IP Library Granted Patent US 9,136,408
Granted Patent B2
US 9,136,408 · App. 14/209,013 · Granted Sep 15, 2015

Perovskite and other solar cell materials

Inventors: Michael D. Irwin (Dallas, TX); Robert D. Maher, III (Plano, TX); Jerred A. Chute (Dallas, TX); Vivek V. Dhas (Dallas, TX)
Assignee: Hunt Energy Enterprises, LLC
H01L31/032H01G9/2031H01L51/42H01L2031/0344
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Quick Facts
Patent No.
US 9,136,408
App. No.
14/209,013
Granted
Sep 15, 2015
Kind
B2
Abstract

Photovoltaic devices such as solar cells, hybrid solar cell-batteries, and other such devices may include an active layer having perovskite material and copper-oxide or other metal-oxide charge transport material. Such charge transport material may be disposed adjacent to the perovskite material such that the two are adjacent and/or in contact. Inclusion of both materials in an active layer of a photovoltaic device may improve device performance. Other materials may be included to further improve device performance, such as, for example: one or more interfacial layers, one or more mesoporous layers, and one or more dyes.

Claims (66)

1. A photovoltaic device comprising:

a first electrode;

a second electrode;

an active layer disposed at least partially between the first and second electrodes, the active layer comprising:

a perovskite material, and

charge transport material comprising a copper-oxide compound.

2. The photovoltaic device of claim 1 , wherein the perovskite material has the formula CMX 3 , wherein C comprises one or more cations, M comprises one or more metals, and X comprises one or more anions.

3. The photovoltaic device of claim 2 , wherein C comprises one or more cations each selected from the group consisting of Group 1 metals, Group 2 metals, organic cations, and combinations thereof;

wherein M comprises one or more metals each selected from the group consisting of Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Zn, and combinations thereof; and

wherein X comprises one or more anions each selected from the group consisting of halides, Group 16 anions, and combinations thereof.

4. The photovoltaic device of claim 3 , wherein M is Pb, and wherein X comprises one or more halides.

5. The photovoltaic device of claim 4 , wherein C is methylammonium.

6. The photovoltaic device of claim 3 , wherein C is Sr, M is Ti, and X comprises oxygen.

7. The photovoltaic device of claim 1 , wherein the active layer further comprises photoactive material selected from the group consisting of: a dye; silicon, cadmium telluride, cadmium sulfide, cadmium selenide, copper indium gallium selenide, gallium arsenide, germanium indium phosphide, semiconducting polymers, and combinations thereof.

8. The photovoltaic device of claim 7 , wherein the photoactive material comprises a dye comprising:

a primary electron donor moiety comprising at least one substituent selected from the group consisting of: aryl amine; aryl phosphine; aryl arsine; aryl stibine; aryl sulfide; aryl selenide; phenyl; phenol; alkoxy phenyl; dialkoxy phenyl; alkyl phenyl; and combinations thereof;

a core moiety comprising at least one aryl substituent selected from the group consisting of: a nitrogen heterocyclic compound; benzothiophene; dibenzothiophene; naphthothiophene; dinaphthothiophene; benzonaphthothiophene; naphthyl; benzothiazole; benzothiadiazole; benzo[b]naphtha[2,3-d]thiophene; 4H-cyclopenta[1,2-b:5,4-b′]bisthiophene; dinaphtho[2,3-d]thiophene; thieno[3,2-b]thiophene; naphthalene; anthracene; and combinations thereof;

a second electron donor moiety comprising at least one pi-electron donor substituent selected from the group consisting of: thiophene, benzothiadiazole, benzene, benzothiophene, thienothiophene, and combinations thereof; and

an electron-withdrawing moiety comprising at least one substituent selected from the group consisting of: a carboxylic acid; a monocyanocomplex; a dicyanocomplex; a thiocyanocomplex; an isothiocyanocomplex; and combinations thereof.

9. The photovoltaic device of claim 1 , wherein the charge transport material is disposed upon the perovskite material so as to achieve high contact surface area between the charge transport material and the perovskite material.

10. The photovoltaic device of claim 7 , further comprising an interfacial layer disposed at least partially between the active layer and either of the first electrode and the second electrode;

wherein the interfacial layer is selected from the group consisting of Al; Bi; In; Mo; Ni; Pt; Si; Ti; V; Nb; zinc; oxides of any of the foregoing metals; a sulfide of any of the foregoing metals; a nitride of any of the foregoing metals; alkyl silyl groups; graphite; graphene; fullerenes; carbon nanotubes; and combinations thereof.

