Optoelectronic devices with organometal perovskites with mixed anions

Patent metadata

Field	Value
Publication number	US-11258024-B2
Application number	US-201715824089-A
Country	US
Kind code	B2
Filing date	Nov 28, 2017
Priority date	May 18, 2012
Publication date	Feb 22, 2022
Grant date	Feb 22, 2022

Abstract

The invention provides an optoelectronic device comprising a mixed-anion perovskite, wherein the mixed-anion perovskite comprises two or more different anions selected from halide anions and chalcogenide anions. The invention further provides a mixed-halide perovskite of the formula (I) [A][B][X]3 wherein: [A] is at least one organic cation; [B] is at least one divalent metal cation; and [X] is said two or more different halide anions. In another aspect, the invention provides the use of a mixed-anion perovskite as a sensitizer in an optoelectronic device, wherein the mixed-anion perovskite comprises two or more different anions selected from halide anions and chalcogenide anions. The invention also provides a photosensitizing material for an optoelectronic device comprising a mixed-anion perovskite wherein the mixed-anion perovskite comprises two or more different anions selected from halide anions and chalcogenide anions.

First claim

The invention claimed is:

1. A photovoltaic device comprising:
a first electrode;
a second electrode; and, disposed between the first and second electrodes:
a sensitizer material which is capable of performing photoinduced charge generation within the photovoltaic device, wherein the sensitizer material is a mixed-halide perovskite of the formula (I)
[A][B][X] 3   (I)

wherein:
[A] is at least one cation, comprising at least one organic cation of the formula (R 5 R 6 N═CH—NR 7 R 8 ) + , wherein:
(i) R 5 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl;
(ii) R 6 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl;
(iii) R 7 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl; and
(iv) R 8 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl:
[B] is at least one divalent metal cation, wherein [B] comprises Pb 2+ ; and

[X] is two or more different halide anions, wherein one of said two or more different halide anions is iodide, and
a p-type layer which comprises a solid-state hole-transporting material which is not said perovskite.

2. A photovoltaic device according to claim 1 wherein the at least one organic cation of the formula (R 5 R 6 N═CH—NR 7 R 8 ) + is an organic cation of the formula (H 2 N═CH—NH 2 ) + .

3. A photovoltaic device according to claim 1 wherein [B] is Pb 2+ .

4. A photovoltaic device according to claim 1 wherein one of said two or more different halide anions is iodide and another of said two or more different halide anions is bromide.

5. A photovoltaic device according to claim 1 , wherein [X] is two or three different halide anions selected from fluoride, chloride, bromide or iodide.

6. A photovoltaic device according to claim 5 , wherein [X] is two different halide anions which are bromide and iodide.

7. A photovoltaic device according to claim 1 wherein the perovskite is a perovskite compound of formula (IIa):
ABX 3z X′ 3(1-z)   (IIa)

wherein:
A is an organic cation of the formula (R 5 R 6 N═CH—NR 7 R 8 ) + , wherein:
(i) R 5 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl;
(ii) R 6 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl;
(iii) R 7 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl; and
(iv) R 8 is hydrogen, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted aryl;
B is Pb 2+ ;
X is a first halide anion wherein the first halide anion is iodide;

X′ is a second halide anion which is different from the first halide anion; and
z is greater than 0 and less than 1.

8. A photovoltaic device according to claim 7 , wherein X is iodide and X′ is bromide.

9. A photovoltaic device according to claim 7 wherein z is from 0.05 to 0.95.

10. A photovoltaic device according to claim 7 wherein the organic cation has the formula (H 2 N═CH—NH 2 ) + .

11. A photovoltaic device according to claim 7 wherein the perovskite has the formula (H 2 N═CH—NH 2 )PbI 3z Br 3(1-z) wherein z is greater than 0 and less than 1.

12. A photovoltaic device according to claim 11 wherein z is from 0.05 to 0.95.

13. A photovoltaic device according to claim 1 wherein the solid-state hole transporting material is a polymeric or molecular hole transporter.

14. A photovoltaic device comprising:
a first electrode;
a second electrode; and, disposed between the first and second electrodes:

(a) a p-type layer which comprises a solid-state hole transporting material, wherein the solid-state hole transporting material is a polymeric or molecular hole transporter which is not said perovskite; and
(b) a sensitizer material which is capable of performing photoinduced charge generation within the photovoltaic device, wherein the sensitizer material is a perovskite of the formula (I)
[A][B][X] 3   (I)

wherein:
[A] is at least one cation, comprising at least one organic cation of the formula (H 2 N═CH—NH 2 ) + ;
[B] is at least one divalent metal cation, wherein [B] comprises Pb 2+ ; and
[X] is iodide, or [X] is two or more different halide anions, wherein one of said two or more different halide anions is iodide.

Assignees

• Univ Oxford Innovation Ltd

Inventors

• Snaith Henry
• Lee Michael
• Murakami Takuro

Classifications

• Y02E10/549

  Organic PV cells · CPC title

• Y02E10/542

  Dye sensitized solar cells · CPC title

• H10K30/86

  Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers · CPC title

• H10K30/85

  Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers · CPC title

• H10K2102/102

  comprising tin oxides, e.g. fluorine-doped SnO2 · CPC title