# US 12,765,250 B2 · Process for producing a layer with mixed solvent system

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- Number: US 12,765,250 B2
- Document ID: US12765250B2
- Status: Granted
- Kind: B2
- Application number: 18/608,872
- Filed: 2024-03-18
- Published: 2024-08-15
- Granted: 2026-10-13
- Earliest claimed: 2018-10-22
- Assignees: Oxford Photovoltaics Limited
- Applicants: Oxford Photovoltaics Limited
- Inventors: Henry James Snaith; Bernard Wenger; Pabitra Kumar Nayak; Nakita Kimberly Noel
- Web page: https://patentgrep.com/patent/US12765250B2

## CPC

- H10K 71/15: characterised by the solvent used
- H10K 85/215: {comprising substituents, e.g. PCBM}
- H10K 85/30: Coordination compounds
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K 30/40: comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
- H10K 30/50: Photovoltaic [PV] devices
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

The present invention relates to a process for producing a layer of a crystalline A/M/X material, which crystalline A/M/X material comprises a compound of formula [A]a[M]b[X]c, wherein: [M] comprises one or more first cations, which one or more first cations are metal or metalloid cations; [A] comprises one or more second cations; [X] comprises one or more halide anions; a is an integer from 1 to 6; b is an integer from 1 to 6; and c is an integer from 1 to 18, wherein the process comprises disposing on a substrate a precursor composition comprising: (a) a first precursor compound comprising a first cation (M), which first cation is a metal or metalloid cation; and (b) a solvent, and wherein the solvent comprises: (i) a non-polar organic solvent which is a hydrocarbon solvent, a chlorohydrocarbon solvent or an ether solvent; and (ii) a first organic amine comprising at least three carbon atoms. Also described are compositions useful in the process of the invention.

## Claims

### Claim 1

A composition comprising:
(i) a compound of formula MXn, wherein: M is Ca2+, Sr2+, Cd2+, Cu2+, Ni2+, Mn2+, Fe2+, Co2+, Pd2+, Ge2+, Sn2+, Pb2+, Yb2+, Eu2+, Bi3+, Sb3+, Pd4+, W4+, Re4+, Os4+, Ir4+, Pt4+, Sn4+, Pb4+, Ge4+ or Te4+; X is I−, Br−, Cl− or F−; and n is 2, 3 or 4;
(ii) a compound of formula AX, wherein A is selected from (R1NH3)+, (NR24)+ and (H2N—C(R1)═NH2)+, wherein R1 is H or an unsubstituted C1-6 alkyl group and each R2 is an unsubstituted C1-6 alkyl group, and X is I−, Br−, Cl− or F−;
(iii) a non-polar organic solvent which is a hydrocarbon solvent, a chlorohydrocarbon solvent or an ether solvent; and
(iv) a first organic amine comprising at least three carbon atoms,
characterized in that the composition comprises the non-polar organic solvent and the first organic amine in a volume ratio (non-polar organic solvent): (first organic amine) of from 40:1 to 1:2.

### Claim 2 (depends on 1)

A composition according to claim 1, wherein the non-polar organic solvent is toluene, benzene, xylene, chlorobenzene, dichlorobenzene, chloroform, anisole, hexane, pentane, cyclohexane or cyclopentane.

### Claim 3 (depends on 1)

A composition according to claim 1, wherein the first organic amine is a first alkylamine of formula RANH2 or a first arylamine of formula ArNH2, wherein RA is an unsubstituted C3-20 alkyl group or a C3-20 alkyl group substituted with a phenyl group; and Ar is an unsubstituted phenyl group or phenyl group substituted with from one to three C1-6 alkyl groups.

### Claim 4 (depends on 3)

A composition according to claim 3, wherein the first organic amine is a first alkylamine which is propylamine, butylamine, pentylamine, hexylamine or phenylethylamine.

### Claim 5 (depends on 1)

A composition according to claim 1, wherein the volume ratio (non-polar organic solvent):(first organic amine) is from 20:1 to 4:1.

### Claim 6 (depends on 1)

A composition according to claim 1, wherein the composition further comprises an organic material.

### Claim 7 (depends on 6)

A composition according to claim 6, wherein the organic material is an organic dielectric material, an organic semiconducting material, an organic polymer, a fullerene derivative, an organic reducing agent or an organic oxidizing agent.

### Claim 8 (depends on 6)

A composition according to claim 6, wherein the organic material is:
an organic semiconducting material selected from poly(4-butylphenyldiphenylamine), poly(N,N′-bis-4-butylphenyl-N,N′-bisphenyl)benzidine (polyTPD), a poly(triarylamine) (PTAA), a spiro-bi-fluorene compound, spiro-OMeTAD, a polymer comprising thiophene, poly(3-hexyl thiophene), poly(3,4-ethylenedioxythiophene) (PEDOT), a rylene derivative, perylene, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4′-(N-(4-sec-butylphenyl) diphenylamine)] (TFB), poly(9,9-dioctylfluorenyl-2,7-diyl) (F8), poly(9-vinylcarbazole) (PVK), 4,4′-Bis(carbazol-9-yl) biphenyl (CBP), poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3] thiadiazol-4,7-diyl)] (F8BT), poly(3-hexylthiophene-2,5-diyl) (P3HT), phenyl-C61-butyric acid methyl ester (PCBM) and diphenylanthracene (DPA);
an organic dielectric material selected from poly(methylmethacrylate) (PMMA), polystyrene, poly(vinyl acetate) and ethylene-vinyl acetate (EVA); or
an organic reducing agent or an organic oxidizing agent selected from 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), hexafluorotetra-cyanonaphthoquinodimethane (F6TCNNQ), a molybdenum compound, molybdenum tris (dithiolene), pentamethylcyclopentadienyl cyclopentadienyl rhodium dimer, decamethylcobaltocene (DMC) and 3-dimethyl-2-phenyl-2,3-dihydro-1H-benzoimidazole (N-DMBI).

### Claim 9 (depends on 1)

A composition according to claim 1, wherein the solvent further comprises a second alkylamine.

### Claim 10 (depends on 1)

A composition according to claim 1, wherein the composition comprises:
(i) PbI2, PbBr2 or PbCl2;
(ii) (H2N—C(H)═NH2)I, (H2N—C(H)═NH2)Br, (H2N—C(H)═NH2)Cl, (CH3NH3)I, (CH3NH3)Br or (CH3NH3)Cl;
(iii) toluene or chlorobenzene; and
(iv) butylamine.

### Claim 11 (depends on 1)

A composition according to claim 1 wherein the composition comprises:
(i) PbI2;
(ii) (CH3NH3)I or (H2N—C(H)═NH2)I;
(iii) toluene;
(iv) butylamine; and
(v) methylamine.

### Claim 12 (depends on 1)

A composition according to claim 1 wherein M is Cu2+, Pb2+, Ge2+ or Sn2+.