# US 2019/0245103 A1 · Copper indium gallium selenide absorption layer and preparation method thereof, solar cell and preparation method thereof

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

- Number: US 2019/0245103 A1
- Document ID: US20190245103A1
- Status: Published application
- Kind: A1
- Application number: 16/263,037
- Filed: 2019-01-31
- Published: 2019-08-08
- Earliest claimed: 2018-02-08
- Assignees: Beijing Apollo Ding Rong Solar Technology Co., Ltd.
- Applicants: Beijing Apollo Ding Rong Solar Technology Co., Ltd.
- Inventors: Yakuan YE; Shuli ZHAO; Lida GUO; Lihong YANG
- Web page: https://patentgrep.com/patent/US20190245103A1

## CPC

- H10F 77/126: {comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]}
- C23C 14/0623: {Sulfides, selenides or tellurides}
- C23C 14/14: Metallic material, boron or silicon
- C23C 14/3464: {using more than one target (C23C14/56 takes precedence)}
- C23C 14/5806: {Thermal treatment}
- C23C 14/5866: {Treatment with sulfur, selenium or tellurium}
- H10F 71/128: {Annealing}
- H10P 14/203: {using transformation of metal, e.g. oxidation or nitridation}
- H10P 14/22: using physical deposition, e.g. vacuum deposition or sputtering
- H10P 14/3436: {being chalcogenide semiconductor materials not being oxides, e.g. ternary compounds}
- Y02E 10/50: Photovoltaic [PV] energy
- 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
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- 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

A preparation method of a copper indium gallium selenide (CIGS) absorption layer, including: forming a prefabricated copper indium gallium film on a substrate; placing the prefabricated copper indium gallium film in a reaction chamber having a first temperature threshold; introducing a selenium atmosphere having a first carrier gas flow value into the reaction chamber, such that the prefabricated copper indium gallium film reacts within a first duration to form an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase on a surface of the prefabricated copper indium gallium film; introducing a selenium atmosphere having a second carrier gas flow value into the reaction chamber, such that the prefabricated copper indium gallium film reacts within a second preset duration to obtain a prefabricated CIGS film; annealing the prefabricated CIGS film within a second preset temperature threshold and a third preset duration to obtain a solar cell absorption layer.

## Claims

### Claim 1

A preparation method of a copper indium gallium selenide absorption layer, comprising:
step 100: forming a copper gallium alloy layer and an indium layer sequentially on a substrate to obtain a prefabricated copper indium gallium film;
step 200: placing the prefabricated copper indium gallium film into a reaction chamber having a first preset temperature threshold; introducing a selenium atmosphere having a first preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film reacting in the selenium atmosphere having the first carrier gas flow value for a first preset duration, such that an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase are formed on a surface of the prefabricated copper indium gallium film;
step 300: introducing a selenium atmosphere having a second preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film having an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase formed on a surface thereof reacting in a selenium atmosphere having the second carrier gas flow value for a second preset duration, such that a selenium source contained in the selenium atmosphere diffuses toward a bottom of the prefabricated copper indium gallium film, and reacts with the copper indium gallium contained in the prefabricated copper indium gallium film to obtain a copper indium gallium selenide prefabricated film formed on a surface of the substrate;
step 400: annealing the copper indium gallium selenide prefabricated film formed on the surface of the substrate within a second preset temperature threshold and a third preset duration to obtain a copper indium gallium selenide absorption layer.

### Claim 2 (depends on 1)

The preparation method of a copper indium gallium selenide absorption layer according to claim 1, wherein a back electrode is deposited on the substrate;
the step 100 includes: sequentially sputtering a copper gallium alloy layer and an indium layer on a surface of the back electrode of the substrate, such that the back electrode, the copper gallium alloy layer and the indium layer are laminated together to obtain a prefabricated copper indium gallium film.