11. The photovoltaic device of claim 9 , further comprising an interfacial layer disposed at least partially between the active layer and either of the first electrode and the second electrode;

wherein the interfacial layer is selected from the group consisting of Al; Bi; In; Mo; Ni; Pt; Si; Ti; V; Nb; zinc; oxides of any of the foregoing metals; a sulfide of any of the foregoing metals; a nitride of any of the foregoing metals; alkyl silyl groups; graphite; graphene; fullerenes; carbon nanotubes; and combinations thereof.

12. The photovoltaic device of claim 1 , wherein the active layer further comprises a mesoporous layer comprising pore-containing material selected from the group consisting of: Al; Bi; In; Mo; Nb; Ni; Pt; Si; Ti; V; Zn; an oxide of any of the foregoing metals; a sulfide of any of the foregoing metals; a nitride of any of the foregoing metals; treated asphaltenes; titania/metal-oxide bilayers; alkyl silyl groups; graphite; graphene; fullerenes; carbon nanotubes; and combinations thereof.

13. The photovoltaic device of claim 10 , wherein the active layer further comprises a mesoporous layer comprising pore-containing material selected from the group consisting of: Al; Bi; In; Mo; Nb; Ni; Pt; Si; Ti; V; Zn; an oxide of any of the foregoing metals; a sulfide of any of the foregoing metals; a nitride of any of the foregoing metals; treated asphaltenes; titania/metal-oxide bilayers; alkyl silyl groups; graphite; graphene; fullerenes; carbon nanotubes; and combinations thereof.

14. The photovoltaic device of claim 13 , wherein:

the perovskite material is disposed between the mesoporous layer and the charge transport material;

the interfacial layer is disposed between the mesoporous layer and one of the first electrode and the second electrode.

15. The photovoltaic device of claim 1 , wherein the copper-oxide compound has the formula Cu x O y , wherein x is between approximately 1 and 3, and wherein y is between approximately 0.1 and 2.

16. The photovoltaic device of claim 15 , wherein the copper-oxide compound comprises nanoparticles sized 50 nm diameter and smaller.

17. The photovoltaic device of claim 13 , wherein the copper-oxide compound has the formula Cu x O y , wherein x is between approximately 1 and 3, and wherein y is between approximately 0.1 and 2; and further wherein the copper-oxide compound comprises nanoparticles sized 50 nm diameter and smaller.

18. A photovoltaic device comprising

a first electrode;

a second electrode;

an active layer disposed at least partially between the first and second electrodes, the active layer comprising:

a photoactive perovskite material; and

hole transport material comprising a copper-oxide compound.

19. The photovoltaic device of claim 18 , wherein the active layer further comprises a perovskite material having the formula CMX 3 ;

wherein C comprises one or more cations each selected from the group consisting of Group 1 metals, Group 2 metals, organic cations, and combinations thereof;

wherein M comprises one or more metals each selected from the group consisting of Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Zn, and combinations thereof; and

wherein X comprises one or more anions selected from the group consisting of halides, Group 16 anions, and combinations thereof.

20. The photovoltaic device of claim 19 , wherein the active layer further comprises photoactive material selected from the group consisting of: a dye; silicon, cadmium telluride, cadmium sulfide, cadmium selenide, copper indium gallium selenide, gallium arsenide, germanium indium phosphide, semiconducting polymers, and combinations thereof.

21. The photovoltaic device of claim 20 , wherein the photoactive material comprises a dye comprising:

a primary electron donor moiety comprising at least one substituent selected from the group consisting of: aryl amine; aryl phosphine; aryl arsine; aryl stibine; aryl sulfide; aryl selenide; phenyl; phenol; alkoxy phenyl; dialkoxy phenyl; alkyl phenyl; and combinations thereof;

a core moiety comprising at least one aryl substituent selected from the group consisting of: a nitrogen heterocyclic compound; benzothiophene; dibenzothiophene; naphthothiophene; dinaphthothiophene; benzonaphthothiophene; naphthyl; benzothiazole; benzothiadiazole; benzo[b]naphtha[2,3-d]thiophene; 4H-cyclopenta[1,2-b:5,4-b′]bisthiophene; dinaphtho[2,3-d]thiophene; thieno[3,2-b]thiophene; naphthalene; anthracene; and combinations thereof;

a second electron donor moiety comprising at least one pi-electron donor substituent selected from the group consisting of: thiophene, benzothiadiazole, benzene, benzothiophene, thienothiophene, and combinations thereof; and

an electron-withdrawing moiety comprising at least one substituent selected from the group consisting of: a carboxylic acid; a monocyanocomplex; a dicyanocomplex; a thiocyanocomplex; an isothiocyanocomplex, and combinations thereof.

22. The photovoltaic device of claim 18 , wherein the charge-transporting compound comprises a copper-oxide compound having the formula Cu x O y , wherein x is between approximately 1 and 3, and wherein y is between approximately 0.1 and 2.

