# US 8,569,102 B2 · Method of manufacturing high density CIS thin film for solar cell and method of manufacturing thin film solar cell using the same

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- Number: US 8,569,102 B2
- Document ID: US8569102B2
- Status: Granted
- Kind: B2
- Application number: 13/695,627
- Filed: 2011-07-19
- Published: 2013-02-21
- Granted: 2013-10-29
- Earliest claimed: 2010-07-20
- Assignees: Korea Institute of Energy Research
- Applicants: Se-Jin Ahn; Jae-Ho Yun; Ji-Hye Gwak; Ara Cho; Kyung-Hoon Yoon; Kee-Shik Shin; Seoung-Kyu Ahn; Ki-Bong Song
- Inventors: Se-Jin Ahn; Jae-Ho Yun; Ji-Hye Gwak; Ara Cho; Kyung-Hoon Yoon; Kee-Shik Shin; Seoung-Kyu Ahn; Ki-Bong Song
- Web page: https://patentgrep.com/patent/US8569102B2

## CPC

- H10F 77/143: {comprising quantum structures}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01B 19/002: {Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions}
- C01G 15/006: {Compounds containing gallium, indium or thallium, with or without oxygen or hydrogen, and containing two or more other elements}
- H10F 71/00: Manufacture or treatment of devices covered by this subclass (patterning processes to connect thin photovoltaic cells in integrated devices, or assemblies of multiple devices, having photovoltaic cells H10F19/33; manufacture or treatment of encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells H10F19/80; manufacture or treatment of integrated devices, or assemblies of multiple devices, comprising at least one element in which radiation controls the flow of current H10F39/00)
- H10F 71/128: {Annealing}
- H10F 77/126: {comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]}
- C01P 2004/03: obtained by SEM
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- 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
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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

Disclosed are a high density CIS thin film and a method of manufacturing the same, which includes coating CIS nanopowders, CIGS nanopowders or CZTS nanopowders on a substrate by non-vacuum coating, followed by heat treatment with cavities between the nanopowders filled with filling elements such as copper, indium, gallium, zinc, tin, and the like. The high density CIS thin film is applied to a photo-absorption layer of a thin film solar cell, thereby providing a highly efficient thin film solar cell.

## Claims

### Claim 1

A method of manufacturing a high density CIS thin film, comprising:
preparing CIS nanoparticles;
dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare CIS slurry;
dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry, wherein the filling element-containing salt is a mixed salt of at least two selected from the group consisting of copper salt, indium salt, gallium salt, zinc salt, and tin salt;
mixing the CIS slurry and the filling element-containing slurry to prepare a slurry mixture; and
coating the slurry mixture onto a substrate to form a CIS thin film, followed by heat treatment.

### Claim 2 (depends on 1)

The method of claim 1, wherein the CIS nanoparticles comprise CIS nanoparticles, CICS nanoparticles, or CZTS nanoparticles.

### Claim 3 (depends on 1)

The method of claim 1, wherein the filling element-containing slurry further comprises a selenium compound.

### Claim 4 (depends on 3)

The method of claim 3, wherein the selenium compound is selected from the group consisting of SeO2, SeCl4, and selenourea.

### Claim 5 (depends on 1)

The method of claim 1, wherein the copper salt is selected from the group consisting of CuCl, Cu-acetate, CuI, and CuSO4.

### Claim 6 (depends on 1)

The method of claim 1, wherein the indium salt is selected from the group consisting of In(NO3)3, In2(SO4)3, and In-acetate.

### Claim 7 (depends on 1)

The method of claim 1, wherein the gallium salt is selected from the group consisting of GaCl3, Gal3, Ga(NO3)3 and Ga-acetate, the zinc salt is selected from the group consisting of ZnCl2, Zn(NO3)2 and Znl2, and the tin salt is SnCl4.

### Claim 8 (depends on 1)

The method of claim 1, wherein the solvent is an alcohol-based solvent including methanol, ethanol, phentanol, propanol, and butanol.

### Claim 9 (depends on 1)

The method of claim 1, wherein the binder is selected from the group consisting of ethylene glycol, propylene glycol, ethyl cellulose, and polyvinylpyrrolidone.

### Claim 10 (depends on 1)

The method of claim 1, wherein the CIS thin film is formed by non-vacuum coating selected from the group consisting of spraying, ultrasonic spraying, spin coating, doctor blade coating, screen printing, and inkjet printing.

### Claim 11 (depends on 1)

The method of claim 1, further comprising:
drying the CIS thin film after forming the CIS thin film and before the heat treatment.

### Claim 12 (depends on 1)

The method of claim 1, wherein the heat treatment is selenization heat treatment performed at 400 to 550° C. while supplying Se vapor.