Hybrid perovskite material processing

• US 9,880,458 B1
• Filed: 04/17/2017
• Issued: 01/30/2018
• Est. Priority Date: 04/17/2017
• Status: Active Grant

• Current Assignee: Cubicpv Incorporated
• Original Assignee: Hee Solar, LLC
• Inventors: Irwin, Michael D., Mielczarek, Kamil, Dhas, Vivek V.
• Primary Examiner(s): Cameron, Erma
• Application Number:
  US15/489,431
• Time in Patent Office: 288 Days
• Field of Search: None
• CPC Class Codes: B05D 1/38 with intermediate treatment intermediate treatment per se B05D3/00
• CPC Class Codes: B05D 3/107 Post-treatment of applied coatings
• CPC Class Codes: C01D 3/12 Iodides
• CPC Class Codes: C01G 21/16 Halides
• CPC Class Codes: C07C 19/00 Acyclic saturated compounds containing halogen atoms
• CPC Class Codes: C07C 233/03 with carbon atoms of carboxamide groups bound to hydrogen atoms
• CPC Class Codes: C07C 317/04 of an acyclic saturated carbon skeleton
• CPC Class Codes: C09D 11/52 Electrically conductive inks
• CPC Class Codes: G03C 2001/03558 Iodide content
• CPC Class Codes: G03C 8/365 containing silver-halide solvents
• CPC Class Codes: H01G 9/2009 Solid electrolytes
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H01G 9/2059 comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H10K 2102/102 comprising tin oxides, e.g. fluorine-doped SnO2
• CPC Class Codes: H10K 30/151 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
• CPC Class Codes: H10K 30/451 comprising a metal-semiconductor-metal [m-s-m] structure
• CPC Class Codes: H10K 71/12 using liquid deposition, e.g. spin coating
• CPC Class Codes: H10K 71/15 characterised by the solvent used
• CPC Class Codes: H10K 71/40 Thermal treatment, e.g. annealing in the presence of a solvent vapour
• CPC Class Codes: H10K 85/50 Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
• CPC Class Codes: Y02E 10/549 : Organic PV cells

Abstract

A method for preparing photoactive perovskite materials. The method comprises the steps of: introducing a lead halide and a first solvent to a first vessel and contacting the lead halide with the first solvent to dissolve the lead halide to form a lead halide solution, introducing a Group 1 metal halide a second solvent into a second vessel and contacting the Group 1 metal halide with the second solvent to dissolve the Group 1 metal halide to form a Group 1 metal halide solution, and contacting the lead halide solution with the Group 1 metal halide solution to form a thin-film precursor ink. The method further comprises depositing the thin-film precursor ink onto a substrate, drying the thin-film precursor ink to form a thin film, annealing the thin film; and rinsing the thin film with a salt solution.

Claims

1. A method comprising the steps of:

preparing a thin-film precursor ink, wherein preparing the thin-film precursor ink comprises the steps of;

introducing a lead halide into a first vessel;

introducing a first solvent to the first vessel;

contacting the lead halide with the first solvent to dissolve the lead halide to form a lead halide solution;

introducing a Group 1 metal halide into a second vessel;

introducing a second solvent into the second vessel; and

contacting the Group 1 metal halide with the second solvent to dissolve the group 1 metal halide to form a Group 1 metal halide solution;

contacting the lead halide solution with the Group 1 metal halide solution to form the thin-film precursor ink;

depositing the thin-film precursor ink onto a substrate;

drying the thin-film precursor ink to form a thin film;

annealing the thin film; and

rinsing the thin film with a salt solution comprising a third solvent and a salt selected from the group consisting of methylammonium halide, formamidinium halide, guanidinium halide, ethene tetramine halide, imidazolium halide, 1,2,2-triaminovinyl ammonium halide, and 5-aminovaleric acid hydrohalide.

2. The method of claim 1, wherein the lead halide comprises lead (II) iodide.

3. The method of claim 1, wherein the Group 1 metal halide comprises cesium iodide.

4. The method of claim 1, wherein the Group 1 metal halide comprises rubidium iodide.

5. The method of claim 1, wherein the Group 1 metal halide comprises sodium iodide.

6. The method of claim 1, wherein the Group 1 metal halide comprises potassium iodide.

7. The method of claim 1, wherein the first solvent and the second solvent are selected from the group consisting of dry N-cyclohexyl-2-pyrrolidone, alkyl-2-pyrrolidone, dimethylformamide (DMF), dialkylformamide, dimethylsulfoxide (DMSO), methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, tert-butylpyridine, pyridine, alkylpyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, and combinations thereof.

8. The method of claim 1, wherein the first solvent comprises dry dimethylformamide (DMF).

9. The method of claim 1, wherein the second solvent comprises dimethylsulfoxide (DMSO).

10. The method of claim 1, wherein the third solvent is selected from the group consisting of dimethylformamide, isopropanol, methanol, ethanol, butanol, chloroform, chlorobenzene, dimethylsulfoxide, water, and combinations thereof.

11. The method of claim 1, wherein the thin-film precursor ink has a molar concentration of the Group 1 metal halide that is between 1% and 25% of the molar concentration of the lead halide.

12. The method of claim 1, wherein annealing the thin film occurs for between about 5 to about 30 minutes at a temperature between about 40°

C. to about 60°

C.

13. The method of claim 1, wherein the salt comprises formamidinium iodide.

14. The method of claim 1, wherein the salt comprises methylammonium iodide.

15. The method of claim 1, wherein rinsing the thin film comprises at least partial submersion in the salt solution.