Strain engineering and epitaxial stabilization of halide perovskites

Patent metadata

Field	Value
Publication number	US-12435442-B2
Application number	US-202017619728-A
Country	US
Kind code	B2
Filing date	Jun 29, 2020
Priority date	Jun 28, 2019
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

Abstract

In accordance with a method of forming a halide perovskite thin film, a first halide perovskite material is chosen from which a halide perovskite thin film is to be formed. An epitaxial substrate formed from a second halide perovskite material is also chosen. The halide perovskite thin film is epitaxially formed on the substrate from the first halide perovskite material. The substrate is chosen such that the halide perovskite thin film formed on the substrate has a selected value of at least one property. The property is selected from the group including crystal structure stability, charge carrier mobility and band gap.

First claim

The invention claimed is:

1. A method of forming a device, comprising:
choosing a first halide perovskite material from which a halide perovskite thin film is to be formed from a solvent-based liquid solution;
choosing an epitaxial substrate formed from a second halide perovskite material;
fabricating a patterned mask to control solvent-based liquid solution growth behavior of the halide perovskite thin film on the epitaxial substrate; and
epitaxially forming the halide perovskite thin film on the epitaxial substrate from the first halide perovskite material, the first halide perovskite material being α-FAPbI 3 , where FA is formamidinium, wherein the epitaxial substrate is chosen such that the halide perovskite thin film formed on the substrate has a selected value of at least one property, the property being selected from the group including crystal structure stability, charge carrier mobility and band gap, and wherein the epitaxially forming includes epitaxially forming an elastically strained halide perovskite thin film on the epitaxial substrate from the first halide perovskite material, wherein the elastically strained halide perovskite thin film has a thickness less than 100 nm, and the first halide perovskite has a compressive strain between 0% and −2.4%, wherein the elastically strained halide perovskite thin film has a room temperature bandgap between 1.488 eV and 1.523 eV, an External Quantum Efficiency (EQE) between 3×10 −4 %, and 6×10 −4 % and a time-of-flight electron mobility between 20 cm 2 V −1 s −1 and 30 cm 2 V −1 s −1 .

2. The method of claim 1 , wherein the second halide perovskite material is MAPbCl x Br 3-x , wherein MA is methyl ammonium and x is between 0 and 1.5.

3. The method of claim 2 , wherein the halide perovskite thin film has a compressive strain up to −2.4% 2.4%.

4. The method of claim 2 , wherein the halide perovskite thin film has a pseudo-cubic lattice structure.

5. The method of claim 1 , further comprising adjusting the compressive strain of the halide perovskite thin film to a particular value so that the halide perovskite thin film has the selected value of the at least one property.

6. The method of claim 1 , wherein forming the thin film from solution includes depositing the solution onto a preheated substrate.

7. The method of claim 1 , further comprising depositing the solution onto a preheated substrate using an inverse temperature growth method.

8. The method of claim 1 , wherein the first and/or second halide perovskite materials are selected from the group consisting of a halide perovskite material having the formula ABX 3 ; wherein: A is at least one monovalent or divalent organic cation, inorganic cation or a combination thereof; X is at least one halide anion, a pseudohalide anion or a combination thereof; and B is at least one metal cation wherein, when combined with A and X, forms a perovskite material; wherein the inorganic cation of A is different from the metal cation of B.

9. A device formed in accordance with the method of claim 1 .

10. The method of claim 1 , wherein the first halide perovskite material is α-FAPbI 3 , where FA is formamidinium and the second halide perovskite material is MAPbCl x Br 3-x , wherein MA is methyl ammonium and x is between 0 and 1.5.

11. The method of claim 1 , further comprising;
prior to epitaxially forming the halide perovskite thin film, sequentially depositing Parylene-C and Au layers on the epitaxial substrate so that the Parylene-C layer prevents an injection of carriers from the Au layer to the epitaxial substrate;
etching the Parylene-C and Au layers to establish a pattern on the epitaxial substrate;
forming an electrode on the halide perovskite thin film.

12. The method of claim 11 wherein epitaxially forming the halide perovskite thin film includes epitaxially forming the halide perovskite thin film from solution.

13. A method of forming a device, comprising:
choosing a first halide perovskite material from which a halide perovskite thin film is to be formed from a solvent-based liquid solution and a single crystal halide perovskite substrate from a second halide perovskite material on which the halide perovskite thin film is to be formed to tune a property of the halide perovskite thin film using strain modulation to thereby impose a compressive or tensile strain on the halide perovskite thin film, wherein the first halide perovskite material is α-FAPbI 3 , where FA is formamidinium;
fabricating a patterned mask to control solvent-based liquid solution growth behavior of the halide perovskite thin film on the single crystal halide perovskite substrate; and
epitaxially forming the halide perovskite thin film on the chosen single crystal halide perovskite substrate from the first halide perovskite material, wherein the epitaxially forming includes epitaxially forming an elastically strained halide perovskite thin film on the epitaxial substrate from the first halide perovskite material, wherein the elastically strained halide perovskite thin film has a thickness less than 100 nm, and the first halide perovskite has a compressive strain between 0% and −2.4%, wherein the elastically strained halide perovskite thin film has a room temperature bandgap between 1.488 eV and 1.523 eV, an External Quantum Efficiency (EQE) between 3×10 −4 %, and 6×10 −4 % and a time-of-flight electron mobility between 20 cm 2 V −1 s −1 and 30 cm 2 V −1 s −1 .

14. The method of claim 13 , wherein the first and second halide perovskite materials have a lattice parameter mismatch that gives rise to the compressive or tensile strain.

15. The method of claim 14 , where the lattice parameter mismatch gives rise to a compressive strain of up to −2.4%.

16. The method of claim 13 , wherein the first and/or second halide perovskite materials are selected from the group consisting of a halide perovskite material having the formula ABX 3 ; wherein: A is at least one monovalent or divalent organic cation, inorganic cation or a combination thereof; X is at least one halide anion, a pseudohalide anion or a combination thereof; and B is at least one metal cation wherein, when combined with A and X, forms a perovskite material; wherein the inorganic cation of A is different from the metal cation of B.

17. The method of claim 16 , wherein forming the thin film from solution includes depositing the solution onto a preheated substrate.

18. The method of claim 13 , further comprising adjusting the compressive strain of the halide perovskite thin film to a particular value so that the halide perovskite thin film has a selected value of the at least one property.

19. The method of claim 18 , wherein the property of halide perovskite thin film is selected from the group consisting of crystal structure stability, charge carrier mobility and band gap.

20. The method of claim 13 , further comprising:
prior to epitaxially forming the halide perovskite thin film, sequentially depositing Parylene-C and Au layers on the single crystal halide perovskite substrate so that the Parylene-C layer prevents an injection of carriers from the Au layer to the single crystal halide perovskite substrate;
etching the Parylene-C and Au layers to establish a pattern on the single crystal halide perovskite substrate;
forming an electrode on the halide perovskite thin film.

21. The method of claim 20 wherein epitaxially forming the halide perovskite thin film includes epitaxially forming the halide perovskite thin film from solution.

Assignees

• Univ California

Inventors

• Xu Sheng
• Chen Yimu
• Lei Yusheng

Classifications

• H10K30/20

  comprising organic-organic junctions, e.g. donor-acceptor junctions · CPC title

• H10K85/50

  Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3 · CPC title

• H10K85/30

  Coordination compounds · CPC title

• H10K71/12

  using liquid deposition, e.g. spin coating · CPC title

• H01G9/2009

  Solid electrolytes · CPC title