# US 11,078,413 B2 · Organic-inorganic hybrid perovskites, devices, and methods

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,078,413 B2
- Document ID: US11078413B2
- Status: Granted
- Kind: B2
- Application number: 15/669,249
- Filed: 2017-08-04
- Published: 2018-02-08
- Granted: 2021-08-03
- Earliest claimed: 2016-08-04
- Assignees: The Florida State University Research Foundation, Inc.
- Applicants: Florida State University Research Foundation, Inc.
- Inventors: Biwu Ma; Zhao Yuan; Chenkun Zhou
- Web page: https://patentgrep.com/patent/US11078413B2

## CPC

- C09K 11/06: containing organic luminescent materials
- C07F 7/24: Lead compounds
- C09K 11/57: containing manganese or rhenium
- C09K 11/664: {Halogenides (C09K11/661 takes precedence)}
- C30B 7/14: the crystallising materials being formed by chemical reactions in the solution
- C30B 29/54: Organic compounds
- H10K 85/30: Coordination compounds
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- C09K 2211/188: of other metals not provided for in one of the previous groups
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/135: comprising mobile ions
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C30B: SINGLE-CRYSTAL GROWTH (by using ultra-high pressure, e.g. for the formation of diamonds, B01J3/06); UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL (zone-refining of metals or alloys C22B); PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (casting of metals, casting of other substances by the same processes or devices B22D; working of plastics B29; modifying the physical structure of metals or alloys C21D, C22F); SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (for producing semiconductor devices or parts thereof H10); APPARATUS THEREFOR
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

Provided herein are organic-inorganic hybrid-perovskites, including metal halide perovskites having a 1D crystal structure. The metal halide perovskites may be luminescent. The metal halide perovskites may include a dopant, including an emitter dopant. Methods of forming metal halide perovskites, and devices including the metal halide perovskites also are provided.

## Claims

### Claim 1

A metal halide perovskite comprising:
a 1D crystal structure comprising a unit cell according to formula (I)—
RMX4 (I);
wherein M is a metal atom selected from Pb, Sn, Cu, Ge, Mn, Co, Bi, Sb, or Eu;
X is a halide ion selected from Cl, Br, or I; and
R is an organic cation comprising at least one secondary ammonium cation, at least one tertiary ammonium cation, or a combination thereof.

### Claim 2 (depends on 1)

The metal halide perovskite of claim 1, wherein the organic cation is N, N′-dimethylethane-1,2-diammonium:

### Claim 3 (depends on 2)

The metal halide perovskite of claim 2, wherein M is Pb, X is Cl, and the unit cell has the following formula:
(C4N2H14)PbCl4.

### Claim 4 (depends on 2)

The metal halide perovskite of claim 2, wherein M is Pb, X is Br, and the unit cell has the following formula:
(C4N2H14)PbBr4.

### Claim 5 (depends on 2)

The metal halide perovskite of claim 2, wherein M is Pb, X is I, and the unit cell has the following formula:
(C4N2H14)PbI4.

### Claim 6 (depends on 1)

The metal halide perovskite of claim 1, wherein the 1D crystal structure further comprises a dopant at a ratio of about 0.995:0.005 to about 0.90:0.1 (metal atom:dopant), as determined by X-ray fluorometer.

### Claim 7 (depends on 6)

The metal halide perovskite of claim 6, wherein the dopant comprises Mn2+ ions, Eu3+ ions, Pr3+ ions, or a combination thereof.

### Claim 8 (depends on 6)

The metal halide perovskite of claim 6, wherein the photoluminescence quantum efficiency (PLQE) of the metal halide perovskite is at least 25%.

### Claim 9 (depends on 1)

The metal halide perovskite of claim 1, wherein the organic cation is a compound according to formula (A):
wherein each of R1-R6 is independently selected from hydrogen or a monovalent C1-C20 hydrocarbyl, and R7 is a divalent C1-C20 hydrocarbyl or a divalent C6-C20 aryl.

