Two-dimensional halide perovskite materials

Patent metadata

Field	Value
Publication number	US-11800784-B2
Application number	US-202017012137-A
Country	US
Kind code	B2
Filing date	Sep 4, 2020
Priority date	Sep 12, 2019
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

The present disclosure relates to novel two-dimensional halide perovskite materials, and the method of making and using the two-dimensional halide perovskite materials.

First claim

We claim:

1. A two-dimensional halide perovskite material, comprising:
a first halide perovskite component of formula L 2 A n−1 M n X 3n+1 and a second halide perovskite component of formula L′ 2 A′ n′−1 M′ n′ X′ 3n′+1 , wherein:
L and L′ represent
an asymmetric mono-ammonium cationic moiety:

wherein R 1 is —H, —F, —Cl, —Br, —I, -Me, -Et, -OMe, -OEt, -SMe, -SEt, —CN, —NO 2 , -COMe, —CHO, -COOMe, or —NH-COMe;
(Ar) m represents a conjugated and optionally substituted aryl or hetero aryl system, or a combination thereof, wherein each aryl or hetero aryl ring in the conjugated and optionally substituted aryl or hetero aryl system may be the same or different;
l is 1-4; and
m is 0-5:
A and A′ each independently represents a cation C s +, Rb + , CH 3 NH 3 + , CH 3 CH 2 NH 3 + , or

M and M′ each independently represents a divalent metal cation Pb 2+ , Sn 2+ , Ge 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , V 2+ , Pd 2+ , or Pt 2+ ;
X and X′ each independently represents F − , Cl − , Br − or I − ;
n and n′ each independently is 1-6; and
wherein the first halide perovskite component and the second halide perovskite component are not the same perovskite, and the first halide perovskite is first formed as a lateral core and the second halide perovskite is formed surrounding the lateral core of the first halide perovskite.

2. The two-dimensional halide perovskite material of claim 1 , wherein R 1 is —F, —Cl, —Br, —I, -Me, -Et, -OMe, -OEt, -SMe, -SEt, —CN, —NO 2 , -COMe, —CHO, -COOMe, or —NH-COMe.

3. The two-dimensional halide perovskite material of claim 1 , wherein R 1 is -Me.

4. The two-dimensional halide perovskite material of claim 1 , wherein (Ar) m represents a conjugated and optionally substituted aryl or hetero aryl system, or a combination thereof, wherein each aryl or hetero aryl ring in the conjugated and optionally substituted aryl or hetero aryl system may be same or different, wherein Ar is selected from the group consisting of:

and any combination thereof.

5. The two-dimensional halide perovskite material of claim 4 , wherein Ar is selected from the group consisting of:

and any combination thereof.

6. The two-dimensional halide perovskite material of claim 1 , wherein L is selected from the group consisting of:

7. The two-dimensional halide perovskite material of claim 1 , wherein the two-dimensional halide perovskite material is formed as a sheet with a thickness of 1 - 1000 nm.

8. The two-dimensional halide perovskite material of claim 1 , wherein lateral joint between the first and the second halide perovskite are substantially free of anion inter-diffusion.

9. The two-dimensional halide perovskite material of claim 1 , wherein the two-dimensional halide perovskite material is used for light-emitting diodes, lasers, infrared photodetectors, transistors, thermoelectric devices, or solar cells.

10. A solution-phase synthetic method of preparing the two-dimensional halide perovskite material comprising a first halide perovskite component of formula L 2 A n−1 M n X 3n+1 and a second halide perovskite component of formula L′ 2 A′ n−1 M′ n′ X′ 3n+1 , wherein:
L and L′ represent an asymmetric mono-ammonium cationic moiety:

wherein R 1 is —H, —F, —Cl, —Br, -I, -Me, -Et, -OMe, -OEt, -SMe, -SEt, —CN, —NO 2 , -COMe, —CHO, -COOMe, or —NH-COMe;
(Ar) m represents a conjugated and optionally substituted aryl or hetero aryl system, or a combination thereof, wherein each aryl or hetero aryl ring in the conjugated and optionally substituted aryl or hetero aryl system may be the same or different
l is 1-4; and
m is 0-5;
A and A′ each independently represents a cation Cs + , Rb + , CH 3 NH 3 + , CH 3 CH 2 NH 3 + , or

M and M′ each independently represents a divalent metal cation Pb 2+ , Sn 2+ , Ge 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , V 2+ , Pd 2+ , or Pt 2+ ;
X and X′ each independently represents F − , Cl − , Br − or I − ;
n and n′ each independently is 1-6; and
wherein the first halide perovskite component and the second halide perovskite component are not the same perovskite, and the first halide perovskite is first formed as a lateral core and the second halide perovskite is formed surrounding the lateral core of the first halide perovskite, wherein the method comprises:
providing a solution of a first precursor and a first solvent system for preparing the first halide perovskite component of formula L 2 A n−1 M n Z 3n+1 ;
adding the solution of the first precursor to a first container with a growth substrate for growing the first halide perovskite component;
placing the first container inside a second container with a second solvent system, wherein the second solvent system is not in direct contact with the solution of the first precursor and the second solvent system is served as an anti-solvent system for slowing down the evaporation of the first solvent system;
capping the second container and elevating the temperature of the second container to allow the growth of a nano-sheet of the first halide perovskite component;
cleaning the substrate with the nano-sheet of the first halide perovskite component and making it ready for growing of the second halide perovskite component of formula L′ 2 A′ n′−1 M′ n′ X′ 3n+1 ; and
repeating the same steps to make the second halide perovskite component of formula L′ 2 A′ n′−1 M′ n′ X′ 3n′+1 surrounding the lateral core of the first halide perovskite.

11. The method of claim 10 , wherein the growth substrate comprises SiO 2 , Si, or a combination thereof.

12. The method of claim 10 , wherein a solution concentration for making the second halide perovskite component of formula L′ 2 A′ n′−1 M′ n′ X′ 3n+1 is lower than a solution concentration for making the first halide perovskite component of formula L 2 A n−1 M n X 3n+1 .

13. The method of claim 10 , wherein the temperature for making the second halide perovskite component of formula L′ 2 A′ n′−1 M′ n′ X′ 3n′+1 is lower than the temperature for making the first halide perovskite component of formula L 2 A n+1 M n X 3n−1 .

14. The method of claim 10 , wherein the first solvent system comprises chlorobenzene, dimethylformide, acetonitrile, and dichlorobenzene, and the second solvent system comprises chlorobenzene.

Assignees

• Purdue Research Foundation

Inventors

• Dou Letian
• Gao Yao
• Shi Enzheng

Classifications

• H10K85/30 Primary

  Coordination compounds · CPC title

• C07F7/24

  Lead compounds · CPC title

• C09K11/06 Primary

  containing organic luminescent materials · CPC title

• H01G9/20

  Light-sensitive devices · CPC title

• H10N10/856

  comprising organic compositions · CPC title