Granted Patent B2

US 12,414,404 · App. 18/325,009 · Granted Sep 9, 2025

Inventors: Shuojian Su (Ningde, CN); Zhaohui Liu (Ningde, CN); Yandong Wang (Ningde, CN); Yanfen Wang (Ningde, CN); Yongsheng Guo (Ningde, CN); Guodong Chen (Ningde, CN); Chuying Ouyang (Ningde, CN)

Assignee: CONTEMPORARY AMPEREX TECHNOLOGY (HONG KONG) LIMITED

H10F77/12C01G21/006H10F10/174H10F71/128H10F77/148H10F77/164C01P2002/34C01P2006/40

Abstract

Claims (110)

1. A photovoltaic device, comprising a photoactive crystalline material layer, wherein the photoactive crystalline material layer comprises a first region;

in the first region, the photoactive crystalline material layer comprises a penetrating crystal grain, wherein the penetrating crystal grain is a crystal grain penetrating through the photoactive crystalline material layer, and a percentage p of a quantity of penetrating crystal grains in a total quantity of crystal grains in the first region of the photoactive crystalline material layer is ≥80%; and

in the first region, the photoactive crystalline material layer comprises a backlight side and a backlight crystal grain, wherein the backlight crystal grain is a crystal grain having at least one face exposed to the backlight side, and the face of the backlight crystal grain exposed to the backlight side is a backlight crystal face, wherein

the backlight side has an average flatness index R avg , wherein 10≤R avg ≤70; and

R avg of the backlight side is calculated according to the following formula:

(

R

a

⁢

v

⁢

g

)

=

∑

i

=

1

i

=

n

⁢

R

i

n

wherein R i is flatness index of the i-th backlight crystal grain in the first region, and R i is calculated according to the following formula:

R i =d i /h i

wherein d i is width of a backlight crystal face of the i-th backlight crystal grain in the first region;

h i is protrusion height of the backlight crystal face of the i-th backlight crystal grain in the first region; and

n is quantity of all backlight crystal grains in the first region.

2. The photovoltaic device according to claim 1 , wherein the photoactive crystalline material comprises an A/M/X crystalline material, and the A/M/X crystalline material has the following general formula:

[A] a [M] b [X] c

wherein [M] comprises one or more first cations, and the first cation comprises a metal ion, a metalloid ion, or a combination thereof;

[A] comprises one or more second cations;

[X] comprises one or more halogen anions;

a is at least 1, 2, 3, 4, 5, or 6;

b is at least 1, 2, 3, 4, 5, or 6; and

c is 1 to 18.

3. The photovoltaic device according to claim 2 , wherein one or more of the following are satisfied:

the one or more first cations are 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+ , P d4+ , W 4+ , Re 4+ , Os 4+ , Ir 4+ , Pt 4+ , Sn 4+ , Pb 4+ , Ge 4+ , or Te 4+ ; and

the one or more second cations are selected from 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 ) + , or (R 1 R 2 N—C(NR 5 R 6 )═R 3 R 4 ) + , wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 each are independently selected from H, substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted aryl; and

the halogen anion is selected from Cl − , Br − , or I − .

4. The photovoltaic device according to claim 2 , wherein the A/M/X crystalline material comprises FAPbI 3 , FAPbBr 3 , FAPbCl 3 , FAPbF 3 , FAPbBr x I 3-x , FAPbBr x Cl 3-x , FAPbI x Br 3-x , FAPbI x Cl 3-x , FAPbCl x Br 3-x , FAPbI 3-x Cl x , CsPbI 3 , CsPbBr 3 , CsPbCl 3 , CsPbF 3 , CsPbBr x I 3-x , CsPbBr x Cl 3-x , CsPbI x Br 3-x , CsPbI x Cl 3-x , CsPbCl x Br 3-x , CsPbI 3-x Cl x , FA 1-y Cs y PbI 3 , FA 1-y Cs y PbBr 3 , FA 1-y Cs y PbCl 3 , FA 1-y Cs y PbF 3 , FA 1-y Cs y PbBr x I 3-x , FA 1-y Cs y PbBr x Cl 3-x , FA 1-y yCs y PbI x Br 3-x , FA 1-y Cs y PbI x Cl 3-x , FA 1-y Cs y PbCl x Br 3-x , FA 1-y Cs y PbI 3-x Cl x , or a combination thereof,

wherein x=0-3, and y=0.01-0.25.

5. The photovoltaic device according to claim 2 , wherein the A/M/X crystalline material comprises FAPbI 3 , CsPbI 3 , FA 1-y Cs y PbI 3 , or a combination thereof, wherein y=0.01-0.25.

6. The photovoltaic device according to claim 2 , wherein thickness of the photoactive crystalline material layer is 100 nm or more.

7. The photovoltaic device according to claim 1 , further comprising a first charge transport layer and a second charge transport layer, wherein the photoactive crystalline material layer is located between the first charge transport layer and the second charge transport layer; and

the first charge transport layer and the second charge transport layer are respectively an electron transport layer and a hole transport layer; or

the first charge transport layer and the second charge transport layer are respectively a hole transport layer and an electron transport layer.

8. The photovoltaic device according to claim 7 , further comprising a first electrode and a second electrode, wherein the electron transport layer, hole transport layer, and photoactive crystalline material layer are located between the first electrode and the second electrode.

