# US 2009/0260670 A1 · Precursor ink for producing IB-IIIA-VIA semiconductors

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- Number: US 2009/0260670 A1
- Document ID: US20090260670A1
- Status: Published application
- Kind: A1
- Application number: 12/148,468
- Filed: 2008-04-18
- Published: 2009-10-22
- Earliest claimed: 2008-04-18
- Inventors: Xiao-Chang Charles Li
- Web page: https://patentgrep.com/patent/US20090260670A1

## CPC

- C09D 11/02: Printing inks (C09D11/30 takes precedence)
- H10F 77/126: {comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]}
- Y02E 10/541: CuInSe2 material PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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)
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- 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

Copper indium diselenide, copper indium gallium diselenide, and other IB-IIIA-VIA compounds are produced by the liquid deposition on a substrate of a precursor-containing ink, followed by heating to produce the desired material. The precursor containing ink is a mixture of three parts. The first part is plurality of particulates of metal compounds of IB, IIIA. The second part is chalcogen source of selenium, sulfur, or organic chalcogen compounds dissolved in a liquid organic solvent. The third part solution function as viscosity adjustment, as introduction of dopant of sodium ion and/or as ink stabilizer. The precursor ink can be coated on substrate at room temperature and it can be transferred into copper indium (gallium) chalcogenide semiconductor thin film upon baking and a chalcogenization process. The resulting thin film semiconducting material can be incorporated into photovoltaic and other electronic devices.

## Claims

### Claim 1

A precursor ink for printing semiconductor photovoltaic cells comprising:
a plurality of particulates of one or more metal compounds selected from IB, IIB and IIIA
a liquid chalcogen solution
a functional solution

### Claim 2 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the metal compounds are oxide, chalcogenide, halide, hydroxide, carboxylic salt, nitrate, sulfonate, triflate of IB, IIB, and IIIA.

### Claim 3 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the metal compounds are compounds of copper, zinc, cadmium, indium, gallium, aluminum

### Claim 4 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the metal compounds are carboxylic salts with the carbon number less than 33.

### Claim 5 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the liquid chalcogen solution is the solution of trioctylphophine dissolved with chalcogen elements of S, Se or Te.

### Claim 6 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the liquid chalcogen solution is the solution of trioctylphophine dissolved with organic chalcogen with the formula of R1XR2 and/or R1XXR2, wherein X=S, Se, and R1/R2 are hydrocarbon with carbon number less than 12.

### Claim 7 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the functional solution is a solvent or solvent mixture function as viscosity adjustment and is selected from those containing heteroatom of N, P, O and the viscosity is preferably between 500 to 10,000 cp.

### Claim 8 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the functional solution is a solvent or solvent mixture function as stabilizing the ink particulates and is selected from those containing heteroatom of N, P, O.

### Claim 9 (depends on 1)

A precursor ink for printing semiconductor photovoltaic cells according to claim 1, wherein the functional solution is a solvent or solvent mixture dissolved with a sodium ion dopant and function as a promoter for CIGS crystal growth.

### Claim 10

A method for making a semiconductor film with the general formula Cu(InaGabAlc)SeyS2-y, where 0.7<a+b+c<1.3 and 0≦y≦2, by the following steps:
a) Selenium, sulfur or both are dissolved in a liquid organic solvent. The chemical composition of this liquid organic solvent includes one or more of the elements phosphorus, sulfur and oxygen.
b) The liquid organic solvent produced in step a) is mixed with a plurality of particulates of metal sources or metal compounds selected from IB, IIB and IIIA.
c) Formulation a precursor ink by mixing a) and b) and a functional solution for adjusting viscosity, increasing ink stability and containing sodium ion to promoting CIGS crystal growth.
d) Apply the precursor ink c) on substrate and followed with a baking process under elevated temperature at vacuum.
e) Chalcogenize the baked film of d) at atmosphere of chalcogen vapor and/or at atmosphere of hydrogen chalcogenide to cause some of the components of the ink produced in step c) and deposited on a substrate in step d) to react and creating the desired polycrystalline semiconductor film.

### Claim 11 (depends on 1, 12)

A thin film photovoltaic cell in which a semiconducting layer is made as in claims 1 and 12.

### Claim 12 (depends on 1, 12)

A thin film photovoltaic cell as in claim 1 in which the semiconducting layer made as in claims 12 is the light-absorbing p layer of the device.

### Claim 13 (depends on 11)

A photovoltaic module made up of photovoltaic cells as in claim 11.