# US 2018/0006254 A1 · Crystalline perovskite thin films and devices that include the films

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- Number: US 2018/0006254 A1
- Document ID: US20180006254A1
- Status: Published application
- Kind: A1
- Application number: 15/539,422
- Filed: 2015-12-23
- Published: 2018-01-04
- Earliest claimed: 2014-12-23
- Assignees: Los Alamos National Security, LLC
- Applicants: Los Alamos National Security, LLC
- Inventors: Aditya Mohite; Gautam Gupta; Hsing-Lin Wang; Wanyi Nie
- Web page: https://patentgrep.com/patent/US20180006254A1

## CPC

- H10K 71/12: using liquid deposition, e.g. spin coating
- H10K 71/40: Thermal treatment, e.g. annealing in the presence of a solvent vapour
- H10K 85/1135: {Polyethylene dioxythiophene [PEDOT]; Derivatives thereof}
- H10K 85/141: {comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE}
- H10K 85/215: {comprising substituents, e.g. PCBM}
- H10K 85/361: {Polynuclear complexes, i.e. complexes comprising two or more metal centers}
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- H10K 30/20: comprising organic-organic junctions, e.g. donor-acceptor junctions
- H10K 30/50: Photovoltaic [PV] devices
- Y02E 10/549: Organic PV cells
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Hybrid organic-inorganic perovskite thin films with average grain sizes of at least 50 micrometers were prepared and employed in solar cells. The PCE values of the solar cells did not degrade with the direction or the scan-rate of the applied voltage. The larger average grain sizes are believed to assist in reducing the influence of defect states on carrier recombination. The tunability of PCE with substrate temperature may be correlated to the quality of the crystalline perovskite formed using the hot-casting procedure. The larger average grain sizes lead to good crystalline quality, low defect density, and high carrier mobility. The process for growing hybrid organic-inorganic perovskites may be applicable to the preparation of other materials to overcome problems related to polydispersity, defect formation, and grain boundary recombination.

## Claims

### Claim 1

A process for preparing a device, comprising:
forming a layer of charge transport material on a transparent conducting substrate;
heating the substrate to a temperature of at least 100° C.;
forming a composition by mixing at least one lead halide compound, methylamine, and a solvent;
aging the composition at a temperature from about 50° C. to about 100° C. for at least 24 hours,
coating the layer of charge transport material with the aged composition;
converting the aged composition to a solid layer of perovskite CH3NH3PbIxCl3-x, wherein 0≦x≦3, the solid layer having a plurality of grains with an average size of at least 50 micrometers;
forming a second layer of charge transport material on the layer of solid perovskite; and
forming an electrode layer on the second layer of charge transport material.

### Claim 2 (depends on 1)

The process of claim 1, wherein the substrate comprises tin oxide.

### Claim 3 (depends on 1)

The process of claim 1, wherein the lead halide compound is selected from PbI2, PbCl2, and combinations thereof.

### Claim 4 (depends on 1)

The process of claim 1, wherein the solvent has a boiling point of 130° C. or higher.

### Claim 5 (depends on 1)

The process of claim 1, wherein the device is a solar cell.

### Claim 6 (depends on 1)

The process of claim 1, wherein the average grain size is at least 100 micrometers.

### Claim 7 (depends on 1)

The process of claim 1, wherein the average grain size is at least 0.50 millimeters.

### Claim 8 (depends on 1)

The process of claim 1, wherein the average grain size is from about 0.50 millimeters to about 2 millimeters.

### Claim 9 (depends on 1)

The process of claim 1, wherein the average grain size is from about 1 millimeter to about 2 millimeters.

### Claim 10

A device prepared by a process comprising the steps of:
forming a layer of charge transport material on a transparent conducting substrate;
heating the substrate to a temperature of at least 100° C.;
forming a composition by mixing at least one lead halide compound, methylamine, and a solvent;
aging the composition at a temperature from about 50° C. to about 100° C. for at least 24 hours,
coating the layer of charge transport material with the aged composition;
converting the aged composition to a solid layer of perovskite having grains with an average size of at least 50 micrometers;
forming a second layer of charge transport material on the layer of solid perovskite; and
forming an electrode layer on the second layer of charge transport material.

### Claim 11 (depends on 10)

The device of claim 10, wherein the substrate comprises tin oxide.

### Claim 12 (depends on 10)

The device of claim 10, wherein the lead halide compound is selected from PbI2, PbCl2, and combinations thereof.

### Claim 13 (depends on 10)

The device of claim 10, wherein the solvent has a boiling point of 130° C. or higher.

### Claim 14 (depends on 10)

The device of claim 10, wherein the device is a solar cell.

### Claim 15 (depends on 10)

The device of claim 10, wherein:
the forming the layer of charge transport material on the transparent conducting substrate comprises forming a layer of poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS) on a substrate of indium tin oxide and thereafter performing the heating the substrate to a temperature of at least 100° C.;
the forming the composition comprises mixing a 1:1 molar ratio of lead iodide and methylamine in a solvent;
the aging the composition comprises aging the composition at a temperature of at least 50° C. for at least 24 hours;
the coating the layer of charge transport material comprises coating the PEDOT:PSS layer with the aged composition;
the converting the aged composition comprises forming a solid layer of perovskite CH3NH3PbIxCl3-x, wherein 0≦x≦3, the solid layer having a plurality of grains with an average size of at least 50 micrometers;
the forming the second layer of charge transport material comprises forming a layer of [6,6]-phenyl-C60 butyric acid methyl ester (PCBM) on the solid layer of CH3NH3PbI3; and
the forming the electrode layer comprises forming a metal electrode on the layer of PCBM.

### Claim 16 (depends on 15)

The device of claim 15, wherein the substrate comprises tin oxide.

### Claim 17 (depends on 10)

The device of claim 10, wherein the lead halide compound is selected from PbI2, PbCl2, and combinations thereof.

### Claim 18 (depends on 10)

The device of claim 10, wherein the solvent has a boiling point of 130° C. or higher.

### Claim 19

A process for preparing a perovskite thin film comprising the steps of:
heating a substrate to a temperature of at least 100° C.;
forming a composition by mixing at least one lead halide compound, methylamine, and a solvent;
aging the composition at a temperature from about 50° C. to about 100° C. for at least 24 hours;
coating the substrate with the aged composition; and
converting the aged composition to a solid layer of perovskite CH3NH3PbIxCl3-x, wherein 0≦x≦3, the solid layer having a plurality of grains with an average size of at least 50 micrometers.

### Claim 20 (depends on 19)

The process of claim 19, wherein the lead halide compound is selected from PbI2, PbCl2, and combinations thereof.

### Claim 21

(canceled)