23. The photovoltaic device of claim 22 , wherein the charge-transporting compound comprises nanoparticles sized 50 nm diameter and smaller.

24. A photovoltaic device comprising:

a first electrode;

a second electrode;

an active layer disposed at least partially between the first and second electrodes, the active layer comprising:

charge transport material comprising Cu x O y , wherein x is between approximately 1 and 3, and wherein y is between approximately 0.1 and 2; and

a perovskite material having the formula CMX 3 , wherein (i) C comprises one or more cations each selected from the group consisting of Group 1 metals, Group 2 metals, organic cations, amine, ammonium, and combinations thereof, (ii) M comprises one or more metals each selected from the group consisting of Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Zn, and combinations thereof, and (iii) X comprises one or more anions each selected from the group consisting of halides, Group 16 anions, and combinations thereof.

25. The photovoltaic device of claim 24 wherein C comprises an alkyl ammonium cation, M comprises Pb, and X comprises one or more halides.

26. The photovoltaic device of claim 24 wherein C is Sr, M is Ti, and X comprises O.

27. The photovoltaic device of claim 24 wherein the charge transport material comprises Cu x O y nanoparticles of diameter 50 nm or smaller.

28. The photovoltaic device of claim 24 wherein the active layer further comprises photoactive material selected from the group consisting of: a dye; silicon, cadmium telluride, cadmium sulfide, cadmium selenide, copper indium gallium selenide, gallium arsenide, germanium indium phosphide, semiconducting polymers, and combinations thereof.

29. The photovoltaic device of claim 28 wherein the photoactive material comprises a dye comprising:

a primary electron donor moiety comprising at least one substituent selected from the group consisting of: aryl amine; aryl phosphine; aryl arsine; aryl stibine; aryl sulfide; aryl selenide; phenyl; phenol; alkoxy phenyl; dialkoxy phenyl; alkyl phenyl; and combinations thereof;

a core moiety comprising at least one aryl substituent selected from the group consisting of: a nitrogen heterocyclic compound; benzothiophene; dibenzothiophene; naphthothiophene; dinaphthothiophene; benzonaphthothiophene; naphthyl; benzothiazole; benzothiadiazole; benzo[b]naphtha[2,3-d]thiophene; 4H-cyclopenta[1,2-b:5,4-b′]bisthiophene; dinaphtho[2,3-d]thiophene; thieno[3,2-b]thiophene; naphthalene; anthracene; and combinations thereof;

a second electron donor moiety comprising at least one pi-electron donor substituent selected from the group consisting of: thiophene, benzothiadiazole, benzene, benzothiophene, thienothiophene, and combinations thereof; and

an electron-withdrawing moiety comprising at least one substituent selected from the group consisting of: a carboxylic acid; a monocyanocomplex; a dicyanocomplex; a thiocyanocomplex; an isothiocyanocomplex, and combinations thereof.

30. The photovoltaic device of claim 28 wherein the active layer further comprises an interfacial layer disposed between the perovskite material and the photoactive material; the interfacial layer comprising a compound selected from the group consisting of: Al; Bi; In; Mo; Ni; Pt; Si; Ti; V; Nb; zinc; oxides of any of the foregoing metals; a sulfide of any of the foregoing metals; a nitride of any of the foregoing metals; alkyl silyl groups; graphite; graphene; fullerenes; carbon nanotubes; and combinations thereof.

Assignments (5)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 15, 2021
From: CUBIC PEROVSKITE LLC
To: CUBICPV INC.
Reel/Frame 058517/0919 →
CHANGE OF NAME Recorded Aug 1, 2021
From: HUNT PEROVSKITE TECHNOLOGIES, L.L.C.
To: CUBIC PEROVSKITE LLC
Reel/Frame 057047/0232 →
CHANGE OF NAME Recorded Apr 13, 2020
From: HEE SOLAR, L.L.C.
To: HUNT PEROVSKITE TECHNOLOGIES, L.L.C.
Reel/Frame 052385/0490 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 2, 2017
From: HUNT ENERGY ENTERPRISES, L.L.C.
To: HEE SOLAR, L.L.C.
Reel/Frame 043174/0690 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 1, 2014
From: IRWIN, MICHAEL D.; MAHER, ROBERT D., III; CHUTE, JERRED A.; DHAS, VIVEK V.
To: HUNT ENERGY ENTERPRISES, L.L.C.
Reel/Frame 033441/0449 →
Continuity (3)
Provisional Application 61909168 · Nov 26, 2013
Provisional Application 61913665 · Dec 9, 2013
Related Publication 20150144195A1 · May 28, 2015