Material production process with alkylamine
The present invention relates to a process for producing a layer of crystalline A/M/X material, 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, wherein the solvent comprises; (i) acetonitrile, propionitrile, acetone or a mixture thereof; and (ii) an alkylamine. The invention also relates to a composition comprising: (i) a compound of formula MX n , (ii) a compound of formula AX, (iii) acetonitrile, propionitrile, acetone or a mixture thereof; and (iv) an alkylamine of formula R A NH 2 , wherein R A is a C 1-8 alkyl group.
1. A process for producing a layer of 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 one or more metal or metalloid cations selected from Ca 2+ , Sr 2+ , Cd 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Fe 2+ , Co 2+ , Pd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , Yb 2+ , Eu 2+ , Bi 3+ , Sb 3+ , Pd 4+ , W 4+ , Re 4+ , Os 4+ , Ir 4+ , Pt 4+ , Sn 4+ , Pb 4+ , Ge 4+ and Te 4+ ;
[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,
and 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,
wherein the solvent comprises;
(i) acetonitrile, propionitrile, acetone or a mixture thereof; and
(ii) an alkylamine.
2. A process according to claim 1 , wherein the alkylamine is a compound of formula R A NH 2 , wherein R A is a C 1-8 alkyl group.
3. A process according to claim 2 , wherein the alkylamine is methylamine, ethylamine, propylamine, butylamine or pentylamine.
4. A process according to claim 1 , wherein the molar ratio of (the alkylamine):(the first precursor compound) is from 1×10 −7 :1 to 0.5:1.
5. A process according to claim 1 , wherein the solvent comprises acetonitrile.
6. A process according to claim 1 , wherein:
the one or more second cations are selected from cations of formula Cs + , (NR 1 R 2 R 3 R 4 ) + , (R 1 R 2 N═CR 3 R 4 ) + , (R 1 R 2 N—C(R 5 )═NR 3 R 4 ) + and (R 1 R 2 N—C(NR 5 R 6 )═NR 3 R 4 ) + , wherein each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently H, a substituted or unsubstituted C 1-20 alkyl group or a substituted or unsubstituted aryl group.
7. A process according to claim 1 , wherein the first precursor compound is a compound of formula MX 2 .
8. A process according to claim 1 , wherein the process further comprises disposing on the substrate a second precursor compound, which second precursor compound comprises a second cation (A) and a first anion (X).
9. A process according to claim 8 , wherein the second precursor compound is a compound of formula AX.
10. A process according to claim 8 , wherein the molar ratio (first precursor compound):(second precursor compound) is from 1:2 to 2:1.
11. A process according to claim 1 , wherein the precursor composition further comprises:
(c) a second precursor compound, which second precursor compound comprises a second cation (A) and a first anion (X).
12. A process according to claim 1 , wherein [A] comprises a second cation which is a cation of formula (R A NH 3 ) + and the alkylamine is a compound of formula R A NH 2 , wherein each R A is the same group, which is a C 1-8 alkyl group.
13. A process according to claim 1 , wherein the crystalline A/M/X material comprises a perovskite compound of formula [A][M][X] 3 , wherein: [A] comprises the one or more second cations; [M] comprises the one or more first cations; and [X] comprises the one or more halide anion.
14. A process according to claim 1 , wherein the crystalline A/M/X material comprises a perovskite compound of formula CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbCl 3 , CH 3 NH 3 PbF 3 , CH 3 NH 3 PbBr x I 3-x , CH 3 NH 3 PbBr x Cl 3-x , CH 3 NH 3 PbIxBr 3-x , CH 3 NH 3 PbI x Cl 3-x , CH 3 NH 3 PbCl x Br 3-x , CH 3 NH 3 PbI 3-x Cl x , CH 3 NH 3 SnI 3 , CH 3 NH 3 SnBr 3 , CH 3 NH 3 SnCl 3 , CH 3 NH 3 SnF 3 , CH 3 NH 3 SnBrI 2 , CH 3 NH 3 SnBr x I 3-x , CH 3 NH 3 SnBr x Cl 3-x , CH 3 NH 3 SnF 3-x Br x , CH 3 NH 3 SnI x Br 3-x , CH 3 NH 3 SnI x Cl 3-x , CH 3 NH 3 SnF 3-x I x , CH 3 NH 3 SnCl x Br 3-x , CH 3 NH 3 SnI 3-x Cl x and CH 3 NH 3 SnF 3-x Cl x , CH 3 NH 3 CuI 3 , CH 3 NH 3 CuBr 3 , CH 3 NH 3 CuCl 3 , CH 3 NH 3 CuF 3 , CH 3 NH 3 CuBrI 2 , CH 3 NH 3 CuBr x I 3-x , CH 3 NH 3 CuBr x Cl 3-x , CH 3 NH 3 CuF 3-x Br x , CH 3 NH 3 CuI x Br 3-x , CH 3 NH 3 CuI x Cl 3-x , CH 3 NH 3 CuF 3-x I x , CH 3 NH 3 CuCl x Br 3-x , CH 3 NH 3 CuI 3-x Cl x , or CH 3 NH 3 CuF 3-x Cl x where x is from 0 to 3.
