. C. with stirring. The
solution was then allowed to cool to room temperature and filtered.
The solvent was removed under vacuum, and the product was extracted
with pentane. The pentane extract was concentrated and cooled for
about 12-14 hours at -60.degree. C. to yield pale yellow crystals.
Yield, 1.4 g, 48%. NMR: (1H) 1.006 (m, 3H); 1.44 (m, 2H) 1.56 (m,
2H), 1.68 (br s, 27H); 1.998 (m, 2H); (13C) 13.86 (s); 23.13 (s);
28.54 (s); 30.51 (s); 37.23 (s); 47.47 (s). Solubility: pentane, s;
diethyl ether, vs, benzene, vs; toluene, vs; THF, vs; CHCl.sub.3,
vs.
[0462] In FIG. 8 is shown the structure of this crystalline MP1
precursor molecule as determined by single crystal X-ray
diffraction. The molecular structure of the compound was of a
dimer, represented by the formula
(Cu--(S.sup.tBu).sub.3In.sup.nBu).sub.2.
[0463] As shown in FIG. 8, the local structure of this molecular
precursor compound regarding the indium atom in the crystalline
compound was a tetrahedral arrangement of four atoms. At one apex
of the indium tetrahedron was the terminal methylene carbon atom of
the .sup.nBu group. The remainder of the tetrahedron was formed by
the sulfur atoms of three (S.sup.tBu) ligands, each attached
through a sulfur atom to indium.
[0464] As shown in FIG. 8, the local structure surrounding the
copper atom was bonding of the copper atom to three sulfur atoms of
three S.sup.tBu ligands. The three S.sup.tBu ligands were bridging
ligands that were each shared through bonding of their sulfur atom
to a copper atom and an indium atom.
[0465] The TGA for this MP1 molecular precursor compound showed a
single transition having a midpoint at 235.degree. C., ending at
248.degree. C. The yield for the transition was 50.4% (w/w), as
compared to a theoretical yield for the formula CuInS.sub.2 of
48.1% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuInS.sub.2 layers and materials, and can be
used as a component to prepare other semiconductor layers,
crystals, and materials.
Example 3
[0466] An MP1 molecular precursor represented by the formula
Cu--(Se.sup.tBu).sub.3In.sup.nBu was synthesized using the
following procedure. .sup.tBuSeH (8.8 mmol) was slowly added to a
pentane solution (30 mL) of .sup.nBu.sub.3In (1.67 g, 5.8 mmol).
The mixture was stirred at 25.degree. C. for 12 h, and the solvent
and excess .sup.tBuSeH were removed under dynamic vacuum. A
colorless oil of .sup.nBu.sub.2In(Se.sup.tBu) was obtained and was
then combined with CuSe.sup.tBu (1.17 g, 5.8 mmol) with 40 mL of
toluene. .sup.tBuSeH (2.10 g, 5.8 mmol) was slowly added to the
reaction mixture, and the reaction mixture was stirred at
60.degree. C. for about 12-14 hours. A deep red solution was
formed. The solvent was removed under dynamic vacuum and the
remaining solid was extracted with pentane (60 mL) and filtered.
Concentration of the filtrate to 20 mL and storage at -60.degree.
C. in a freezer afforded 2.02 g (54%) of yellow crystals. NMR: (1H)
1.00 (t, 3H, .sup.3J.sub.HH=7.6), 1.54 (m, 2H), 1.80 (s, 29H), 2.01
(m, 2H) in C6D6; (13C) 13.9, 21.6, 28.4, 30.7, 37.9 in C6D6; (77Se)
154.0 in C6D6. Solubility: pentane, s; diethyl ether, vs, benzene,
vs; toluene, vs; THF, vs; CHCl.sub.3, vs.
[0467] The TGA for this MP1 molecular precursor showed a single
transition having a midpoint at 174.degree. C., ending at
196.degree. C. The yield for the transition was 48.5% (w/w), as
compared to a theoretical yield for the formula CuInSe.sub.2 of
52.3% (w/w). Thus, the TGA data showed that this MP1 molecular
precursor can be used to prepare CuInSe.sub.2 layers and materials,
and can be used as a component to prepare other semiconductor
layers, crystals, and materials.
Example 4
[0468] An MP1 molecular precursor represented by the formula
Cu--(S.sup.tBu).sub.3In.sup.tBu was synthesized using the following
procedure. A 100 mL Schlenk tube was charged with
.sup.tBu.sub.2In(S.sup.tBu) (1.5 g, 5.2 mmol) and Cu(S.sup.tBu)
(0.80 g, 5.2 mmol) in an inert atmosphere glovebox. To this mixture
was added 30 mL of dry benzene via cannula transfer using a Schlenk
line. The mixture was heated until it became homogeneous, then
filtered and allowed to cool to room temperature. One equivalent of
HS.sup.tBu (0.6 mL, 5.2 mmol) was added via syringe and the Schlenk
tube was kept under static N.sub.2. The mixture was stirred for
about 12-14 hours, and a pale yellow precipitate was formed. The
solution was filtered and the remaining solid was washed with
benzene at room temperature. The solid product was dried under
vacuum. Yield 2.15 g (83%). The physical state of the molecular
precursor Cu--(S.sup.tBu).sub.3In.sup.tBu was a pale yellow solid
at room temperature.
[0469] Elemental analysis: C, 38.3; H, 7.2; Cu, 13.1; In, 21.8; S,
18.5. NMR: C6D6: 1.627 (s, 9H); 1.69 (s, 27H); CDCl.sub.3: 1.45 (s,
9H); 1.56 (s, 27H). Solubility: pentane, nil; diethyl ether, nil,
benzene, ss heat; toluene, s heat; THF, ss; CHCl.sub.3, s.
[0470] In FIG. 9 is shown the TGA for this MP1 molecular precursor.
The TGA showed a single sharp transition ending at about
240.degree. C. The yield for the transition was 48.1% (w/w), as
compared to a theoretical yield for the formula CuInS.sub.2 of
48.1% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuInS.sub.2 layers and materials, and can be
used as a component to prepare other semiconductor layers,
crystals, and materials.