### Claim 10 (depends on 9)

The metal halide perovskite of claim 9, wherein R7 is a divalent, unsubstituted C1-C4 hydrocarbyl; R2, R3, R5, and R6 are hydrogen; each of R1 and R4 is independently a monovalent, unsubstituted C1-C3 hydrocarbyl, and the organic cation is a compound according to the following formula (D):

### Claim 11 (depends on 1)

The metal halide perovskite of claim 1, wherein R7 is a divalent, unsubstituted C6 aryl; each of R2, R3, R5, and R6 is hydrogen; each of R1 and R4 is independently a monovalent, unsubstituted C1-C3 hydrocarbyl; and the organic cation is a compound according to the following formula (G):

### Claim 12 (depends on 1)

The metal halide perovskite of claim 1, wherein the organic cation is a compound according to the following formula (H):
wherein each of R1 and R3 is independently selected from a divalent C1-C20 hydrocarbyl, and each of R2, R4, and R5 is independently selected from hydrogen or a monovalent C1-C20 hydrocarbyl.

### Claim 13 (depends on 12)

The metal halide perovskite of claim 12, wherein R2 is hydrogen; each of R4 and R5 is independently a monovalent, unsubstituted C1-C3 hydrocarbyl; each of R1 and R3 is independently a divalent, unsubstituted C2-C4 hydrocarbyl; and the organic cation is a compound according to the following formula (I):

### Claim 14 (depends on 12)

The metal halide perovskite of claim 12, wherein R2 is a divalent C2-C4 hydrocarbyl substituted with a secondary amine; each of R4 and R5 is independently a monovalent, unsubstituted C1-C3 hydrocarbyl; each of R1 and R3 is independently a divalent, unsubstituted C2-C4 hydrocarbyl; and the organic cation is a compound according to the following formula (J):

### Claim 15 (depends on 1)

The metal halide perovskite of claim 1, wherein the organic cation is a compound according to the following formula (K):
wherein R1 and R5 are independently selected from a monovalent C1-C20 hydrocarbyl or hydrogen, R2 and R4 are independently selected from a divalent C1-C20 hydrocarbyl, and R3 is a divalent C1-C20 hydrocarbyl or a divalent C6-C20 aryl.

### Claim 16 (depends on 15)

The metal halide perovskite of claim 15, wherein R1 and R5 are independently selected from an unsubstituted, monovalent C1-C3 hydrocarbyl; R2, R3, and R4 are independently selected from an unsubstituted, divalent C2-C4 hydrocarbyl, and the organic cation has a structure according to the following formula (L):

### Claim 17 (depends on 1)

The metal halide perovskite of claim 1, wherein the organic cation is a compound according to the following formula (M):
wherein n is 0 or 1, each of R1-R4 and R8 is independently selected from a divalent C1-C20 hydrocarbyl, and each of R5-R7 is independently selected from a monovalent C1-C20 hydrocarbyl or hydrogen.

### Claim 18 (depends on 17)

The metal halide perovskite of claim 17, wherein n is 1, R1-R4 are independently selected from an unsubstituted, divalent C1-C4 hydrocarbyl; R8 is an unsubstituted, divalent C1-C3 hydrocarbyl; R5-R7 are independently selected from an unsubstituted, monovalent C1-C3 hydrocarbyl; and the organic cation is a compound according to the following formula (N):

### Claim 19 (depends on 17)

The metal halide perovskite of claim 17, wherein n is 0, R1-R3 are independently selected from an unsubstituted, divalent C1-C4 hydrocarbyl; R5-R7 are independently selected from an unsubstituted, monovalent C1-C3 hydrocarbyl; and the organic cation is a compound according to the following formula (O):

### Claim 20 (depends on 1)

The metal halide perovskite of claim 1, wherein the organic cation is a compound according to the following formula (P):
wherein m is 0 or 1, n is 1-4, each R1 is independently selected from a divalent C1-C20 hydrocarbyl, and each R2 is independently selected from a monovalent C1-C20 hydrocarbyl or hydrogen.

### Claim 21 (depends on 20)

The metal halide perovskite of claim 20, wherein m is 0, n is 3, R2 is independently selected from an unsubstituted, monovalent C1-C3 hydrocarbyl, and the organic cation is a compound according to the following formula (Q):

### Claim 22 (depends on 1)

The metal halide perovskite of claim 1, wherein the organic cation comprises a compound according to one of structures (1)-(10):

### Claim 23 (depends on 1)

An optoelectronic device comprising the metal halide perovskite of claim 1, wherein the metal halide perovskite is a light emitting material.

### Claim 24 (depends on 23)

The device of claim 23, wherein the metal halide perovskite emits light that is white, blue, green, yellow, orange, or red.

### Claim 25 (depends on 23)

The device of claim 23, wherein the optoelectronic device is a light emitting diode, a light emitting electrochemical cell, or an optically pumped laser.