Perovskite materials and methods of making the same

Patent metadata

Field	Value
Publication number	US-11427757-B2
Application number	US-201916271358-A
Country	US
Kind code	B2
Filing date	Feb 8, 2019
Priority date	Feb 8, 2018
Publication date	Aug 30, 2022
Grant date	Aug 30, 2022

Abstract

The present disclosure relates to a perovskite sheet that includes two outer layers, each including A′X′; and a first layer that includes BX2, where B is a first cation, A′ is a second cation, X is a first anion, X′ is a second anion, and the first BX2 layer is positioned between the two outer layers.

First claim

What is claimed is:

1. A perovskite sheet comprising, in order:
a first layer comprising A′X′;
a second layer comprising BX 2 ;
a third layer comprising AX;
a fourth layer comprising BX 2 ; and
a fifth layer comprising A′X′, wherein:
B is a first cation comprising lead,
A′ is a second cation comprising at least one of hydrogen, methylammonium (MA), formamidinium (FA), or cesium,
A is a third cation comprising at least one of MA, FA, or cesium,
X is a first anion comprising bromide,
X′ is a second anion comprising at least one of bromide or acetate (AC), and
the first layer and the fifth layer form interlayers between neighboring perovskite sheets, wherein:
the perovskite sheet has a composition comprising A′ 2 AB 2 X 5 X′ 2 .

2. The perovskite sheet of claim 1 , further comprising:
a sixth layer comprising AX, and
a seventh layer comprising BX 2 , wherein:
the second AX layer and the third BX 2 are positioned between the first layer and the fifth layer,
the first layer is adjacent to a first BX 2 layer,
the fifth layer is adjacent to a second BX 2 layer, and
the BX 2 layers and AX layers alternate positions in the sheet, wherein:
the perovskite sheet has a composition comprising A′ 2 A 2 B 3 X 8 X′ 2 .

3. The perovskite sheet of claim 2 , further comprising:
n BX 2 layers, wherein:
n is greater than three, and
the outer layers, the BX 2 layers, and the AX layers result in a stoichiometry defined by A′ 2 A n-1 B n X 3n-1 X′ 2 .

4. The perovskite sheet of claim 3 , wherein 4≤n≤10,000.

5. The perovskite sheet of claim 1 , wherein B further comprises at least one of tin or germanium.

6. The perovskite sheet of claim 1 , wherein X further comprises at least one of fluoride, chloride, or iodide.

7. The perovskite sheet of claim 1 , wherein X′ further comprises a charged form of at least one of a phosphonate group, a carboxylate group, a thiolate, a thiocyanate, an isocyanate, a carbonate, a chromate, a phosphate, a sulfite, a hydroxide, a nitrite, or a percholorate.

8. The perovskite sheet of claim 7 , wherein X′ comprises at least one of acetate, propionate, butyrate, phenolate, formate, an alkylphosphonate, or an alkylthiolate.

9. The perovskite sheet of claim 1 , wherein the perovskite sheet comprises a nanocrystal.

10. The perovskite sheet of claim 9 , wherein the nanocrystal is suspended in a solution comprising a solvent.

11. The perovskite sheet of claim 10 , wherein the solution further comprises a ligand comprising a binding group, where the binding group is physically associated with a surface of the nanocrystal.

12. The perovskite sheet of claim 11 , wherein the nanocrystal emits light when exposed to UV light.

13. The perovskite sheet of claim 12 , wherein the light is at an energy level between about 1.7 eV and about 3.0 eV.

14. A perovskite network comprising:
a first perovskite sheet having the stoichiometry of A′ 2 A n-1 B n X 3n-1 X′ 2 , and
a second perovskite sheet having the stoichiometry of A′ 2 A m-1 B m X 3m-1 X′ 2 , wherein:
B is a first cation comprising lead,
A′ is a second cation comprising at least one of hydrogen, methylammonium (MA), formamidinium (FA), or cesium,
A is a third cation comprising at least one of MA, FA, or cesium,
X is a first anion comprising bromide,
X′ is a second anion comprising at least one of bromide or acetate,
the first perovskite sheet and the second perovskite sheet each comprise an A′X′ layer,
the A′X′ layer of the first perovskite sheet is physically associated with the A′X′ layer of the second perovskite sheet, and
m does not equal n, m is greater than or equal to zero, and n is greater than or equal to one.