[0471] The structure of this crystalline MP1 precursor molecule was
determined by single crystal X-ray diffraction. The molecular
structure of the compound was of a dimer, represented by the
formula (Cu--(S.sup.tBu).sub.3In.sup.tBu).sub.2.
Example 5
[0472] An MP1 molecular precursor represented by the formula
Cu--(Se.sup.tBu).sub.3Ga.sup.tBu was synthesized using the
following procedure. .sup.tBuSeH (8.7 mmol) was slowly added to a
pentane solution (30 mL) of .sup.tBu.sub.3Ga (2.1 g, 8.7 mmol). The
mixture was stirred at 25.degree. C. for 30 min., and the solvent
was removed under dynamic vacuum. Solid
.sup.tBu.sub.2Ga(Se.sup.tBu) (0.68 g, 2.1 mmol) was combined with
CuSe.sup.tBu (0.42 g, 2.1 mmol) with 40 mL of toluene. .sup.tBuSeH
(0.76 g, 2.1 mmol) was slowly added to the reaction mixture, and
the reaction mixture was stirred at 90.degree. C. for about 24 h. A
deep red solution was formed with a light brown solid precipitate.
The light brown solid was collected and washed with toluene at
25.degree. C., then dried under vacuum to yield 0.65 g. (Yield,
52%) NMR: (1H) 1.62 (s, 9H), 1.80 (s, 27H) in C6D6. Solubility:
pentane, nil; diethyl ether, nil, benzene, ss heat; toluene, s
heat.
[0473] In FIG. 10 is shown the TGA for this MP1 molecular
precursor. The TGA showed a single sharp transition ending at about
210.degree. C. The yield for the transition was 48.3% (w/w), as
compared to a theoretical yield for the formula CuGaSe.sub.2 of
48.7% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuGaSe.sub.2 layers and materials, and can
be used as a component to prepare other semiconductor layers,
crystals, and materials.
[0474] The structure of this crystalline MP1 precursor molecule was
determined by single crystal X-ray diffraction. The molecular
structure of the compound was of a dimer, represented by the
formula (Cu--(Se.sup.tBu).sub.3Ga.sup.tBu).sub.2.
Example 6
[0475] An MP1 molecular precursor represented by the formula
Cu--(S.sup.tBu).sub.3Ga.sup.tBu was synthesized using the following
procedure.
[0476] Benzene (ca. 30 mL) was added to a solid mixture of CuStBu
(0.97 g, 6.3 mmol) and .sup.tBu.sub.2GaS.sup.tBu (1.73 g, 6.3 mmol)
and the resulting mixture was stirred briefly at about 85.degree.
C. to produce a homogeneous solution. Tert-butylthiol (0.72 mL, 6.4
mmol) was added and the mixture was heated for about 12-14 hours at
85-90.degree. C. to produce a pale yellow precipitate. The
precipitate was isolated by filtration, washed with benzene
(1.times.10 mL) and dried under vacuum to give 2.6 g (Yield, 90%).
Elemental analysis: C, 41.4; H, 8.0; Cu, 14.3; Ga, 15.8; S, 18.8.
NMR: (1H) 1.58 (9H), 1.69 (27H) in C6D6. Solubility: pentane, nil;
diethyl ether, nil, benzene, ss heat; toluene, s heat.
[0477] In FIG. 11 is shown the TGA for this MP1 molecular
precursor. The TGA showed a single sharp transition ending at about
225.degree. C. The yield for the transition was 45.7% (w/w), as
compared to a theoretical yield for the formula CuGaS.sub.2 of
43.1% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuGaS.sub.2 layers and materials, and can be
used as a component to prepare other semiconductor layers,
crystals, and materials.
Example 7
[0478] An MP1 molecular precursor represented by the formula
Cu--(Se.sup.tBu).sub.3In.sup.tBu was synthesized using the
following procedure. Solid .sup.tBu.sub.2In(Se.sup.tBu) (0.71 g,
1.9 mmol) was combined with CuSe.sup.tBu (0.31 g, 1.6 mmol) with 40
mL of toluene. .sup.tBuSeH (1.9 mmol) was slowly added to the
reaction mixture, and the reaction mixture was stirred at
60.degree. C. for about 12-14 h. A pale yellow solid was formed
during the reaction. This solid was collected, washed with toluene
at room temperature and dried under vacuum to yield 0.55 g (Yield,
53%). Elemental analysis: C, 30.0; H, 5.4; Cu, 10.7; In, 18.9; Se,
37.2. NMR: (1H) 1.62 (s, 9H), 1.80 (s, 27H) in C6D6; 1.42 (s, 9H),
1.68 (s, 27H) in CDCl.sub.3; (13C) 32.2, 38.2 in CDCl.sub.3.
Solubility: pentane, nil; diethyl ether, nil, benzene, ss heat;
toluene, heat; THF, ss; CHCl.sub.3, s.
[0479] In FIG. 12 is shown the TGA for this MP1 molecular
precursor. The TGA showed a single sharp transition ending at about
192.degree. C. The yield for the transition was 53.1% (w/w), as
compared to a theoretical yield for the formula CuInSe.sub.2 of
52.3% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuInSe.sub.2 layers and materials, and can
be used as a component to prepare other semiconductor layers,
crystals, and materials.
Example 8
[0480] An MP1 molecular precursor represented by the formula
Cu--(Se.sup.tBu).sub.3In.sup.iPr was synthesized using the
following procedure. .sup.tBuSeH (5.9 mmol) was slowly added to a
pentane solution (30 mL) of .sup.iPr.sub.3In (3.9 mmol). The
mixture was stirred at 25.degree. C. for 12 h, and the solvent and
excess .sup.tBuSeH were removed under dynamic vacuum. Oily
.sup.iPr.sub.2In(Se.sup.tBu) was obtained and was combined with
CuSe.sup.tBu (0.77 g, 3.9 mmol) with 40 mL of toluene. .sup.tBuSeH
(3.9 mmol) was slowly added to the reaction mixture, and the
reaction mixture was stirred at 60.degree. C. for about 12-14
hours. A deep red solution with suspended yellow solid was formed.