15. A process according to claim 1 , wherein the process further comprises removing the solvent to form the layer comprising the perovskite compound.
16. A process according to claim 1 , wherein the process further comprises heating the substrate with the precursor composition disposed thereon.
17. A process according to claim 1 , wherein disposing the precursor composition on the substrate comprises spin-coating the precursor composition on the substrate.
18. A process according to claim 1 , wherein the layer comprising the perovskite compound has a thickness of from 5 to 3000 nm.
19. A process according to claim 1 , which process comprises disposing on a substrate a precursor composition comprising:
(a) PbI 2 ;
(b) a solvent which comprises acetonitrile and methylamine; and
(c) (CH 3 NH 3 )I.
20. A process according to claim 1 , wherein the substrate comprises a layer of a first electrode material and optionally one or more additional layers that are each selected from: a layer of an n-type semiconductor, a layer of a p-type semiconductor, and a layer of insulating material.
21. A process according to claim 1 , wherein a surface of the substrate on which the precursor composition is disposed comprises one or more of a first electrode material, a layer of an n-type semiconductor, a layer of a p-type semiconductor, and a layer of insulating material.
22. A process according to claim 1 , wherein a surface of the substrate on which the precursor composition is disposed comprises a layer of material that is soluble in dimethylformamide.
23. A process according to claim 1 , wherein the solvent further comprises dimethylsulfoxide (DMSO).
24. A process according to claim 23 , wherein the solvent comprises DMSO in an amount of from 1.0 to 2.0 equivalents of the amount of the first cation M in the first precursor compound.
25. A process for producing a semiconductor device, which process comprises a process as defined in claim 1 .
26. A process according to claim 1 , wherein the alkylamine is methylamine.
27. A process according to claim 1 , wherein the molar ratio of (the alkylamine):(the first precursor compound) is from 1×10−6:1 to 0.1:1.
28. A process according to claim 1 , wherein the one or more first cations are selected from Cu2+, Pb2+, Ge2+ and Sn2+.
29. A process according to claim 1 , wherein the one or more second cations are selected from (CH3NH3)+ and (H2N—C(H)═NH2)+.
30. A process according to claim 1 , wherein the first precursor compound is a compound of formula SnI2, SnBr2, SnCl2, PbI2, PbBr2 or PbCl2.
31. A process according to claim 1 , wherein the second precursor compound is a compound of formula [A][X] wherein: [A] comprises the one or more second cations; and [X] comprises the one or more halide anion.
32. A process according to claim 1 , wherein the second precursor compound is (CH3NH3)I, (CH3NH3)Br or (CH3NH3)Cl.
33. A process according to claim 1 , wherein the second cation is methylammonium and the alkylamine is methylamine.
34. A process according to claim 1 , wherein the perovskite compound is CH3NH3PbI3.
35. A process according to claim 1 , wherein the substrate is heated to a temperature of from 50° C. to 200° C.
36. A process according to claim 1 , wherein the substrate is heated to a temperature of from 50° C. to 200° C. for a time of from 10 to 100 minutes.
37. A composition comprising:
a compound of formula MX n , wherein: M is Ca 2+ , Sr 2+ , Cd 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Fe 2+ , Co 2+ , Pd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , Yb 2+ , Eu 2+ , Bi 3+ , Sb 3+ , Pd 4+ , W 4+ , Re 4+ , Os 4+ , Ir 4+ , Pt 4+ , Sn 4+ , Pb 4+ , Ge 4+ or Te 4+ ; X is I − , Br − , Cl − or F − ; and n is 2, 3 or 4;
(ii) a compound of formula AX, wherein A is (R 1 NH 3 ) + , (NR 2 4 ) + and (H 2 N—C(R 1 )═NH 2 ) + , wherein R 1 is H or an unsubstituted C 1-6 alkyl group and each R 2 is an unsubstituted C 1-6 alkyl group, and X is I − , Br − , Cl − or F − ;
(iii) acetonitrile, propionitrile, acetone or a mixture thereof; and
(iv) an alkylamine of formula R A NH 2 , wherein R A is a C 1-8 alkyl group.
38. A composition according to claim 37 , which composition comprises:
(i) PbI 2 , PbBr 2 or PbCl 2 ;
(ii) (CH 3 NH 3 )I, (CH 3 NH 3 )Br or (CH 3 NH 3 )Cl; and
(iii) acetonitrile; and
(iv) methylamine.
39. A composition according to claim 38 , wherein the composition comprises PbI2.
40. A composition according to claim 38 , wherein the composition comprises (CH3NH3)I.
41. A composition according to claim 37 , wherein the molar ratio (MX n ):(AX) is from 1:2 to 2:1 and the molar ratio of (alkylamine):(MX n ) is from 1×10 −7 :1 to 0.5:1.
42. A composition according to claim 37 , wherein M is Cu2+, Pb2+, Ge2+ or Sn2+.
43. A composition according to claim 37 , wherein the molar ratio of (alkylamine):(MX n ) is from 1×10−7:1 to 0.1:1.