# US 2017/0288075 A1 · Method of preparing metal chalcogenide nanoparticles and method of producing light absorption layer thin film based thereon

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2017/0288075 A1
- Document ID: US20170288075A1
- Status: Published application
- Kind: A1
- Application number: 15/508,825
- Filed: 2015-10-27
- Published: 2017-10-05
- Earliest claimed: 2014-11-13
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Eun Ju PARK; Seokhee YOON; Seokhyun YOON; Hosub LEE
- Web page: https://patentgrep.com/patent/US20170288075A1

## CPC

- H10F 77/127: {comprising only Group IV-VI or only Group II-IV-VI chalcogenide materials, e.g. PbSnTe}
- C01G 9/08: Sulfides
- C01G 19/006: {Compounds containing tin, with or without oxygen or hydrogen, and containing two or more other elements}
- C09D 11/52: Electrically conductive inks
- H10F 71/128: {Annealing}
- H10F 77/211: {for photovoltaic cells}
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/74: by peak-intensities or a ratio thereof only
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/03: obtained by SEM
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2004/84: one phase coated with the other
- C01P 2006/40: Electric properties
- Y02E 10/543: Solar cells from Group II-VI materials
- 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
- 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)
- 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)
- 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 single-source precursor for synthesizing metal chalcogenide nanoparticles for producing a light absorption layer of solar cells comprising a Group VI element linked as a ligand to any one metal selected from the group consisting of copper (Cu), zinc (Zn) and tin (Sn), metal chalcogenide nanoparticles produced by heat-treating at least one type of the single-source precursor, a method of preparing the same, a thin film produced using the same and a method of producing the thin film.

## Claims

### Claim 1

A single-source precursor for synthesizing metal chalcogenide nanoparticles for producing a light absorption layer of solar cells comprising a Group VI element linked as a ligand to any one metal selected from the group consisting of copper (Cu), zinc (Zn) and tin (Sn).

### Claim 2 (depends on 1)

The single-source precursor according to claim 1, wherein the single-source precursor comprises a copper (Cu)-ligand complex, a tin (Sn)-ligand complex or a zinc (Zn)-ligand complex.

### Claim 3 (depends on 1)

The single-source precursor according to claim 1, wherein the ligand comprises one or more selected from the following:

### Claim 4 (depends on 1)

Metal chalcogenide nanoparticles produced by heat-treating at least one type of single-source precursor comprising the single-source precursor according to claim 1.

### Claim 5 (depends on 4)

The metal chalcogenide nanoparticles according to claim 4, wherein the metal chalcogenide nanoparticles comprise copper (Cu)-containing chalcogenide nanoparticles, tin (Sn)-containing chalcogenide nanoparticles, or zinc (Zn)-containing chalcogenide nanoparticles.

### Claim 6 (depends on 4)

The metal chalcogenide nanoparticles according to claim 4, wherein the metal chalcogenide nanoparticles comprise copper (Cu)-tin (Sn)-containing chalcogenide nanoparticles, copper (Cu)-zinc (Zn)-containing chalcogenide nanoparticles, or tin (Sn)-zinc (Zn)-containing chalcogenide nanoparticles.

### Claim 7 (depends on 4)

The metal chalcogenide nanoparticles according to claim 4, wherein the metal chalcogenide nanoparticles comprise copper (Cu)-tin (Sn)-zinc (Zn)-containing chalcogenide nanoparticles.

### Claim 8 (depends on 4)

The metal chalcogenide nanoparticles according to claim 4, wherein the metal chalcogenide nanoparticles comprise composite nanoparticles comprising copper (Cu)-containing chalcogenide and tin (Sn)-containing chalcogenide, or composite nanoparticles comprising copper (Cu)-containing chalcogenide and zinc (Zn)-containing chalcogenide, or comprise composite nanoparticles comprising tin (Sn)-containing chalcogenide and zinc (Zn)-containing chalcogenide.

### Claim 9 (depends on 8)

The metal chalcogenide nanoparticles according to claim 8, wherein the composite nanoparticles comprising copper (Cu)-containing chalcogenide and tin (Sn)-containing chalcogenide are core-shell structure nanoparticles comprising a core comprising copper (Cu)-containing chalcogenide and a shell comprising tin (Sn)-containing chalcogenide; the composite nanoparticles comprising copper (Cu)-containing chalcogenide and zinc (Zn)-containing chalcogenide are core-shell structure nanoparticles comprising a core comprising copper (Cu)-containing chalcogenide and a shell comprising zinc (Zn)-containing chalcogenide; and the composite nanoparticles comprising tin (Sn)-containing chalcogenide and zinc (Zn)-containing chalcogenide are core-shell structure nanoparticles comprising a core comprising tin (Sn)-containing chalcogenide and a shell comprising zinc (Zn)-containing chalcogenide.

### Claim 10 (depends on 4)

The metal chalcogenide nanoparticles according to claim 4, wherein the metal chalcogenide nanoparticles comprise composite nanoparticles comprising copper (Cu)-tin (Sn)-containing chalcogenide and zinc (Zn)-containing chalcogenide, or composite nanoparticles comprising copper (Cu)-zinc (Zn)-containing chalcogenide and tin (Sn)-containing chalcogenide, or composite nanoparticles comprising tin (Sn)-zinc (Zn)-containing chalcogenide and copper (Cu)-containing chalcogenide.