The yellow solid was collected and the filtrate was concentrated to
20 mL. The yellow solid was washed with 60 mL pentane, and dried
under vacuum to yield 0.6 g. Storage of the filtrate at -60.degree.
C. in a freezer afforded another 0.35 g of yellow crystals.
Combined yield 35%. Elemental analysis: C, 29.1; H, 5.3; Cu, 16.5;
In, 18.9; Se, 37.4. NMR: (1H) 1.52 (b, 7H, .sup.3 J.sub.HH=7.6),
1.67 (s, 27H) in CDCl.sub.3; (13C) 23.2, 32.5, 38.0, 45.8 in
CDCl.sub.3. Solubility: pentane, nil; diethyl ether, ss, benzene, s
heat; toluene, vs heat; THF, s; CHCl.sub.3, s.
[0481] The TGA for this MP1 molecular precursor showed a single
transition having a midpoint at 192.degree. C., ending at
199.degree. C. The yield for the transition was 52.1% (w/w), as
compared to a theoretical yield for the formula CuInSe.sub.2 of
53.4% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuInSe.sub.2 layers and materials, and can
be used as a component to prepare other semiconductor layers,
crystals, and materials.
[0482] The structure of this crystalline MP1 precursor molecule was
determined by single crystal X-ray diffraction. The molecular
structure of the compound was of a dimer, represented by the
formula (Cu--(Se.sup.tBu).sub.3In.sup.iPO.sub.2.
Example 9
[0483] An MP1 molecular precursor represented by the formula
Cu--(S.sup.nBu).sub.2(S.sup.tBu)In.sup.tBu was synthesized using
the following procedure. To a suspension of CuS.sup.tBu (0.43 g,
2.8 mmol) and HS.sup.nBu (0.3 mL, 5.6 mmol) in 5 mL toluene was
added a solution of freshly prepared .sup.tBu.sub.2InS.sup.nBu (2.8
mmol) in 5 mL toluene. The reaction mixture was heated at
80.degree. C. for about 12-14 hours. The solvent was removed under
vacuum, and the crude product was extracted with pentane. The
solvent was removed under vacuum, leaving a pale yellow sticky foam
(Yield, 0.40 g, 28%). NMR: (1H) 0.94 (br s, 3H); 1.50 (br s, 2 H);
1.75 (s, 9H); 1.95 (br s, 2H); 3.19 (br s, 2H); (13C) 14.04 (s);
22.58 (s); 31.50 (s); 37.19 (s); 47.10 (s).
[0484] The TGA for this MP1 molecular precursor showed a single
transition having a midpoint at 235.degree. C., ending at
295.degree. C. The yield for the transition was 47.9% (w/w), as
compared to a theoretical yield for the formula CuInS.sub.2 of
48.1% (w/w). Thus, the TGA showed that this MP1 molecular precursor
can be used to prepare CuInS.sub.2 layers and materials, and can be
used as a component to prepare other semiconductor layers,
crystals, and materials.
Example 10
[0485] A 75:25 molar mixture of MP1 molecular precursors
represented by the formulas
(Cu--(Se.sup.tBu).sub.3In.sup.tBu).sub.2 (0.190 g) and
(Cu--(Se.sup.tBu).sub.3Ga.sup.tBu).sub.2 (0.060 g) was made and
ground to a fine powder.
[0486] FIG. 13 shows the TGA for this mixture of MP1 molecular
precursors. The TGA showed a single sharp transition ending at
about 195.degree. C. The yield for the transition was 52.9% (w/w),
as compared to a theoretical yield for the formula
CuIn.sub.0.75Ga.sub.0.25Se.sub.2 of 51.4% (w/w). Thus, the TGA
showed that this mixture of MP1 molecular precursors can be used to
prepare CuIn.sub.0.75Ga.sub.0.25Se.sub.2 layers and materials, and
can be used as a component to prepare other semiconductor layers,
crystals, and materials.
Example 11
[0487] A 50:50 molar mixture of MP1 molecular precursors
represented by the formulas
(Cu--(Se.sup.tBu).sub.3In.sup.tBu).sub.2 (0.100 g) and
(Cu--(Se.sup.tBu).sub.3Ga.sup.tBu).sub.2 (0.093 g) was made and
ground to a fine powder.
[0488] The TGA for this mixture of MP1 molecular precursors showed
a single sharp transition ending at about 195.degree. C. The yield
for the transition was 51.3% (w/w), as compared to a theoretical
yield for the formula CuIn.sub.0.50Ga.sub.0.50Se.sub.2 of 50.5%
(w/w). Thus, the TGA showed that this mixture of MP1 molecular
precursors can be used to prepare CuIn.sub.0.50Ga.sub.0.50Se.sub.2
layers and materials, and can be used as a component to prepare
other semiconductor layers, crystals, and materials.
Example 12
[0489] An MP1 molecular precursor represented by the formula
Cu--(S.sup.tBu).sub.3Ga.sup.iPr was synthesized using the following
procedure. .sup.tBuSH (1.0 mL, 8.8 mmol) was added to a solution of
.sup.iPr.sub.3Ga--OEt.sub.2 (1.21 g, 4.4 mmol) in benzene (ca. 10
mL) and the resulting mixture was stirred for 1 h at about
60.degree. C. The solvent was removed under reduced pressure giving
.sup.iPr.sub.2GaS.sup.tBu. CuS.sup.tBu (0.68 g, 4.4 mmol),
.sup.tBuSH (0.5 mL, 4.4 mmol) and benzene (ca. 15 mL) were added to
the flask containing .sup.iPr.sub.2GaS.sup.tBu and the mixture was
heated for about 12-14 h at 85.degree. C. to produce a pale yellow
precipitate. The precipitate was isolated by filtration and dried
under vacuum to give 1.6 g (Yield, 82%). NMR: (1H, C6D6) 1.61 (d,
6H), 1.66 (s, 27H).