9. A preparation method of A/M/X crystalline material, wherein the A/M/X crystalline material has the following general formula:

[A] a [M] b [X] c

wherein [M] comprises one or more first cations, and the first cation comprises a metal ion, a metalloid ion, or a combination thereof;

[A] comprises one or more second cations;

[X] comprises one or more halogen anions;

a is 1 to 6;

b is 1 to 6; and

c is 1 to 18; and

the method comprises providing a precursor composition on a substrate, wherein the precursor composition comprises:

(a) at least one precursor compound;

(b) a solvent;

(c) a surfactant, the surfactant being an amphoteric surfactant; and

(d) an amino compound comprising one or more selected from a nitrile-amine compound, an amino acid compound, a hydrazine compound, a urea compound, a guanidine compound, or a salt or hydrate thereof.

10. The method according to claim 9 , wherein the surfactant comprises dodecyl aminopropionate, dodecyl ethoxy sulphobetaine, dodecyl dimethyl hydroxypropyl sulphobetaine, zwitterionic polyacrylamide, octadecyl dihydroxyethyl amine oxide, tetradecyl dihydroxyethyl amine oxide, lauramidopropylamine oxide, lauryl betaine, L-α-phosphatidylcholine, 3-(N,N-dimethylmyristylammonio)propanesulfonate, dodecylbenzene sulfonate, or a combination thereof.

11. The method according to claim 9 , wherein the amino compound comprises urea formaldehyde (C 3 H 8 N 2 O 3 ), N,N″-(isobutylidene)diurea (C 6 H 14 N 4 O 2 ), hydrazine (H 4 N 2 ), guanidine (CH 3 N 3 O), cyanamide (CH 2 N 2 ), or a combination thereof.

12. The method according to claim 9 , wherein the precursor composition comprises a first solvent and a second solvent, a boiling point of the first solvent is 40° C.-165° C., and a boiling point of the second solvent is 170° C.-250° C.

13. The method according to claim 12 , wherein, one or more of the following are satisfied:

(1) the first solvent is selected from one or more of N,N-dimethylformamide (DMF), 2-methoxyethanol, and acetonitrile (ACN);

(2) the second solvent is selected from one or more of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and diphenyl sulfoxide (DPSO); and

(3) a volume ratio of the first solvent to the second solvent is (4-10):1.

14. The method according to claim 9 , wherein the precursor composition comprises:

a first precursor compound, wherein the first precursor compound contains a first cation; and

a second precursor compound, wherein the second precursor compound contains a second cation.

15. The method according to claim 14 , wherein one or more of the following are satisfied:

(1) the first precursor compound contains a first halogen anion; and

(2) the second precursor compound contains a second halogen anion.

16. The method according to claim 14 wherein, one or more of the following are satisfied:

(1) the first precursor compound comprises lead iodide (PbI 2 ), lead bromide (PbBr 2 ), or a combination thereof; and

(2) the second precursor compound comprises formamidinium iodide (FAI), formamidinium bromide (FABr), cesium iodide (CsI), cesium bromide (CsBr), or a combination thereof.

17. The method according to claim 9 , further comprising implementing curing treatment on the precursor composition provided on a surface of the substrate.

18. The method according to claim 17 , further comprising implementing annealing treatment on a resulting product of the curing treatment.

19. A method for preparing a photovoltaic device

the method comprises:

providing a first electrode;

providing a first charge transport layer on a surface of the first electrode;

forming an A/M/X crystalline material layer on a surface of the first charge transport layer, wherein forming the A/M/X crystalline material layer further comprises:

providing a precursor composition on the surface of the first charge transport layer, wherein the precursor composition comprises:

(a) a first precursor compound and a second precursor compound, the first precursor compound comprising a first cation and a first halogen anion, and the second precursor compound comprising a second cation and a second halogen anion;

(b) a solvent;

(c) a surfactant, the surfactant being an amphoteric surfactant; and

(d) an amino compound comprising one or more selected from a nitrile-amine compound, an amino acid compound, a hydrazine compound, a urea compound, a guanidine compound, or a salt or hydrate thereof;

implementing curing treatment on the precursor composition; and

implementing annealing treatment on a resulting product of the curing treatment;

forming a second charge transport layer on the A/M/X crystalline material layer; and

forming a second electrode on the second charge transport layer,

wherein the A/M/X crystalline material has the following general formula:

[A] a [M] b [X] c

wherein [M] represents the first cation;

[A] represents the second cations;

[X] represents the first and second halogen anions;

a is 1 to 6;

b is 1 to 6; and

c is 1 to 18;

wherein the first charge transport layer and the second charge transport layer are respectively an electron transport layer and a hole transport layer; or

the first charge transport layer and the second charge transport layer are respectively a hole transport layer and an electron transport layer.

20. The method according to claim 19 , wherein

the first precursor compound comprises lead iodide (PbI 2 ), lead bromide (PbBr 2 ), or a combination thereof,

the second precursor compound comprises formamidinium iodide (FAI), formamidinium bromide (FABr), cesium iodide (CsI), cesium bromide (CsBr), or a combination thereof,

the surfactant comprises dodecyl aminopropionate, dodecyl ethoxy sulphobetaine, dodecyl dimethyl hydroxypropyl sulphobetaine, zwitterionic polyacrylamide, octadecyl dihydroxyethyl amine oxide, tetradecyl dihydroxyethyl amine oxide, lauramidopropylamine oxide, lauryl betaine, L-α-phosphatidylcholine, 3-(N,N-dimethylmyristylammonio) propanesulfonate, dodecylbenzene sulfonate, or a combination thereof,

the amino compound comprises urea formaldehyde (C 3 H 8 N 2 O 3 ), N,N″-(isobutylidene)diurea (C 6 H 14 N 4 O 2 ), hydrazine (H 4 N 2 ), guanidine (CH 3 N 3 O), cyanamide (CH 2 N 2 ), or a combination thereof.

Assignments (2)

Continuity (2)

References Cited (26)