# US 12,120,892 B2 · Organic-inorganic hybrid perovskites

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- Number: US 12,120,892 B2
- Document ID: US12120892B2
- Status: Granted
- Kind: B2
- Application number: 16/632,582
- Filed: 2018-07-19
- Published: 2021-03-11
- Granted: 2024-10-15
- Earliest claimed: 2017-07-20
- Assignees: Universite D'Angers; Centre National de la Recherche Scientifique (CNRS); Chimie Paristech
- Applicants: Université D'Angers; Centre National De La Recherche Scientifique; Chimie Paristech
- Inventors: Nicolas Mercier; Antonin Leblanc; Thierry Pauporté
- Web page: https://patentgrep.com/patent/US12120892B2

## CPC

- C07F 7/24: Lead compounds
- H10F 77/12: Active materials
- H10F 77/311: {for photovoltaic cells}
- H10K 30/10: comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- H10K 30/50: Photovoltaic [PV] devices
- H10K 50/15: Hole transporting layers
- H10K 50/16: Electron transporting layers
- H10K 2102/102: {comprising tin oxides, e.g. fluorine-doped SnO2}
- Y02E 10/542: Dye sensitized solar cells
- Y02E 10/549: Organic PV cells
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The application relates to organic-inorganic hybrid perovskites of formula (I): [(A)1−2.48p−b(B)3.48p+b](1+2p−y)/1+p)(Pb)1−p−m(M)m(X1)3−y−q(X2)q(I), and perovskite photovoltaic cells comprising the same.

## Claims

### Claim 1

An organic-inorganic hybrid perovskite of formula (I) below:
[(A)1−2.48p−b(B)3.48p+b](1+2p−y)/(1+p)(Pb)1−p−m(M)m(X1)3−y−q(X2)q (I)
in which:
A represents a cation chosen from Cs, Rb and a monovalent organic cation comprising an ammonium or carboxamidamidium group,
B represents a monovalent organic cation of formula (II) below:
R1—(CH2)2—R2 (II)
in which:
R2 represents an ammonium or carboxamidamidium group,
z represents 1, 2 or 3, and
R1 represents —H, —OH, —SH, —CN or a halogen, with the proviso that B is other than A,
X1 and X2 represent a halide, with the proviso that X1 and X2 are different from each other,
p is a number from 0.05 to 0.23,
b is a number greater than or equal to −0.30 and less than or equal to 0.30, with the proviso that b is greater than −3.48p and is less than (1−2.48p),
y represents a number greater than 0 and less than or equal to p,
q represents a number greater than or equal to 0 and less than or equal to (3−y),
M represents a divalent metal cation, and
m represents a number greater than or equal to 0 and less than or equal to (1−p).

### Claim 2 (depends on 1)

The perovskite as claimed in claim 1, in which X1 represents an iodide and q represents 0.

### Claim 3 (depends on 1)

The perovskite as claimed in claim 1, in which m represents 0.

### Claim 4 (depends on 1)

The perovskite as claimed in claim 1, in which:
the divalent metal cation is chosen from Pb, Sn, Cu, Cd and Mn, and/or
the halide is chosen from an iodide, a chloride and a bromide, and/or
the monovalent organic cation A is chosen from Cs, Rb, methylammonium and formamidinium, and/or
y is equal to p, and/or
b is a number greater than or equal to −0.20 and less than or equal to 0.20, and/or
m represents 0, and/or
q represents 0.

### Claim 5 (depends on 4)

The perovskite as claimed in claim 4, in which b is a number greater than or equal to −0.10 and less than or equal to 0.10.

### Claim 6 (depends on 4)

The perovskite as claimed in claim 4, in which b is a number greater than or equal to −0.07 and less than or equal to 0.07.

### Claim 7 (depends on 1)

The perovskite as claimed in claim 1, in which the monovalent organic cation B of formula (II) is HO—(CH2)2—NH3+.

### Claim 8 (depends on 1)

The perovskite as claimed in claim 1, of formula (VII) below:
[(A)1−2.48p−b(HO—(CH2)2—NH3+)3.48p+b](1+2p−y)/(1+p)(Pb)1−p(I)3−y (VII)
in which A, p, b and y are as defined in claim 1.

### Claim 9 (depends on 8)

The perovskite as claimed in claim 8, in which A represents CH3NH3+ and/or y=p.

### Claim 10

The perovskite as claimed in any one of the preceding claims, of formula (90), (92), (89), (93) or (88) below:
(CH3NH3)0.8138(HO—(CH2)2—NH3)0.2848[Pb0.9014I2.9014] (90),
(CH3NH3)0.6744(HO—(CH2)2—NH3)0.4586[Pb0.8670I2.8670] (92),
(CH3NH3)0.5821(HO—(CH2)2—NH3)0.5763[Pb0.8416I2.8416] (89),
(CH3NH3)0.5383(HO—(CH2)2—NH3)0.6405[Pb0.8212I2.8212] (93), or
(CH3NH3)0.4730(HO—(CH2)2—NH3)0.7331[Pb07940I2.7940] (88).

### Claim 11 (depends on 1)

The perovskite as claimed in claim 1, in which the monovalent organic cation B of formula (II) is HS—(CH2)2—NH3+.

### Claim 12 (depends on 1)

The perovskite as claimed in claim 1 of formula (VIII) below:
[(A)1−2.48p−b(HS—(CH2)2—NH3+)3.48p+b](1+2p−y)/(1+p)(Pb)1−p(I)3−y (VIII)
in which A, p, b and y are as defined above.

### Claim 13 (depends on 12)

The perovskite as claimed in claim 12, in which A represents FA and/or y=p.

### Claim 14 (depends on 1)

The perovskite as claimed in claim 1, of formula (T1) below:
(HC—(NH2)2)0.9177(HS—(CH2)2—NH3)0.1193[Pb0.9630I2.9630] (T1).

### Claim 15 (depends on 1)

The perovskite as claimed in claim 1, in the form of crystals, the crystalline system of which is of tetragonal symmetry.

### Claim 16 (depends on 1)

The perovskite as claimed in claim 1, in the form of a thin layer at least partly covering the surface of a substrate.

### Claim 17 (depends on 1)

A perovskite solar cell, at least one of the layers of which contains the perovskite as claimed in claim 1.

### Claim 18 (depends on 1)

The perovskite as claimed in claim 1, having a three-dimensional structure.

### Claim 19 (depends on 1)

The perovskite as claimed in claim 1, in which the monovalent organic cation B of formula (II) is chosen from CH3CH2NH3+, CH3C(NH2)2+, HO—(CH2)2—NH3+ and HS—(CH2)2—NH3+.