[0490] The TGA for this MP1 molecular precursor showed a single
transition ending at 220.degree. C. The yield for the transition
was 46.0% (w/w), as compared to a theoretical yield for the formula
CuGaS.sub.2 of 44.5% (w/w).
Example 13
[0491] An MP1 molecular precursor represented by the formula
Cu--(Se.sup.tBu).sub.3Ga.sup.iPr was synthesized using the
following procedure. .sup.tBuSeH (1.71 mL of 3.4 M solution in
Et.sub.2O, 5.9 mmol) was added to a solution of
.sup.iPr.sub.3Ga--OEt.sub.2 (1.60 g, 5.9 mmol) in benzene (ca. 10
mL) and the resulting mixture was stirred for 1 h at about
60.degree. C. The solvent was removed under reduced pressure giving
.sup.iPr.sub.2GaSe.sup.tBu. CuSe.sup.tBu (1.17 g, 5.9 mmol),
.sup.tBuSeH (1.71 mL of 3.4 M solution in Et.sub.2O, 5.9 mmol) and
benzene (ca. 30 mL) were added to the flask containing
.sup.iPr.sub.2GaSe.sup.tBu, and the mixture was heated for about
12-14 hours at about 85.degree. C. A tan precipitate was isolated
by filtration, washed with pentane (1.times.30 mL) and dried under
vacuum to give 2.6 g (Yield, 77%). NMR: (1H, C6D6) 1.60 (d, 6H),
1.77 (s, 27H).
Example 14
[0492] An MP1 molecular precursor represented by the formula
Cu--(Se.sup.tBu).sub.3In.sup.sBu was synthesized using the
following procedure. .sup.tBuSeH (6.82 mmol) was slowly added to a
pentane solution (30 mL) of .sup.sBu.sub.3In (1.5 g, 5.2 mmol). The
solution was stirred at 25.degree. C. for 12 h. The solvent and
excess .sup.tBuSeH were then removed under dynamic vacuum. Oily
.sup.sBu.sub.2In(Se.sup.tBu) was obtained and combined with
CuSe.sup.tBu (1.00 g, 5.0 mmol) and 40 mL of toluene. .sup.tBuSeH
(5.2 mmol) was slowly added to the reaction mixture via cannula
using a Schlenk line, and the reaction mixture was stirred at
60.degree. C. for about 12 h to afford a deep red solution. Upon
cooling of the reaction mixture to 25.degree. C., 1.32 g of pale
yellow crystals were obtained. Concentration and storage of the
solution at -60.degree. C. afforded an additional 0.41 g. (Yield,
52%) NMR: (1H, C6D6) 1.25 (m, 1H), 1.67 (d, 3 H, 3J.sub.HH=6.8 Hz),
1.74 (m, 2H), 1.80 (s, 27H), 1.96 (m, 3H); (13C, C6D6) 15.5, 20.1,
30.8, 38.2, 45.7.
[0493] The TGA for this MP1 molecular precursor showed a single
transition having a midpoint at 191.degree. C., ending at
204.degree. C. The yield for the transition was 52.3% (w/w), as
compared to a theoretical yield for the formula CuInSe.sub.2 of
52.3% (w/w).
Example 15
Molecular Precursor Ink Compositions
[0494] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by dissolving an MP1 molecular
precursor represented by the formula
Cu--(S.sup.tBu).sub.3In.sup.nBu in toluene to a concentration of 5%
(w/w). To this solution is added In(S.sup.nBu).sub.3, in an amount
representing 0.1 atom-equivalents of indium relative to copper in
the MP1 molecular precursor. To this solution is added 0.3% (w/w)
polyurethane. Viscosity of the molecular precursor ink is
determined with a SVM 3000 Viscometer (Anton Paar, Graz,
Austria).
Example 16
[0495] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by dissolving an MP1 molecular
precursor represented by the formula
Cu--(S.sup.tBu).sub.3In.sup.nBu in decane, and heating the decane
to dissolve the molecular precursor to a concentration of 5% (w/w).
To this solution is added In(S.sup.nBu).sub.3, in an amount
representing 0.1 atom-equivalents of indium relative to copper in
the MP1 molecular precursor.
Example 17
[0496] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by dissolving two MP1 molecular
precursors represented by the formulas
Cu--(Se.sup.tBu).sub.3In.sup.nBu and
Cu--(Se.sup.tBu).sub.3Ga.sup.nBu in acetonitrile to a total
concentration of 1% (w/w). 0.75 indium-atom-equivalents of
Cu--(Se.sup.tBu).sub.3In.sup.nBu are added to 0.25
gallium-atom-equivalents of Cu--(Se.sup.tBu).sub.3Ga.sup.nBu,
relative to the total amount of copper.
Example 18
Molecular Precursor Compounds
[0497] A molecular precursor compound having the formula
(.sup.iPrIn(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga.sup.iPr)
is prepared in an inert atmosphere using a glovebox and a Schlenk
line system by reacting 0.75 equivalents of In.sup.iPr.sub.3 and
0.25 equivalents of Ga.sup.iPr.sub.3 with HS.sup.tBu to form
.sup.iPr.sub.2InS.sup.tBu and .sup.iPr.sub.2GaS.sup.tBu. The
products .sup.iPr.sub.2InS.sup.tBu and .sup.iPr.sub.2GaS.sup.tBu
are contacted with a compound Cu(S.sup.tBu) in the presence of one
equivalent of HS.sup.tBu to form a mixture of the MP2 molecular
precursor compound
(.sup.iPrIn(S.sup.tBu).sub.3-Cu)(Cu--(S.sup.tBu).sub.3Ga.sup.iPr)
along with other compounds.
