IP Library Granted Patent US 11,258,024
Granted Patent B2
US 11,258,024 · App. 15/824,089 · Granted Feb 22, 2022

Optoelectronic devices with organometal perovskites with mixed anions

Inventors: Henry Snaith (Oxfordshire, GB); Michael Lee (Oxfordshire, GB); Takuro Murakami (Yokohama, JP)
Assignee: OXFORD UNIVERSITY INNOVATION LIMITED
H01L51/4213C07F7/2284C07F7/24H01L51/0032H01L51/0077H01L51/4226H01G9/2027H01G9/2031H01L51/0036H01L2251/306Y02E10/549Y02P70/50
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Quick Facts
Patent No.
US 11,258,024
App. No.
15/824,089
Granted
Feb 22, 2022
Kind
B2
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.

Claims (47)

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.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 11, 2025
From: OXFORD UNIVERSITY INNOVATION LIMITED
To: OXFORD PHOTOVOLTAICS LIMITED
Reel/Frame 070469/0137 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 19, 2021
From: SNAITH, HENRY JAMES; LEE, MICHAEL; MURAKAMI, TAKURO
To: ISIS INNOVATION LIMITED
Reel/Frame 057828/0885 →
CHANGE OF NAME Recorded Oct 19, 2021
From: ISIS INNOVATION LIMITED
To: OXFORD UNIVERSITY INNOVATION LIMITED
Reel/Frame 057846/0055 →
Cited By (2)
US 12,193,317 US 12,274,109