Perovskite film, precursor composition thereof, method for preparing the same, and semiconductor element including the same

Patent metadata

Field	Value
Publication number	US-2022123242-A1
Application number	US-202017121887-A
Country	US
Kind code	A1
Filing date	Dec 15, 2020
Priority date	Oct 20, 2020
Publication date	Apr 21, 2022
Grant date	—

Abstract

Provided is a perovskite film including crystal grains with a crystalline structure of [A][B][X] 3 .n[C], wherein [A], [B], [X], [C] and n are as defined in the specification.
The present disclosure further provides a precursor composition of perovskite film, method for producing of perovskite film, and semiconductor element including such films, as described above. With the optimal lattice arrangement, the perovskite film shows the effects of small surface roughness, and the semiconductor element thereof can thus achieve high efficiency and stability even with large area of film formation, thereby indeed having prospect of the application.

First claim

What is claimed is:

1 . A method for preparing a perovskite film, comprising:
dispersing or dissolving a perovskite precursor salt and a crown ether compound in a mixed solvent containing a dispersant and a polar solvent to prepare a precursor composition, wherein the dispersant is at least one selected from the group consisting of C 1-5 alkyl alcohol, C 2-6 alkoxy alcohol and C 5-8 alkoxyalkyl ester; and the polar solvent is at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl propylene urea, and N-methylpyrrolidone; and coating the precursor composition on a heated substrate to form a perovskite film.

2 . The method of claim 1 , wherein the polar solvent comprises γ-butyrolactone and dimethyl sulfoxide, and the volume ratio of the γ-butyrolactone to the dimethyl sulfoxide is 10:1 to 1:10

3 . The method of claim 2 , wherein the precursor composition is prepared by the steps of:
dispersing or dissolving the perovskite precursor salt in the mixed solvent containing γ-butyrolactone and dimethyl sulfoxide to form a first solution; dissolving the crown ether compound in γ-butyrolactone to form a second solution; and adding the dispersant after mixing the first solution and the second solution to obtain the precursor composition.

4 . The method of claim 1 , wherein the perovskite precursor salt comprises a compound of the chemical formula [A][X] and a compound of the chemical formula [B][X] 2 ,
wherein the [A] contains monovalent cations of M 1 , M 2 and M 3 ; M 1 is a substituted or unsubstituted ammonium ion, M 2 is a substituted or unsubstituted amidine ion, M 3 is at least one alkali-metal ion selected from the group consisting of Cs + , Rb + , Li + and Na + , and each of the substituents of the above M 1 and M 2 is C 1-20 alkyl or C 6-20 aryl when the M 1 and M 2 are substituted; [B] is at least one divalent cation selected from the group consisting of 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+ and Eu 2+ ; and [X] is at least two monovalent anions selected from the group consisting of F − , Cl − , Br − , I − , SCN − , and OCN − .

5 . The method of claim 1 , wherein the crown ether compound is at least one selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, and 30-crown-10, and the molarity of the crown ether compound is 0.2 to 1.6 mM in the precursor composition.

6 . The method of claim 1 , wherein the volume ratio of the polar solvent to the dispersant is 4:1 to 20:1.

7 . The method of claim 1 , wherein the step of coating comprises slit coating, blade coating, air blade coating or inkjet coating.

8 . A precursor composition for preparing a perovskite film, comprising:
a mixed solvent containing a dispersant and a polar solvent, wherein the dispersant is at least one selected from the group consisting of C 1-5 alkyl alcohol, C 2-6 alkoxy alcohol, and C 5-8 alkoxyalkyl ester, and the polar solvent is at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl propylene urea and N-methylpyrrolidone; and a perovskite precursor salt and a crown ether compound dispersed or dissolved in the mixed solvent.

9 . The precursor composition of claim 8 , wherein the perovskite precursor salt comprises a compound of the chemical formula [A][X] and a compound of the chemical formula [B][X] 2 ;
wherein [A] contains monovalent cations of M 1 , M 2 and M 3 ; M 1 is a substituted or unsubstituted ammonium ion, M 2 is a substituted or unsubstituted amidine ion, M 3 is at least one alkali-metal ion selected from the group consisting of Cs + , Rb + , Li + and Na + , and each of the substituents of the M 1 and the M 2 is C 1-20 alkyl or C 6-20 aryl when the M 1 and the M 2 are substituted; [B] is at least one divalent cation selected from the group consisting of 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+ and Eu 2+ ; and [X] is at least two monovalent anions selected from the group consisting of F − , Cl − , Br − , I − , SCN − , and OCN − .

10 . The precursor composition of claim 9 , further comprising a colloidal particle with a size of less than 500 nm, and the colloidal particles comprise the [A], the [B], the [X] and the crown ether compound.

11 . The precursor composition of claim 8 , wherein the crown ether compound is at least one selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, and 30-crown-10, and the molarity of the crown ether compound is 0.2 to 1.6 mM in the precursor composition.

12 . The precursor composition of claim 8 , wherein the polar solvent comprises γ-butyrolactone and dimethyl sulfoxide, and the volume ratio of the γ-butyrolactone to the dimethyl sulfoxide is 10:1 to 1:10.

13 . The precursor composition of claim 8 , wherein the volume ratio of the polar solvent to the dispersant is 4:1 to 20:1.

14 . A perovskite film, comprising crystal grains with a crystalline structure represented by the following formula:
[A][B][X] 3 .n [C] wherein [A] contains monovalent cations of M 1 , M 2 and M 3 ; M 1 is a substituted or unsubstituted ammonium ion, M 2 is a substituted or unsubstituted amidine ion, M 3 is at least one alkali-metal ion selected from the group consisting of Cs + , Rb + , Li + and Nat, and each of the substituents of the M 1 and the M 2 is C 1-20 alkyl or C 6-20 aryl when the M 1 and the M 2 is substituted; [B] is at least one divalent cation selected from the group consisting of 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+ and Eu 2+ ; [X] is at least two monovalent anions selected from the group consisting of F − , Cl − , Br, SCN − , and OCN − ; [C] is a crown ether compound; and n is a value of 0.01 to 10.

15 . The perovskite film of claim 14 , wherein the M 1 is a methylamine ion and the stoichiometric ratio of the M 1 in the [A] is in the range of 0.05 to 0.3, the M 2 is a formamidine ion and the stoichiometric ratio of the M 2 in the [A] is in the range of 0.6 to 0.9, and the M 3 is a cesium ion and the stoichiometric ratio of the M 3 in the [A] is in the range of 0.01 to 0.1.

16 . The perovskite film of claim 14 , wherein the crown ether compound is at least one selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, and 30-crown-10.

17 . The perovskite film of claim 14 , which has a characteristic peak in the range of 1100 to 1300 cm −1 in the Fourier transform infrared spectrum.

18 . The perovskite film of claim 14 , wherein the average size of the crystal grains is 200 to 300 microns.

19 . The perovskite film of claim 14 , wherein the crystal grains have a radially symmetric morphology from the center outward.

20 . A semiconductor element, comprising the perovskite film of claim 14 .

Assignees

• Ind Tech Res Inst

Inventors

• Huang Kuo-Wei
• Tung Yung-Liang
• Chiou Jung-Pin
• Chiu Pei-Ting
• Wu Shih-Hsiung

Classifications

• H10K85/50 Primary

  Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3 · CPC title

• H10K30/151

  the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2 · CPC title

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H10K30/10

  comprising heterojunctions between organic semiconductors and inorganic semiconductors · CPC title

• C01B13/18 Primary

  by thermal decomposition of compounds, e.g. of salts or hydroxides · CPC title