Example 19
[0498] A molecular precursor compound having the formula
(.sup.iPrIn(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga.sup.nBu)
is prepared in an inert atmosphere using a glovebox and a Schlenk
line system by reacting 0.5 equivalents of In.sup.iPr.sub.3 and 0.5
equivalents of Ga.sup.nBu.sub.3 with one equivalent of HSe.sup.tBu
to form .sup.iPr.sub.2InSe.sup.tBu and .sup.nBu.sub.2GaSe.sup.tBu.
The products .sup.iPr.sub.2InSe.sup.tBu and
.sup.nBu.sub.2GaSe.sup.tBu are contacted with one equivalent of
Cu(Se.sup.tBu) in the presence of one equivalent of HSe.sup.tBu to
form the MP2 molecular precursor compound
(.sup.iPrIn(Se.sup.tBu).sub.3-Cu)(Cu--(Se.sup.tBu).sub.3Ga.sup.nBu).
Example 20
Molecular Precursor Compounds
[0499] A molecular precursor compound having the formula
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3In.sup.iPr is prepared in an inert
atmosphere using a glovebox and a Schlenk line system by reacting
In.sup.iPr.sub.3 with HSe.sup.tBu to form
.sup.iPr.sub.2InSe.sup.tBu. The product .sup.iPr.sub.2InSe.sup.tBu
is contacted with a compound Cu(Se.sup.tBu).sub.2 in the presence
of HSe.sup.tBu to form a molecular precursor compound.
Example 21
[0500] A molecular precursor compound having the formula
(.sup.tBuSe)Cu(Se.sup.tBu).sub.3Ga.sup.tBu is prepared in an inert
atmosphere using a glovebox and a Schlenk line system by reacting
Ga.sup.tBu.sub.3 with HSe.sup.tBu to form
.sup.tBu.sub.2GaSe.sup.tBu. The product .sup.tBu.sub.2GaSe.sup.tBu
is contacted with a compound Cu(Se.sup.tBu).sub.2 in the presence
of HSe.sup.tBu to form a molecular precursor compound.
Example 22
Molecular Precursor Compounds
[0501] A molecular precursor compound having the formula
Cu(Se(CH.sub.2).sub.2Se)(Se.sup.tBu)(Se.sup.tBu)Ga.sup.iPr is
prepared in an inert atmosphere using a glovebox and a Schlenk line
system by reacting Ga.sup.iPr.sub.3 with
(CH.sub.3).sub.3SiSe(CH.sub.2).sub.2SeH to form
.sup.iPr.sub.2GaSe(CH.sub.2).sub.2SeSi(CH.sub.3).sub.3. The product
.sup.iPr.sub.2GaSe(CH.sub.2).sub.2SeSi(CH.sub.3).sub.3 is contacted
with a compound Cu(Se.sup.tBu)Cl in the presence of HSe.sup.nBu to
form a molecular precursor compound.
Example 23
[0502] A molecular precursor compound having the formula
Cu(Se(CH.sub.2).sub.2SeCH.sub.3)(Se.sup.tBu).sub.2In.sup.tBu is
prepared in an inert atmosphere using a glovebox and a Schlenk line
system by reacting In.sup.tBu.sub.3 with
HSe(CH.sub.2).sub.2SeCH.sub.3 to form
.sup.tBu.sub.2InSe(CH.sub.2).sub.2SeCH.sub.3. The product
.sup.tBu.sub.2InSe(CH.sub.2).sub.2SeCH.sub.3 is contacted with a
compound Cu(Se.sup.tBu).sub.2 in the presence of one equivalent of
HSe.sup.tBu to form a molecular precursor compound.
Example 24
Molecular Precursor Compounds
[0503] An MP1-Ag molecular precursor represented by the formula
Ag--(Se.sup.tBu).sub.3In.sup.nBu was synthesized using the
following procedure. .sup.tBuSeH (4.2 mmol) was slowly added to a
pentane solution (30 mL) of .sup.nBu.sub.3In (1.00 g, 3.5 mmol).
The reaction mixture was stirred at 25.degree. C. for 12 h, and the
solvent and excess .sup.tBuSeH were removed under dynamic vacuum. A
colorless oil, .sup.nBu.sub.2In(Se.sup.tBu), was obtained and
combined with AgSe.sup.tBu (0.76 g, 3.1 mmol) in toluene (40 mL).
.sup.tBuSeH (3.5 mmol) was slowly added to the reaction mixture,
and the reaction mixture was stirred at 60.degree. C. for 12-14 h.
A brown solution with a small amount of black precipitate formed.
This solution was filtered (black precipitate discarded), and the
solvent was removed under dynamic vacuum. The remaining solid was
washed with pentane (2.times.30 mL) and dried under dynamic vacuum.
1.26 g (52%) of white solid was obtained.
[0504] Elemental analysis: C, 28.11; H, 5.27; Ag, 15.56; In, 18.78;
Se, 34.18. NMR: (1H) 0.94 (t, 3H, 3JHH=7.2 Hz), 1.34 (m, 2H), 1.47
(m, 2H), 1.67 (s, 27H), 1.75-1.81 (m, 2H) in CDCl.sub.3; (13C)
13.8, 21.5, 28.0, 30.5, 38.5 and 45.2 in CDCl.sub.3; (77Se)
193.4.
[0505] In FIG. 14 is shown the TGA for this MP1-Ag molecular
precursor. The TGA for this MP1-Ag molecular precursor showed a
transition ending at about 205.degree. C. The total yield for the
TGA transition was 54.6% (w/w) at about 205.degree. C. and 52.5% at
400.degree. C., as compared to a theoretical yield for the formula
AgInSe.sub.2 of 55.3% (w/w). Thus, the TGA showed that this MP1-Ag
molecular precursor can be used to prepare AgInSe.sub.2 layers and
materials, and can be used as a component to prepare other
semiconductor layers, crystals, and materials.
[0506] The unit cell of this crystalline MP1-Ag precursor molecule
was determined by single crystal X-ray diffraction.