### Claim 3 (depends on 1)

The preparation method of a copper indium gallium selenide absorption layer according to claim 1, wherein the prefabricated copper indium gallium film comprises Cu, In, and Ga, and a molar ratio of Cu, In, and Ga contained in the prefabricated copper indium gallium film satisfies: 0.8<nCu/(nIn+nGa)<0.96 and 0.25≤nGa/(nIn+nGa)≤0.35.

### Claim 4 (depends on 3)

The preparation method of a copper indium gallium selenide absorption layer according to claim 3, wherein the second carrier gas flow value is less than the first carrier gas flow value.

### Claim 5 (depends on 3)

The preparation method of a copper indium gallium selenide absorption layer according to claim 3, wherein a ratio of the first carrier gas flow value to the second carrier gas flow value is greater than five.

### Claim 6 (depends on 5)

The preparation method of a copper indium gallium selenide absorption layer according to claim 5, wherein the first carrier gas flow value is greater than or equal to 5 slm and less than or equal to 15 slm, and the second carrier gas flow value is greater than zero and less than or equal to 2 slm.

### Claim 7 (depends on 1)

The preparation method of a copper indium gallium selenide absorption layer according to claim 1, wherein before the step 200, the preparation method of the copper indium gallium selenide absorption layer further comprises:
heating a solid selenium source to a temperature within a third preset temperature threshold in a vacuum or an inert gas with set pressure to obtain a selenium atmosphere.

### Claim 8 (depends on 7)

The preparation method of a copper indium gallium selenide absorption layer according to claim 7, wherein the first preset temperature threshold is 550° C.˜580° C., the second preset temperature threshold is 500° C.˜600° C., the third preset temperature threshold is 250° C.˜470° C., and the set pressure is 1 Pa˜1 atm.

### Claim 9 (depends on 8)

The preparation method of a copper indium gallium selenide absorption layer according to claim 8, wherein the first preset duration is 25 s to 35 s, the second preset duration is 260 s to 275 s, and the third preset duration is 5 min to 30 min.

### Claim 10 (depends on 7)

The preparation method of a copper indium gallium selenide absorption layer according to claim 7, wherein the first preset temperature threshold is 620° C.˜700° C., the second preset temperature threshold is 500° C.˜600° C., the third preset temperature threshold is 380° C.˜500° C., and the set pressure is 1 Pa·1 atm.

### Claim 11 (depends on 10)

The preparation method of a copper indium gallium selenide absorption layer according to claim 10, wherein the first preset duration is 15 s to 25 s, the second preset duration is 15 s to 35 s, and the third preset duration is 5 min to 30 min.

### Claim 12 (depends on 7)

The preparation method of a copper indium gallium selenide absorption layer according to claim 7 wherein the prefabricated copper indium gallium film in the step 200 has an average temperature-rising rate of greater than 3° C./s in the reaction chamber.

### Claim 13 (depends on 1)

The preparation method of a copper indium gallium selenide absorption layer according to claim 1, wherein the selenium atmosphere comprises selenium vapor and/or hydrogen selenide gas.

### Claim 14 (depends on 4)

The preparation method of a copper indium gallium selenide absorption layer according to claim 4, wherein the annealing treatment is performed in a vacuum or in a selenium atmosphere having a third preset carrier gas flow value; when the annealing process is performed in a selenium atmosphere having a third preset carrier gas flow value, the third preset carrier gas flow value is less than the second preset carrier gas flow value.

### Claim 15 (depends on 6)

The preparation method of a copper indium gallium selenide absorption layer according to claim 6, wherein the annealing treatment is performed in a vacuum or in a selenium atmosphere having a third preset carrier gas flow value; when the annealing process is performed in a selenium atmosphere having a third preset carrier gas flow value, the third preset carrier gas flow value is less than the second preset carrier gas flow value.