15. A perovskite network comprising:
a first perovskite sheet having the stoichiometry of A′ 2 A n-1 Pb n Br 3n-1 X″, and
a second perovskite sheet having the stoichiometry of A′ 2 A m-1 Pb m Br 3m-1 X″, wherein:
B is a first cation comprising lead,
A′ is a second cation comprising at least one of hydrogen, methylammonium (MA), formamidinium (FA), or cesium,
A is a third cation comprising at least one of MA, FA, or cesium,
X is a first anion comprising bromide,
X″ is a second anion comprises terephthalate,
the first perovskite sheet and the second perovskite sheet are physically associated by sharing at least one X″, and
m does not equal n, m is greater than or equal to zero, and n is greater than or equal to one.

16. A method for making a perovskite, the method comprising:
removing A and X from a first nanocrystal comprising ABX 3 , resulting in the forming of a second nanocrystal comprising BX 2 ; and
contacting the second nanocrystal with A′X′, resulting in the forming of a third nanocrystal comprising A′ 2 A n-1 B n X 3n-1 X′ 2 , wherein:
n is greater than or equal to two,
the third nanocrystal includes a perovskite sheet comprising:
a first layer comprising A′X′;
a second layer comprising BX 2 ;
a third layer comprising AX;
a fourth layer comprising BX 2 ; and
a fifth layer comprising A′X′,

B is a first cation comprising lead,
A′ is a second cation comprising at least one of hydrogen, methylammonium (MA), formamidinium (FA), or cesium,
A is a third cation comprising at least one of MA, FA, or cesium,
X is a first anion comprising bromide,
X′ is a second anion comprising at least one of bromide or acetate, and
the first layer and the fifth layer form interlayers between neighboring perovskite sheets.

17. The method of claim 16 , wherein:
the removing is achieved by immersing the first nanocrystal in a first solution comprising a first solvent,
the first solution has a first solubility for the A and the X,
the first solution has a second solubility for the second nanocrystal, and
the first solubility is higher than the second solubility.

18. The method of claim 17 , wherein the first solvent comprises at least one of water, an alcohol, ether, a halogenated alkane, a halogenated benzene, a ketone, an alkylnitrile, or an ester.

19. The perovskite sheet of claim 1 , wherein the first layer and the fifth layer are substantially free of a ligand.

20. The perovskite sheet of claim 19 , wherein the ligand comprises at least one of oleic acid, oleylamine, oleylammonium, phenylammonium, or dodecylammonium.

21. The perovskite sheet of claim 1 , comprising at least one of MA 2 CsPb 2 Br 5 Ac 2 , FA 2 CsPb 2 Br 5 Ac 2 , H 2 CsPb 2 Br 5 Ac 2 , MA 2 CsPb 2 Br 7 , FA 2 CsPb 2 Br 7 , H 2 CsPb 2 Br 7 , Cs 3 Pb 2 Br 7 , Cs 3 Pb 2 Br 5 Ac 2 , Cs 3 Pb 2 Br 5 Ac 2 , or Cs 3 Pb 2 Br 5 Ac 2 .

Assignees

• Alliance Sustainable Energy

Inventors

• Wheeler Lance Michael
• Neale Nathan Richard
• Anderson Nicholas Charles
• Hautzinger Matthew Peter
• Bliss Taylor Sierra

Classifications

• C09K11/665 Primary

  with alkali or alkaline earth metals · CPC title

• C01P2004/04

  obtained by TEM, STEM, STM or AFM · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C07F7/24

  Lead compounds · CPC title

• C01G21/16

  Halides · CPC title