Example 25
[0507] An MP1-Ag molecular precursor represented by the formula
Ag--(Se.sup.tBu).sub.3Ga.sup.nBu was synthesized using the
following procedure. .sup.tBuSeH (3.5 mmol) was slowly added to a
pentane solution (20 mL) of .sup.nBu.sub.3Ga (0.70 g, 2.9 mmol).
The reaction mixture was stirred at 25.degree. C. for 12 h, and the
solvent and excess .sup.tBuSeH were removed under dynamic vacuum. A
colorless oil, .sup.nBu.sub.2Ga(Se.sup.tBu), was obtained and
combined with AgSe.sup.tBu (0.64 g, 2.6 mmol) in toluene (40 mL).
.sup.tBuSeH (2.9 mmol) was slowly added to the reaction mixture,
and the reaction mixture was stirred at 60.degree. C. for 12-14 h.
A brown solution with a small amount of black precipitate formed.
This solution was filtered (black precipitate discarded), and the
solvent was removed under dynamic vacuum. The remaining solid was
washed with pentane (2.times.30 mL) and dried under dynamic vacuum.
1.29 g (69%) of grey solid was obtained.
[0508] Elemental analysis: C, 30.42; H, 5.71; Ag, 15.84; Ga, 10.81;
Se, 37.35. NMR: (1H) 0.94 (t, 3H, 3JHH=7.6 Hz), 1.18 (m, 2H), 1.43
(m, 2H), 1.65 (s, 27H), 1.86-2.18 (m, 3H) in CDCl.sub.3; (13C)
13.9, 21.9, 27.5, 29.4, 37.8 and 46.1 in CDCl.sub.3; (77Se)
230.4.
[0509] In FIG. 15 is shown the TGA for this MP1-Ag molecular
precursor. The TGA for this MP1-Ag molecular precursor compound
showed a transition ending at about 210.degree. C. The yield for
the transition was 53.9% (w/w) at about 210.degree. C. and 47.7%
(w/w) at about 400.degree. C., as compared to a theoretical yield
for the formula AgGaSe.sub.2 of 52.2% (w/w). Thus, the TGA showed
that this MP1-Ag molecular precursor can be used to prepare
AgGaSe.sub.2 layers and materials, and can be used as a component
to prepare other semiconductor layers, crystals, and materials.
[0510] The unit cell of this crystalline MP1-Ag precursor molecule
was determined by single crystal X-ray diffraction.
Example 26
[0511] An MP1-Ag molecular precursor represented by the formula
Ag--(Se.sup.tBu).sub.3In.sup.sBu was synthesized using the
following procedure: .sup.tBuSeH (4.2 mmol) was slowly added to a
pentane solution (30 mL) of .sup.sBu.sub.3In (1.00 g, 3.5 mmol).
The reaction mixture was stirred at 25.degree. C. for 12 h, and the
solvent and excess .sup.tBuSeH were removed under dynamic vacuum. A
colorless oil, .sup.sBu.sub.2In(Se.sup.tBu), was obtained and part
of this oil (0.5 g, 1.4 mmol) was combined with AgSe.sup.tBu (0.33
g, 1.4 mmol) in toluene (40 mL). .sup.tBuSeH (1.4 mmol) was slowly
added to the reaction mixture, and the reaction mixture was stirred
at 60.degree. C. for 12-14 h. A brown solution with a small amount
of black precipitate formed. This solution was filtered (black
precipitate discarded), and the solvent was removed under dynamic
vacuum. The remaining solid was washed with pentane (2.times.30 mL)
and dried under dynamic vacuum. 0.64 g (66%) of pale yellow solid
was obtained.
[0512] Elemental analysis: C, 28.78; H, 5.30; Ag, 14.57; In, 17.67;
Se, 33.28. NMR: (1H) 1.15 (t, 3H, 3JHH=7.2 Hz), 1.50 (d, 3H,
3JHH=7.2 Hz), 1.66 (s, 27H), 1.82-2.15 (m, 3H) in CDCl.sub.3; (13C)
14.2, 17.2, 28.1, 30.2, 38.0 and 46.5 in CDCl.sub.3; (77Se)
233.3.
[0513] In FIG. 16 is shown the TGA for this MP1-Ag molecular
precursor. The TGA for this MP1-Ag molecular precursor showed a
transition ending at about 195.degree. C. The yield for the
transition was 54.9% (w/w), as compared to a theoretical yield for
the formula AgInSe.sub.2 of 55.3% (w/w). Thus, the TGA data showed
that this MP1-Ag molecular precursor can be used to prepare
AgInSe.sub.2 layers and materials, and can be used as a component
to prepare other semiconductor layers, crystals, and materials.
[0514] The unit cell of this crystalline MP1-Ag precursor molecule
was determined by single crystal X-ray diffraction.
Example 27
[0515] An MP1-Ag molecular precursor represented by the formula
Ag--(Se.sup.tBu).sub.3Ga.sup.sBu was synthesized using the
following procedure: .sup.tBuSeH (3.6 mmol) was slowly added to a
pentane solution (20 mL) of .sup.sBu.sub.3Ga (0.68 g, 2.8 mmol).
The reaction mixture was stirred at 25.degree. C. for 12 h, and the
solvent and excess .sup.tBuSeH were removed under dynamic vacuum. A
colorless oil, .sup.sBu.sub.2Ga(Se.sup.tBu), was obtained and
combined with AgSe.sup.tBu (0.69 g, 2.8 mmol) in toluene (40 mL).
.sup.tBuSeH (2.8 mmol) was slowly added to the reaction mixture,
and the reaction mixture was stirred at 60.degree. C. for 12-14 h.
A brown solution with a small amount of black precipitate formed.
This solution was filtered (black precipitate discarded), and the
solvent was removed under dynamic vacuum. The remaining solid was
washed with pentane (2.times.30 mL) and dried under dynamic vacuum.
0.53 g (29%) of pale yellow solid was obtained.
