Mechanically robust and self-healable perovskite solar cells

Patent metadata

Field	Value
Publication number	US-11877504-B2
Application number	US-202217720348-A
Country	US
Kind code	B2
Filing date	Apr 14, 2022
Priority date	Apr 14, 2021
Publication date	Jan 16, 2024
Grant date	Jan 16, 2024

Abstract

A perovskite-polymer composite comprising a perovskite and a polymer, wherein the polymer has a structural unit comprising a thiourea (—HN(C═S)NH—) fragment and a (—R1—O—R2—) fragment, wherein R1 and R2 are each independently a C1-C6 alkyl or a cycloalkyl linker; a mechanically robust and self-healable solar cell comprising same; and a method of making same.

First claim

We claim:

1. A perovskite-polymer composite comprising a perovskite and a polymer, wherein the polymer has a formula I:

which has a structural unit comprising a thiourea (—HN(C═S)NH—) fragment and a (—R 1 —O—R 2 —) fragment, alone or in a further combination with a (—O—Si(CH3) 2 —O—) fragment, wherein R 1 and R 2 are each independently a C 1 -C 2 alkyl linker and R 3 and R 4 are each independently —NH2or

wherein —NH2 and/or

can be in protonated form, and n is 10-300.

2. The perovskite-polymer composite of claim 1 , wherein R 1 and R 2 are —CH 2 —CH 2 —.

3. The perovskite-polymer composite of claim 1 , wherein the perovskite has a formula of ABX 3 , where A is Cs + , CH 3 NH 3 + (MA), NH 2 (CH)NH 2 + (FA), or any combination thereof, B is Ge 2+ , Sn 2+ , Pb 2+ , or any combination thereof; and X is Cl − , Br − , I − or any combination thereof.

4. The perovskite-polymer composite of claim 1 , wherein the polymer has a weight percentage of about 2-25% of the total weight of the perovskite and the polymer.

5. The perovskite-polymer composite of claim 1 , wherein the perovskite-polymer composite is a film with a thickness of 10 nm-10 μm.

6. The perovskite-polymer composite of claim 5 , wherein the perovskite-polymer composite is a film with a thickness of 1 nm-1.0 μm.

7. A solar cell comprising a transparent conducting layer, a hole transporting layer, a perovskite layer, an electron transporting layer, and a counter electrode layer, wherein the perovskite layer comprises the perovskite-polymer composite film with a thickness of 10 nm-10 μm, wherein the perovskite-polymer composite comprises a perovskite and a polymer of formula I:

which has a structural unit comprising a thiourea (—HN(C═S)NH—) fragment and a (—R 1 —O—R 2 —) fragment, alone or in a further combination with a (—O—Si(CH3) 2 —O—) fragment, wherein R 1 and R 2 are each independently a C 1 -C 2 alkyl linker and R 3 and R 4 are each independently —NH2or

wherein —NH2 and/or

can be in protonated form, and n is 10-300.

8. The solar cell of claim 7 , wherein R 1 and R 2 are —CH 2 —CH 2 —.

9. The solar cell of claim 7 , wherein the perovskite has a formula of ABX 3 , where A is Cs + , CH 3 NH 3 + (MA), NH 2 (CH)NH 2 + (FA), or any combination thereof; B is Ge 2+ , Sn 2+ , Pb 2+ , or any combination thereof; and X is Cl − , Br − , I − or any combination thereof.

10. The solar cell of claim 7 , wherein the polymer in the perovskite-polymer composite has a weight percentage of about 2-25% of the total weight of the perovskite and the polymer.

11. The solar cell of claim 7 , wherein the transparent conducting layer is selected from the group comprising of indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), ZnO—Ga 2 O 3 , ZnO—Al 2 O 3 , tin oxide, antimony doped tin oxide (ATO), SrGeO 3 , zinc oxide, or any combination thereof.

