# US 12,112,897 B2 · Methods for perovskite device processing by vapor transport deposition

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

- Number: US 12,112,897 B2
- Document ID: US12112897B2
- Status: Granted
- Kind: B2
- Application number: 17/801,093
- Filed: 2021-02-19
- Published: 2023-03-16
- Granted: 2024-10-08
- Earliest claimed: 2020-02-19
- Assignees: First Solar, Inc.
- Applicants: First Solar, Inc.
- Inventors: Le Chen; David Ho; Xiaoping Li; Rick Powell; Tze-Bin Song; Vera Steinmann; Aravamuthan Varadarajan; Dirk Weiss; Gang Xiong; Zhibo Zhao
- Web page: https://patentgrep.com/patent/US12112897B2

## CPC

- C23C 14/0694: {Halides}
- C23C 14/228: {Gas flow assisted PVD deposition}
- C23C 14/243: {Crucibles for source material (C23C14/28, C23C14/30 take precedence)}
- C23C 14/50: Substrate holders
- C23C 14/5806: {Thermal treatment}
- H01G 9/0036: {Formation of the solid electrolyte layer}
- H01G 9/2009: {Solid electrolytes}
- H10F 77/12: Active materials
- H10K 30/40: comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
- H10K 30/50: Photovoltaic [PV] devices
- H10K 30/82: Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K 71/164: {using vacuum deposition}
- H10K 85/30: Coordination compounds
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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)
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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

Structures and methods for manufacturing photovoltaic devices by forming perovskite layers and perovskite precursor layers using vapor transport deposition (VTD) are described.

## Claims

### Claim 1

A method of forming a perovskite precursor layer comprising:
providing a substrate stack in a deposition chamber, the substrate stack having a first charge transport layer on an electrode;
depositing a first perovskite-forming composition on the substrate stack in the deposition chamber by a vapor transport deposition (VTD) process, comprising:
heating a source material to a temperature in a range of 375° C. to 550° C., wherein the source material comprises at least one of: lead iodide (PbI2), lead bromide (PbBr2), cesium bromide (CsBr), cesium lead iodide (CsPbI3), cesium tin iodide (CsSnI3), lead chloride (PbCl2), tin iodide (SnI2), tin bromide (SnBr2), or tin chloride (SnCl2);
providing a vapor curtain to direct vapor of the source material using a carrier gas toward the substrate stack in the deposition chamber, wherein the vapor curtain has a width greater than 1 meter, the deposition chamber having a pressure in a range of 0.1 to 2.0 Torr; and
forming the precursor layer, at a deposition rate in a range of 0.01 to 1.50 μm per minute, to a thickness of 100-2000 nm, wherein the precursor layer comprises a plurality of metal halide crystal grain structures, wherein: the grain structures have a height, normal to the surface of the substrate stack, and a width, parallel to the surface of the substrate stack, and an average grain width is less than a third of an average grain height.

### Claim 2 (depends on 1)

The method of claim 1, wherein:
the deposition chamber has a pressure in a range of 0.1 to 1.0 Torr;
the deposition chamber has a temperature in a range of 20° C. to 150° C.;
the source material is heated to a temperature in a range of 400° C. to 525° C.; and
a carrier gas flow rate in a range from 80 sccm to 150 sccm.

### Claim 3 (depends on 1)

The method of claim 1, wherein the source material is provided as a powder.

### Claim 4 (depends on 1)

The method of claim 1, wherein the precursor layer comprises at least one metal halide in a crystal matrix having a porosity in a range from 35% to 65%.

### Claim 5 (depends on 1)

The method of claim 1, wherein forming the precursor layer to the thickness comprises forming the precursor layer to a thickness in a range of 200-1500 nm.

### Claim 6 (depends on 1)

The method of claim 1, wherein the precursor layer comprises at least one of: lead iodide (PbI2), lead bromide (PbBr2), cesium bromide (CsBr), or cesium tin iodide (CsSnI3), in a crystal matrix having a porosity greater than 35%.

### Claim 7 (depends on 1)

The method of claim 1, wherein the precursor layer comprises a plurality of lead iodide crystal grain structures, wherein: the grain structures have a height, normal to the surface of the substrate stack, and a width, parallel to the surface of the substrate stack, and at least a quarter of grain structures of the precursor layer have a height that is in a range of 200 nm to 700 nm and a width that is less than 100 nm.

### Claim 8 (depends on 1)

The method of claim 1, wherein the deposition rate is in a range of 0.05 to 0.50 μm per minute.

### Claim 9 (depends on 1)

The method of claim 1, wherein the carrier gas comprises at least one of: argon, helium, or nitrogen.

### Claim 10 (depends on 1)

The method of claim 1, wherein the precursor layer comprises a plurality of crystalline grains, and wherein 30-100% of the grains have a size with at least one dimension having a length in a range of 200-800 nm.

### Claim 11

A method of forming a perovskite precursor layer for a photovoltaic device, the method comprising:
providing a substrate stack in a deposition chamber, the substrate stack having a first charge transport layer on an electrode;
depositing a first perovskite-forming composition on the substrate stack in the deposition chamber by a vapor transport deposition (VTD) process, comprising:
heating a source material to a temperature in a range of 400° C. to 525° C.;
providing a vapor curtain to direct vapor of the source material using a carrier gas toward the substrate stack in the deposition chamber, wherein:
the deposition chamber has a pressure in a range of 0.1 to 1.0 Torr;
the deposition chamber has a temperature in a range of 20° C. to 150° C.;
the source material comprises at least one of: lead iodide (PbI2), lead bromide (PbBr2), cesium bromide (CsBr), cesium lead iodide (CsPbI3), cesium tin iodide (CsSnI3), lead chloride (PbCl2), tin iodide (SnI2), tin bromide (SnBr2), or tin chloride (SnCl2);
a carrier gas flow rate is in a range from 80 sccm to 150 sccm; and
forming the precursor layer to a thickness in a range of 200 nm to 1500 nm,
whereby the precursor layer comprises a plurality of metal halide crystal grain structures.

### Claim 12 (depends on 11)

The method of claim 11, wherein the metal halide grain structures have a height, normal to the surface of the substrate stack, and a width, parallel to the surface of the substrate stack, and at least a quarter of grain structures of the precursor layer have a height that is in a range of 200 nm to 700 nm, and a width that is less than 100 nm.