[0516] Elemental analysis: C, 30.31; H, 5.71; Ag, 16.02; Ga, 10.83;
Se, 35.96. NMR: (1H) 1.07 (t, 3H, 3JHH=7.2 Hz), 1.38 (d, 2H,
3JHH=6.8 Hz), 1.66 (s, 27H), 2.04-2.15 (m, 3H) in CDCl.sub.3; (13C)
14.8, 17.2, 28.1, 30.2, 38.0 and 46.5 in CDCl.sub.3; (77Se)
233.3.
[0517] In FIG. 17 is shown the TGA for this MP1-Ag molecular
precursor. The TGA showed a transition ending at about 195.degree.
C. The yield for the transition was 50.4% (w/w) at about
195.degree. C. and 45.1% (w/w) at about 400.degree. C., as compared
to a theoretical yield for the formula AgGaSe.sub.2 of 52.2% (w/w).
Thus, the TGA showed that this MP1-Ag molecular precursor can be
used to prepare AgGaSe.sub.2 layers and materials, and can be used
as a component to prepare other semiconductor layers, crystals, and
materials.
[0518] The unit cell of this crystalline MP1-Ag precursor molecule
was determined by single crystal X-ray diffraction.
Example 28
[0519] An MP1-Ag molecular precursor represented by the formula
Ag--(Se.sup.tBu).sub.3In.sup.iPr was synthesized using the
following procedure: .sup.tBuSeH (4.0 mmol) was slowly added to a
pentane solution (30 mL) of .sup.iPr.sub.3In (0.80 g, 3.3 mmol).
The reaction mixture was stirred at 25.degree. C. for 12 h, and the
solvent and excess .sup.tBuSeH were removed under dynamic vacuum.
1.00 g of a colorless oil, .sup.iPr.sub.2In(Se.sup.tBu), was
obtained and combined with AgSe.sup.tBu (0.72 g, 3.0 mmol) in
toluene (40 mL). .sup.tBuSeH (3.0 mmol) was slowly added to the
reaction mixture, and the reaction mixture was stirred at
60.degree. C. for 12-14 h. A brown solution with a small amount of
black precipitate formed. This solution was filtered (black
precipitate discarded), and the solvent was removed under dynamic
vacuum. The remaining solid was washed with pentane (2.times.30 mL)
and dried under dynamic vacuum. 1.02 g (46%) of grey solid was
obtained.
[0520] Elemental analysis: C, 26.83; H, 5.21; Ag, 14.06; In, 16.48;
Se, 31.00. NMR: (1H) 1.51 (d, 6H, 3JHH=7.2 Hz), 1.67 (s, 27H),
1.74-1.83 (m, 1H) in CDCl.sub.3; (13C) 23.3, 25.8, 38.7 and 45.0 in
CDCl.sub.3; (77Se) 193.3.
[0521] In FIG. 18 is shown the TGA for this MP1-Ag molecular
precursor. The TGA showed a transition ending at about 205.degree.
C. The yield for the transition was 56.2% (w/w), as compared to a
theoretical yield for the formula AgInSe.sub.2 of 56.5% (w/w).
Thus, the TGA showed that this MP1-Ag molecular precursor can be
used to prepare AgInSe.sub.2 layers and materials, and can be used
as a component to prepare other semiconductor layers, crystals, and
materials.
[0522] The unit cell of this crystalline MP1-Ag precursor molecule
was determined by single crystal X-ray diffraction.
Example 29
Molecular Precursor Ink Compositions
[0523] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by dissolving an MP1-Ag molecular
precursor represented by the formula
Ag--(Se.sup.tBu).sub.3In.sup.nBu in toluene to a concentration of
1% (w/w).
Example 30
[0524] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by dissolving an MP1-Ag molecular
precursor represented by the formula
Ag--(Se.sup.tBu).sub.3In.sup.nBu in decane, and heating the decane
to dissolve the molecular precursor to a concentration of 5% (w/w).
To this solution is added In(Se.sup.nBu).sub.3, in an amount
representing 0.1 atom-equivalents of indium relative to silver in
the MP1-Ag molecular precursor.
Example 31
[0525] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by dissolving two MP1-Ag molecular
precursors represented by the formulas
Ag--(Se.sup.tBu).sub.3In.sup.sBu and
Ag--(Se.sup.tBu).sub.3Ga.sup.sBu in xylene to a total concentration
of 10% (w/w). 0.25 indium-atom-equivalents of
Ag--(Se.sup.tBu).sub.3In.sup.sBu are added to 0.75
gallium-atom-equivalents of Ag--(Se.sup.tBu).sub.3Ga.sup.sBu,
relative to the total amount of silver.
Example 32
[0526] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by slurrying an MP1-Ag molecular
precursor represented by the formula
Ag--(Se.sup.tBu).sub.3Ga.sup.tBu in toluene to a concentration of
8% (w/w). To this slurry is added 0.3% (w/w) polyurethane and 0.1
mol % of sodium as NaSe.sup.nBu relative to silver.
Example 33
[0527] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by slurrying equimolar amounts of
two MP1-Ag molecular precursors represented by the formulas
Ag--(Se.sup.tBu).sub.3Ga.sup.tBu and
Ag--(Se.sup.tBu).sub.3In.sup.tBu in heated xylene to a total
concentration of 50% (w/w). To this slurry is added
In(Se.sup.nBu).sub.3 and Ga(Se.sup.nBu).sub.3, in an amount
representing 0.1 atom-equivalents of indium and 0.1
atom-equivalents of gallium, respectively, relative to total
silver.
Example 34
[0528] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by dissolving MP1-Ag molecular
precursors Ag--(Se.sup.tBu).sub.3In.sup.sBu and
Ag--(Se.sup.tBu).sub.3Ga.sup.sBu in a molar equivalent ratio of
1:3, respectively, in heated toluene to a total concentration of
10% (w/w). To this solution is added Ga(Se.sup.sBu).sub.3 in an
amount representing 0.111 molar equivalents of indium relative to
total copper in the slurry, so that the final ratio of the elements
is Ag/Ga/In=0.90/0.77/0.23. To this solution is added 0.1 mol % of
sodium as NaIn(Se.sup.sBu).sub.4 relative to silver.