12. The solar cell of claim 7 , wherein the hole transporting layer is selected from the group comprising of triphenylamine, carbazole, N,N,(diphenyl)-N′,N′di-(alkylphenyl)-4,4′-biphenyldiamine, (pTPDs), diphenylhydrazone, poly [N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (polyTPD), polyTPD substituted by one or more electron donor groups and/or acceptor groups, poly(9,9-dioctylfluorene-alt-N-(4-butylphenyl-diphenylamine (TFB), 2,2′,7,7′-tetrakis-N,N-di-p-methoxyphenylamine-9,9′-spirobifluorene) (spiro-OMeTAD), N,N,N′,N′-tetraphenylbenzidine (TPD), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA), poly(3-hexylthiophene) (P3HT), NiO, or MoO 3 .

13. The solar cell of claim 7 , wherein the perovskite layer comprises dimethylsulfoxide (DMSO) and a perovskite with an ABX 3 crystal structure where A is CH 3 NH 3 + (MA), NH 2 (CH)NH 2 + (FA), or Cs + ; B is Pb 2+ or Sn 2+ , and X is Cl − , Br − , or I − , or any combination thereof.

14. The solar cell of claim 7 , wherein the electron transporting layer is selected from the group comprising of [6,6]-phenyl-C 61 -butyric acid methyl ester (P 61 CBM), 1,4,5,8,9,11-hexazatriphenylene-hexacarbonitrile (HAT-CN), (C 60 —I h )[5,6]fullerene (C 60 ), (C 70 -D5h)[5,6]fullerene (C 70 ), [6,6]-Phenyl C 71 butyric acid methyl ester (PC 71 BM), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tri(phenyl-2-benzimi-dazolyl)-benzene (TPBI), polyethyleneimine ethoxylated (PEIE), poly [(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN), or a metal oxide, wherein the metal oxide is an oxide of a metal selected from the group consisting of Ti, Sn, Cs, Fe, Zn, W, Nb, SrTi, Si, Ti, Al, Cr, Sn, Mg, Mn, Zr, Ni, and Cu.

15. The solar cell of claim 7 , wherein the counter electrode layer comprises Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, conductive carbon, indium doped tin oxide, a conductive polymer, or a combination thereof.

16. A solar cell comprising a transparent conducting layer, a hole transporting layer, a perovskite layer, an electron transporting layer, and a counter electrode layer, wherein the perovskite layer comprises the perovskite-polymer composite film with a thickness of 10 nm-10 μm, wherein the perovskite-polymer composite comprises a perovskite and a polymer of formula I:

which has a structural unit comprising a thiourea (—HN(C═S)NH—) fragment and a (—R 1 —O—R 2 —) fragment, alone or in a further combination with a (—O—Si(CH3) 2 —O—) fragment, wherein R 1 and R 2 are each independently a C 1 -C 2 alkyl linker and R 3 and R 4 are each independently —NH2or

wherein —NH2 and/or

can be in protonated form, and n is 10-300.

17. The solar cell of claim 16 , wherein R 1 and R 2 are —CH 2 —CH 2 —.

18. The solar cell of claim 16 , wherein the perovskite has a formula of ABX 3 , where A is Cs + , CH 3 NH 3 + (MA), NH 2 (CH)NH 2 + (FA), or any combination thereof; B is Ge 2+ , Sn 2+ , Pb 2+ , or any combination thereof; and X is Cl − , Br − , I − or any combination thereof.

19. The solar cell of claim 16 , wherein the polymer in the perovskite-polymer composite has a weight percentage of about 2-25% of the total weight of the perovskite and the polymer.

20. The solar cell of claim 16 , wherein the transparent conducting layer is selected from the group comprising of indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), ZnO—Ga 2 O 3 , ZnO—Al 2 O 3 , tin oxide, antimony doped tin oxide (ATO), SrGeO 3 , zinc oxide, or any combination thereof.

21. The solar cell of claim 16 , wherein the hole transporting layer is selected from the group comprising of triphenylamine, carbazole, N,N,(diphenyl)-N′,N′di-(alkylphenyl)-4

Assignees

• Purdue Research Foundation

Inventors

• Dou Letian
• Finkenauer Blake Peter

Classifications

• H10K85/50

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

• H10K30/30

  comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains · CPC title

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H10K30/10

  comprising heterojunctions between organic semiconductors and inorganic semiconductors · CPC title

• H10K85/10 Primary

  Organic polymers or oligomers · CPC title