# US 10,872,734 B2 · Solvent-free, solid phase synthesis of hybrid lead halide perovskites with superior purity

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- Number: US 10,872,734 B2
- Document ID: US10872734B2
- Status: Granted
- Kind: B2
- Application number: 15/854,596
- Filed: 2017-12-26
- Published: 2018-07-19
- Granted: 2020-12-22
- Earliest claimed: 2017-01-18
- Assignees: Iowa State University Research Foundation, Inc.
- Applicants: Javier Vela-Becerra; Bryan A. Rosales
- Inventors: Javier Vela-Becerra; Bryan A. Rosales
- Web page: https://patentgrep.com/patent/US10872734B2

## CPC

- C07F 7/24: Lead compounds
- H01G 9/0029: {Processes of manufacture}
- H01G 9/2004: {characterised by the electrolyte, e.g. comprising an organic electrolyte}
- H01G 9/2077: {Sealing arrangements, e.g. to prevent the leakage of the electrolyte}
- H10K 30/81: Electrodes
- H10K 30/88: Passivation; Containers; Encapsulations
- H10K 71/311: {Purifying organic semiconductor materials}
- H10K 85/30: Coordination compounds
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- H10K 85/60: Organic compounds having low molecular weight (H10K85/10 - H10K85/50 take precedence)
- H10K 30/15: Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 (photo-electrochemical devices comprising a liquid electrolyte or a solid electrolyte H01G9/20)
- H10K 30/50: Photovoltaic [PV] devices
- Y02E 10/542: Dye sensitized solar cells
- Y02E 10/549: Organic PV cells
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A method of synthesizing a mixed-halide perovskite is disclosed herein. The method includes the steps of mixing a first single-halide perovskite and a second single-halide perovskite to form a solid phase mixture and heating the solid phase mixture at a temperature below a first decomposition temperature of the first single-halide perovskite and below a second decomposition temperature of the second single-halide perovskite for a time sufficient to form the mixed-halide perovskite. During the mixing, the first and second single-halide perovskite are both in the solid phase. A mixed-halide perovskite made according to the method is also disclosed herein. The mixed-halide perovskite is free of amorphous and/or semicrystalline phases. The mixed-halide perovskite can be utilized in a photovoltaic cell in a solar panel.

## Claims

### Claim 1

A method of synthesizing a mixed-halide perovskite, comprising the steps of:
mixing a first single-halide perovskite and a second single-halide perovskite to form a solid- phase mixture, wherein the first single-halide perovskite and the second single- halide perovskite are both in the solid phase during mixing; and
heating the solid phase mixture at a temperature below a first decomposition temperature of the first single-halide perovskite and below a second decomposition temperature of the second single-halide perovskite for a time sufficient to form the mixed- halide perovskite;
wherein the first-single halide perovskite and the second single-halide perovskite each comprise at least one of lead or tin.

### Claim 2 (depends on 1)

The method of claim 1, wherein the heating step comprises forming the mixed-halide perovskite free of any semicrystalline phases.

### Claim 3 (depends on 1)

The method of claim 1, further comprising the step of annealing the mixed-halide perovskite at a temperature of approximately 200° C. for between 1 hour and 72 hours.

### Claim 4 (depends on 1)

A mixed-halide perovskite made according to the method of claim 1, wherein the mixed-halide perovskite is free of amorphous and/or semicrystalline phases.

### Claim 5 (depends on 4)

A photovoltaic cell capable of powering an electrical load, the photovoltaic cell comprising:
a transparent cover;
an n-type semiconductor;
a first electrical contact strip, the first electrical contact strip being disposed between the transparent cover and the n-type semiconductor and being in electrical communication with the n-type semiconductor;
a p-type semiconductor;
a junction layer disposed between the n-type semiconductor and the p-type semiconductor; and
a second electrical contact strip, the second contact strip being in electrical communication with the p-type semiconductor,
wherein the junction layer is comprised of a mixed-halide perovskite according to claim 4.

### Claim 6 (depends on 5)

The photovoltaic cell of claim 5, wherein the mixed-halide perovskite has the formula CH3NH3PbX3-aX′a, wherein X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 7 (depends on 5)

The photovoltaic cell of claim 5, wherein the mixed-halide perovskite has the formula HC(NH2)2PbX3-aX′a, wherein X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 8 (depends on 5)

The photovoltaic cell of claim 5, wherein the mixed-halide perovskite has the formula APbX3-aX′a, wherein A is an alkali metal, wherein X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 9 (depends on 8)

The photovoltaic cell of claim 8, wherein A is Rb or Cs.