Example 35
[0529] A molecular precursor ink composition is prepared in a
glovebox in an inert atmosphere by mixing together MP1-Ag molecular
precursors Ag--(Se.sup.tBu).sub.3In.sup.iPr and
Ag--(Se.sup.tBu).sub.3Ga.sup.nBu in a molar equivalent ratio of
3:1, respectively. The mixture is dissolved in heated xylene to a
total concentration of 5% (w/w). To this mixture is added
In(Se.sup.nBu).sub.3 in an amount representing 0.176 molar
equivalents of indium relative to total silver in the slurry, so
that the final ratio of the elements is
Ag/In/Ga=0.85/0.79/0.21.
Example 36
Spin Casting Deposition of a Molecular Precursor Compound
[0530] A molecular precursor ink composition is prepared according
to Example 31. The molecular precursor ink is filtered with a 0.45
micron polyvinylidene difluoride (PVDF) filter. The ink is
deposited onto a Mo-coated glass substrate using a spin casting
unit in a glovebox in inert argon atmosphere. The substrate is spin
coated with the molecular precursor ink to a film thickness of
about 0.1 to 5 microns, with a SCS 6800 Spin Coater (Specialty
Coating Sys., Indianapolis, Ind.).
[0531] The substrate is removed and is heated at a temperature of
400.degree. C. in an inert atmosphere. A thin film material is
produced which is a photovoltaic absorber layer.
Example 37
[0532] A molecular precursor ink composition is prepared according
to Example 30. The ink is deposited onto a Mo-coated glass
substrate using a spin casting unit in a glovebox in inert
atmosphere. The substrate is spin coated with the molecular
precursor ink to a film thickness of about 0.1 to 5 microns, with a
SCS 6800 Spin Coater.
[0533] The substrate is removed and is heated at a temperature of
450.degree. C. in an inert atmosphere. A thin film material is
produced which is a photovoltaic absorber layer.
Example 38
Rod Coating a Molecular Precursor Ink Composition
[0534] A molecular precursor ink composition is prepared according
to Example 34. The ink is rod coated onto a Mo-coated glass
substrate using a K CONTROL COATER MODEL 201 (R K Print-Coat
Instr., Litlington, UK) in a glovebox in an inert atmosphere. A
film of 1 micron thickness is deposited on the substrate.
[0535] The substrate is removed and is heated at a temperature of
400.degree. C. in an inert atmosphere. A thin film material is
produced which is a photovoltaic absorber layer.
Example 39
Slot Die Coating a Molecular Precursor Ink Composition
[0536] A molecular precursor ink composition is prepared according
to Example 32. The ink is slot die coated onto a polyethylene
terephthalate substrate in an inert atmosphere. A film of 1.5
microns thickness is deposited on the substrate.
[0537] The substrate is removed and is heated at a temperature of
250.degree. C. in an inert atmosphere A thin film material is
produced which is a photovoltaic absorber layer.
Example 40
Screen Printing a Molecular Precursor Ink Composition
[0538] A molecular precursor ink composition is prepared according
to Example 33. The molecular precursor ink is screen printed onto a
Mo-coated stainless steel substrate in an inert atmosphere. A film
of 2.8 microns thickness is deposited on the substrate.
[0539] The substrate is removed and is heated at a temperature of
230.degree. C. in an inert atmosphere. A thin film material is
produced which is a photovoltaic absorber layer.
Example 41
Spraying a Molecular Precursor Ink Composition
[0540] A molecular precursor ink composition is prepared according
to Example 35. The molecular precursor ink is filtered with a 0.45
micron polyvinylidene difluoride (PVDF) filter. The ink is printed
onto a MYLAR substrate using an M3D Aerosol Jet Deposition System
(Optomec, Albuquerque) in a glovebox in an inert atmosphere. A film
of 120 nm thickness is deposited on the substrate.
[0541] The substrate is removed and is heated at a temperature of
200.degree. C. in an inert atmosphere. A thin film material is
produced which is a photovoltaic absorber layer.
Example 42
Printing a Molecular Precursor Ink Composition
[0542] A molecular precursor ink composition is prepared according
to Example 31. The ink is printed onto a molybdenum-coated glass
substrate using a DIMATIX DMP-2831 materials printer (Fujifilm
Dimatix, Lebanon, N.H.) in a glovebox in an inert atmosphere. A
film of 1 micron thickness is deposited on the substrate. The
substrate is removed and is heated at a temperature of 200.degree.
C. in an inert atmosphere A thin film material is produced which is
a photovoltaic absorber layer.
Example 43
Spray Pyrolysis of a Molecular Precursor on a Substrate
[0543] A molecular precursor ink composition is prepared according
to Example 29. The ink is sprayed onto a stainless steel substrate
using a spray pyrolysis unit in a glovebox in an inert atmosphere,
the spray pyrolysis unit having an ultrasonic nebulizer, precision
flow meters for inert gas carrier, and a tubular quartz reactor in
a furnace.
[0544] The spray-coated substrate is heated at a temperature of
250.degree. C. in an inert atmosphere. A thin film material is
produced which is a photovoltaic absorber layer.
Example 44
[0545] A molecular precursor ink composition is prepared according
to Example 30. The ink is sprayed onto an aluminum substrate using
a spray pyrolysis unit in a glovebox in an inert atmosphere, the
spray pyrolysis unit having an ultrasonic nebulizer, precision flow
meters for inert gas carrier, and a tubular quartz reactor in a
furnace.
[0546] The spray-coated substrate is heated at a temperature of
250.degree. C. in an inert atmosphere. A thin film material is
produced which is a photovoltaic absorber layer.
Example 45
Preparation of a Solar Cell
[0547] A solar cell is made by depositing an electrode layer on a
polyethylene terephthalate substrate. A thin film material
photovoltaic absorber layer is coated onto the electrode layer
according to Example 39. A CdS window layer is deposited on the
absorber layer. An aluminum-doped ZnO TCO layer is deposited onto
the window layer.
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