### Claim 11 (depends on 10)

The metal chalcogenide nanoparticles according to claim 10, wherein the composite nanoparticles comprising copper (Cu)-tin (Sn)-containing chalcogenide and zinc (Zn)-containing chalcogenide are core-shell structure nanoparticles comprising a core comprising copper (Cu)-tin (Sn)-containing chalcogenide and a shell comprising zinc (Zn)-containing chalcogenide; the composite nanoparticles comprising copper (Cu)-zinc (Zn)-containing chalcogenide and tin (Sn)-containing chalcogenide are core-shell structure nanoparticles comprising a core comprising copper (Cu)-zinc (Zn)-containing chalcogenide and a shell comprising tin (Sn)-containing chalcogenide; and the composite nanoparticles comprising tin (Sn)-zinc (Zn)-containing chalcogenide and copper (Cu)-containing chalcogenide are core-shell structure nanoparticles comprising a core comprising tin (Sn)-zinc (Zn) chalcogenide and a shell comprising copper (Cu)-containing chalcogenide.

### Claim 12 (depends on 4)

A method of preparing the metal chalcogenide nanoparticles according to claim 4 comprising heat-treating at least one type of single-source precursor comprising a Group VI element linked as a ligand to any one metal selected from the group consisting of copper (Cu), zinc (Zn) and tin (Sn).

### Claim 13 (depends on 4)

A method of preparing the metal chalcogenide nanoparticles according to claim 4 comprising:
(a) heat-treating a mixture including at least one type of single-source precursor including a Group VI element linked as a ligand to any one metal selected from the group consisting of copper (Cu), zinc (Zn) and tin (Sn); and
(b) adding, to the heat-treated mixture, a mixture including at least one type of single-source precursor including a Group VI element linked as a ligand to any one selected from metals, among the copper (Cu), zinc (Zn) and tin (Sn), not selected in step (a), and heat-treating the resulting mixture.

### Claim 14 (depends on 13)

The method according to claim 13, further comprising:
after step (b), adding a mixture including at least one type of single-source precursor including a Group VI element linked as a ligand to any one selected from metals, among the copper (Cu), zinc (Zn) and tin (Sn), not selected in steps (a) and (b), and heat-treating the resulting mixture.

### Claim 15 (depends on 12)

The method according to claim 12, wherein the heat-treatment is carried out at a temperature of 50 to 300° C.

### Claim 16 (depends on 4)

An ink composition comprising at least one type of the metal chalcogenide nanoparticles according to claim 4 dispersed in a solvent.

### Claim 17 (depends on 16)

The ink composition according to claim 16, wherein the metal chalcogenide nanoparticles comprised in the ink composition have a composition of CujZnkSn (1.0≦j≦4.0, 0.5≦k≦2.0).

### Claim 18 (depends on 16)

The ink composition according to claim 16, wherein a molar ratio of the Group VI element of the metal chalcogenide nanoparticles comprised in the ink composition is 0.5 to 4.0, with respect to 1 mole of the total metal amount.

### Claim 19 (depends on 4)

A method of producing a thin film using the metal chalcogenide nanoparticles according to claim 4 comprising:
(i) dispersing, in a solvent, at least one type of the metal chalcogenide nanoparticles according to claim 4 to prepare an ink;
(ii) coating a substrate provided with an electrode with the ink; and
(iii) drying the ink coated on the substrate provided with an electrode, and conducting heat treatment.

### Claim 20 (depends on 19)

The method according to claim 19, wherein the solvent of step (i) comprises at least one organic solvent selected from the group consisting of alkane, alkene, alkyne, aromatic, ketone, nitrile, ether, ester, organic halide, alcohol, amine, thiol, carboxylic acid, phosphine, phosphate, sulfoxide and amide.

### Claim 21 (depends on 19)

The method according to claim 19, further comprising adding an additive to prepare the ink in step (i).

### Claim 22 (depends on 21)

The method according to claim 21, wherein the additive comprises at least one selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), Anti-terra 204, Anti-terra 205, ethyl cellulose, and DispersBYK110.

### Claim 23 (depends on 19)

The method according to claim 19, wherein the coating of step (ii) is carried out by wet coating, spray coating, doctor blade coating, or inkjet-printing.

### Claim 24 (depends on 19)

The method according to claim 19, wherein the heat-treatment of step (iii) is carried out in the presence of S or Se.

### Claim 25 (depends on 24)

The method according to claim 24, wherein the presence of S or Se is carried out by supplying H2S or H2Se gas or supplying Se or S gas through heating.

### Claim 26 (depends on 19)

The method according to claim 19, further comprising supplying S or Se as a particle and supplying the same during heat-treating.

### Claim 27 (depends on 19)

The method according to claim 19, further comprising supplying S or Se on a thin film by deposition.

### Claim 28 (depends on 19)

A thin film produced by the method according to claim 19.

### Claim 29 (depends on 28)

A thin film solar cell produced using the thin film according to claim 28.