### Claim 10 (depends on 5)

The photovoltaic cell of claim 5, wherein the mixed-halide perovskite has the formula A1-bA′bPbX3-aX′a, wherein A is Rb or Cs, A′ is CH3NH3 or HC(NH2)2, and X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 11 (depends on 10)

The photovoltaic cell of claim 10, wherein A is Rb or Cs and A′ is CH3NH3 or HC(NH2)2.

### Claim 12 (depends on 5)

A solar panel comprised of one or more photovoltaic cells according to claim 5.

### Claim 13

A method of synthesizing a mixed-halide perovskite, comprising the steps of:
mixing a first single-halide perovskite and a second single-halide perovskite to form a solid- phase mixture, wherein the first single-halide perovskite and the second single-halide perovskite are both in the solid phase during mixing; and
heating the solid phase mixture at a temperature below a first decomposition temperature of the first single-halide perovskite and below a second decomposition temperature of the second single-halide perovskite for a time sufficient to form the mixed-halide perovskite;
wherein the heating step comprises forming a mixed-halide perovskite with a formula of CH3NH3PbX3-aX′a, wherein X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 14 (depends on 13)

The method of claim 13, wherein the heating step comprises heating the solid phase mixture to a temperature of approximately 200° C.

### Claim 15 (depends on 14)

The method of claim 14, wherein the heating step comprises heating the solid phase mixture for between 0.5 and 1 hour.

### Claim 16 (depends on 13)

A mixed-halide perovskite made according to the method of claim 13, wherein the mixed-halide perovskite is free of amorphous and/or semicrystalline phases.

### Claim 17

A method of synthesizing a mixed-halide perovskite, comprising the steps of:
mixing a first single-halide perovskite and a second single-halide perovskite to form a solid- phase mixture, wherein the first single-halide perovskite and the second single-halide perovskite are both in the solid phase during mixing; and
heating the solid phase mixture at a temperature below a first decomposition temperature of the first single-halide perovskite and below a second decomposition temperature of the second single-halide perovskite for a time sufficient to form the mixed-halide perovskite;
wherein the heating step comprises forming a mixed-halide perovskite with a formula of HC(NH2)2PbX3-aX′a, wherein X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 18 (depends on 17)

A mixed-halide perovskite made according to the method of claim 17, wherein the mixed-halide perovskite is free of amorphous and/or semicrystalline phases.

### Claim 19

A method of synthesizing a mixed-halide perovskite, comprising the steps of:
mixing a first single-halide perovskite and a second single-halide perovskite to form a solid- phase mixture, wherein the first single-halide perovskite and the second single-halide perovskite are both in the solid phase during mixing; and
heating the solid phase mixture at a temperature below a first decomposition temperature of the first single-halide perovskite and below a second decomposition temperature of the second single-halide perovskite for a time sufficient to form the mixed- halide perovskite;
wherein the heating step comprises forming a mixed-halide perovskite with a formula of APbX3-aX′a, wherein A is an alkali metal, wherein X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 20 (depends on 19)

The method of claim 19, wherein the step of forming a mixed-halide perovskite includes selecting A to be Rb or Cs.

### Claim 21 (depends on 19)

A mixed-halide perovskite made according to the method of claim 19, wherein the mixed-halide perovskite is free of amorphous and/or semicrystalline phases.

### Claim 22 (depends on 21)

The mixed-halide perovskite of claim 21, wherein A is Rb or Cs.

### Claim 23

A method of synthesizing a mixed-halide perovskite, comprising the steps of:
mixing a first single-halide perovskite and a second single-halide perovskite to form a solid- phase mixture, wherein the first single-halide perovskite and the second single-halide perovskite are both in the solid phase during mixing; and
heating the solid phase mixture at a temperature below a first decomposition temperature of the first single-halide perovskite and below a second decomposition temperature of the second single-halide perovskite for a time sufficient to form the mixed-halide perovskite;
wherein the heating step comprises forming a mixed-halide perovskite with a formula of A1-bA′bPbX3-aX′a, wherein A is an alkali metal and A′ is an organic cation, wherein X and X′ are selected from the group consisting of I, Br, and Cl, and wherein 0>a>3.

### Claim 24 (depends on 23)

The method of claim 23, wherein the step of forming a mixed-halide perovskite with a formula of A1-bA′bPbX3-aX′a comprises selecting A to be Rb or Cs and A′ to be CH3NH3 or HC(NH2)2.

### Claim 25 (depends on 23)

A mixed-halide perovskite made according to the method of claim 23, wherein the mixed-halide perovskite is free of amorphous and/or semicrystalline phases.

### Claim 26 (depends on 25)

The mixed-halide perovskite of claim 25, wherein A is Rb or Cs and A′ is CH3NH3 or HC(NH2)2.