# US 8,465,679 B2 · Methods for CAIGAS aluminum-containing photovoltaics

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- Number: US 8,465,679 B2
- Document ID: US8465679B2
- Status: Granted
- Kind: B2
- Application number: 12/869,683
- Filed: 2010-08-26
- Published: 2011-02-10
- Granted: 2013-06-18
- Earliest claimed: 2009-08-04
- Assignees: Precursor Energetics, Inc.
- Applicants: Kyle L. Fujdala; Wayne A. Chomitz; Zhongliang Zhu; Matthew C. Kuchta
- Inventors: Kyle L. Fujdala; Wayne A. Chomitz; Zhongliang Zhu; Matthew C. Kuchta
- Web page: https://patentgrep.com/patent/US8465679B2

## CPC

- H10F 77/126: {comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]}
- C07C 391/00: Compounds containing selenium
- C07F 1/005: {without C-Metal linkages}
- C09D 11/03: characterised by features other than the chemical nature of the binder
- H10F 71/128: {Annealing}
- Y02E 10/541: CuInSe2 material PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

This invention relates to methods for making materials using compounds, polymeric 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, polymeric compounds, compositions, materials and methods directed ultimately toward photovoltaic applications, transparent conductive materials, as well as devices and systems for energy conversion, including solar cells. This invention further relates to methods for making CA(I,G,A)S, CAIGAS, A(I,G,A)S, AIGAS, C(I,G,A)S, and CIGAS materials by providing one or more polymeric precursor compounds or inks thereof, providing a substrate, depositing the compounds or inks onto the substrate; and heating the substrate at a temperature of from about 20° C. to about 650° C.

## Claims

### Claim 1

A method for making a material comprising,
(a) providing one or more CA(I,G,A)S, CAIGAS, A(I,G,A)S, AIGAS, C(I,G,A)S, CIGAS, CAIAS, CAGAS, AIAS, AGAS, CIAS, or CGAS polymeric precursor compounds or inks thereof comprising repeating unit structures {MB(ER)(ER)} and {MA(ER)(ER)};
(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° C. to about 650° C. in an inert atmosphere, thereby producing a material;
wherein MA is Cu or Ag and MB is In, Ga or Al, each E is S, Se or Te, and R represents R groups independently selected from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands.

### Claim 2 (depends on 1)

The method of claim 1, wherein the polymeric precursor compound has the empirical formula (Cu1−xAgx)u(In1−y−tGayAlt)v((S1−zSez)R)w, wherein x is from 0 to 1, y is from 0 to 1 minus t, t is from 0.001 to 1, the sum of y plus t is from 0.001 to 1, z is from 0 to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, w is from 2 to 6, and R represents R groups, of which there are w in number, and are independently selected from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands.

### Claim 3 (depends on 1)

The method of claim 1, wherein the material is a CA(I,G,A)S, CAIGAS, A(I,G,A)S, AIGAS, C(I,G,A)S, CIGAS, CAIAS, CAGAS, AIAS, AGAS, CIAS, or CGAS material.

### Claim 4 (depends on 1)

The method of claim 1, wherein the material is enriched or deficient in a Group 11 atom.

### Claim 5 (depends on 1)

The method of claim 1, wherein the substrate is heated at a temperature of from about 100° C. to about 550° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein the substrate is heated at a temperature of from about 200° C. to about 400° C.

### Claim 7 (depends on 1)

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/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, 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.

### Claim 8 (depends on 1)

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.

### Claim 9 (depends on 1)

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.

### Claim 10 (depends on 1)

The method of claim 1, wherein the substrate is a layer of a solar cell.

### Claim 11 (depends on 1)

The method of claim 1, further comprising an optional step of selenization or sulfurization, either before, during or after steps (c) or (d).

### Claim 12 (depends on 1)

The method of claim 1, wherein the material is a semiconductor.

### Claim 13 (depends on 1)

The method of claim 1, wherein the material is a photovoltaic.

### Claim 14 (depends on 1)

The method of claim 1, wherein the material is a thin film.

### Claim 15 (depends on 1)

The method of claim 1, wherein the material is a thin film with a thickness of from 0.001 to 100 micrometers.

### Claim 16 (depends on 1)

The method of claim 1, wherein the material is a thin film with a thickness of from 0.1 to 10 micrometers.