### Claim 16

A preparation method of a solar cell, wherein comprises the preparation method of a copper indium gallium selenide absorption layer as follows:
step 100: forming a copper gallium alloy layer and an indium layer sequentially on a substrate to obtain a prefabricated copper indium gallium film;
step 200: placing the prefabricated copper indium gallium film into a reaction chamber having a first preset temperature threshold; introducing a selenium atmosphere having a first preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film reacting in the selenium atmosphere having the first carrier gas flow value for a first preset duration, such that an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase are formed on a surface of the prefabricated copper indium gallium film;
step 300: introducing a selenium atmosphere having a second preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film having an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase formed on a surface thereof reacting in a selenium atmosphere having the second carrier gas flow value for a second preset duration, such that a selenium source contained in the selenium atmosphere diffuses toward a bottom of the prefabricated copper indium gallium film, and reacts with the copper indium gallium contained in the prefabricated copper indium gallium film to obtain a copper indium gallium selenide prefabricated film formed on a surface of the substrate;
step 400: annealing the copper indium gallium selenide prefabricated film formed on the surface of the substrate within a second preset temperature threshold and a third preset duration to obtain a copper indium gallium selenide absorption layer.

### Claim 17

A copper indium gallium selenide absorption layer prepared by the preparation method of the copper indium gallium selenide absorption layer, wherein the method comprises:
step 100: forming a copper gallium alloy layer and an indium layer sequentially on a substrate to obtain a prefabricated copper indium gallium film;
step 200: placing the prefabricated copper indium gallium film into a reaction chamber having a first preset temperature threshold; introducing a selenium atmosphere having a first preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film reacting in the selenium atmosphere having the first carrier gas flow value for a first preset duration, such that an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase are formed on a surface of the prefabricated copper indium gallium film;
step 300: introducing a selenium atmosphere having a second preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film having an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase formed on a surface thereof reacting in a selenium atmosphere having the second carrier gas flow value for a second preset duration, such that a selenium source contained in the selenium atmosphere diffuses toward a bottom of the prefabricated copper indium gallium film, and reacts with the copper indium gallium contained in the prefabricated copper indium gallium film to obtain a copper indium gallium selenide prefabricated film formed on a surface of the substrate;
step 400: annealing the copper indium gallium selenide prefabricated film formed on the surface of the substrate within a second preset temperature threshold and a third preset duration to obtain a copper indium gallium selenide absorption layer.

### Claim 18 (depends on 17)

The copper indium gallium selenide absorption layer according to claim 17, wherein a back electrode is deposited on the substrate;
the step 100 includes: sequentially sputtering a copper gallium alloy layer and an indium layer on a surface of the back electrode of the substrate, such that the back electrode, the copper gallium alloy layer and the indium layer are laminated together to obtain a prefabricated copper indium gallium film.

### Claim 19

A solar cell comprising the copper indium gallium selenide absorption layer, wherein the copper indium gallium selenide absorption layer is prepared as following steps:
step 100: forming a copper gallium alloy layer and an indium layer sequentially on a substrate to obtain a prefabricated copper indium gallium film;
step 200: placing the prefabricated copper indium gallium film into a reaction chamber having a first preset temperature threshold; introducing a selenium atmosphere having a first preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film reacting in the selenium atmosphere having the first carrier gas flow value for a first preset duration, such that an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase are formed on a surface of the prefabricated copper indium gallium film;
step 300: introducing a selenium atmosphere having a second preset carrier gas flow value into the reaction chamber; the prefabricated copper indium gallium film having an unsaturated In—Se binary phase and an unsaturated Cu—Se binary phase formed on a surface thereof reacting in a selenium atmosphere having the second carrier gas flow value for a second preset duration, such that a selenium source contained in the selenium atmosphere diffuses toward a bottom of the prefabricated copper indium gallium film, and reacts with the copper indium gallium contained in the prefabricated copper indium gallium film to obtain a copper indium gallium selenide prefabricated film formed on a surface of the substrate;
step 400: annealing the copper indium gallium selenide prefabricated film formed on the surface of the substrate within a second preset temperature threshold and a third preset duration to obtain a copper indium gallium selenide absorption layer.