Oriented perovskite crystals and methods of making the same

Patent metadata

Field	Value
Publication number	US-11535639-B2
Application number	US-202016773065-A
Country	US
Kind code	B2
Filing date	Jan 27, 2020
Priority date	Oct 14, 2016
Publication date	Dec 27, 2022
Grant date	Dec 27, 2022

Abstract

An aspect of the present disclosure is a method that includes combining a first organic salt (A 1 X 1 ), a first metal salt (M 1 (X 2 ) 2 ), a second organic salt (A 2 X 3 ), a second metal salt (M 2 Cl 2 ), and a solvent to form a primary solution, where A 1 X 1 and M 1 (X 2 ) 2 are present in the primary solution at a first ratio between about 0.5 to 1.0 and about 1.5 to 1.0, and A 2 X 3 to M 2 Cl 2 are present in the primary solution at a second ratio between about 2.0 to 1.0 and about 4.0 to 1.0. In some embodiments of the present disclosure, at least one of A 1 or A 2 may include at least one of an alkyl ammonium, an alkyl diamine, cesium, and/or rubidium.

First claim

What is claimed is:

1. A method comprising:
combining a first organic salt (A 1 X 1 ), a first metal salt (M 1 (X 2 ) 2 ) a second organic salt (A 2 X 3 ), a second metal salt (M 2 Cl 2 ), and a solvent to form a primary solution, wherein:
A 1 X 1 and M 1 (X 2 ) 2 are present in the primary solution at a first molar ratio between about 0.5 to 1.0 and about 1.5 to 1.0,
A 2 X 3 to M 2 Cl 2 are present in the primary solution at a second molar ratio between about 2.0 to 1.0 and about 4.0 to 1.0,
the primary solution is capable of producing a plurality of organic-inorganic perovskite crystals comprising A 1 ( 1−x )A 2 x M 1 z M 2 (1−z) X 1 a X 2 b X 3 c Cl d ,
a+b+c+d=3.0, d>0, and 0<x<1.

2. The method of claim 1 , wherein at least one of A 1 or A 2 independently comprises an alkyl ammonium, an alkyl diamine, cesium, or rubidium.

3. The method of claim 1 , wherein at least one of A 1 or A 2 comprises methylammonium (MA), ethylammonium, propylammonium, or butylammonium.

4. The method of claim 1 , wherein at least one of A 1 or A 2 comprises formamidinium (FA).

5. The method of claim 1 , wherein at least one of M 1 or M 2 comprises a metal having a 2+ valence state.

6. The method of claim 5 , wherein each of M 1 and M 2 independently comprises lead, tin, or germanium.

7. The method of claim 1 , wherein each of X 1 , X 2 , and X 3 comprises a halogen.

8. The method of claim 7 , wherein at least onceach of X 1 , X 2 , and X 3 independently comprises fluorine, bromine, iodine, or astatine.

9. The method of claim 1 , wherein the solvent comprises an organic solvent.

10. The method of claim 9 , wherein the organic solvent comprises at least one of dimethylformamide, dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide, or N-methyl-2-pyrrolidone.

11. The method of claim 1 , wherein:
A 1 X 1 and M 1 (X 2 ) 2 form a first reactant pair,
A 2 X 3 to M 2 Cl 2 form a second reactant pair, and
the first reactant pair and the second reactant pair are present in the primary solution at a third molar ratio between about 1.0 to 1.0 and about 1.5 to 1.0.

12. The method of claim 1 , further comprising:
depositing at least a portion of the primary solution onto a solid surface, wherein:
the depositing forms a liquid layer comprising the primary solution on the solid surface.

13. The method of claim 12 , wherein the depositing is performed using at least one of spin coating, blade coating, curtain coating, or dip coating.

14. The method of claim 12 , further comprising, after the depositing:
treating at least the liquid layer, wherein:
the treating converts at least a portion of the liquid layer to a solid layer comprising the plurality of organic-inorganic perovskite crystals, and
the solid layer is adhered to the solid surface.

15. The method of claim 14 , wherein the treating is performed by thermal treating.

16. The method of claim 1 , wherein the plurality of organic-inorganic perovskite crystals comprises FA (1−x) MA x Pb z Cs 1−z I a Br b Cl d .

17. The method of claim 1 , wherein the plurality of organic-inorganic perovskite crystals comprises FA (1−x) MA x PbI a Cl d .

18. The method of claim 1 , wherein:
each crystal of the plurality of organic-inorganic perovskite crystals has a length dimension and a width dimension, and
the length dimension (L) and the width dimension (W) define an aspect ratio of L to W between about 1.5 to 1.0 and about 50 to 1.0.

19. The method of claim 18 , wherein L is between about 100 nm and about 3000 nm.

20. The method of claim 1 , wherein the plurality of organic-inorganic perovskite crystals form grains measuring between about 2 μm and about 5 μm.

Assignees

• Alliance Sustainable Energy

Inventors

• Zhu Kai
• Kim Donghoe
• Berry Joseph Jonathan
• Park Jaehong

Classifications

• C07F7/22

  Tin compounds · CPC title

• C07B2200/13

  Crystalline forms, e.g. polymorphs · CPC title

• C23C18/02

  by thermal decomposition · CPC title

• C30B29/22

  Complex oxides · CPC title

• C07F7/24 Primary

  Lead compounds · CPC title