Hybrid solar cells with thermal deposited semiconductive oxide layer

• US 6,706,962 B2
• Filed: 11/21/2001
• Issued: 03/16/2004
• Est. Priority Date: 11/24/2000
• Status: Expired due to Fees

• Current Assignee: Sony Deutschland GmbH (Sony Group Corp.)
• Original Assignee: Sony International Europe Gmbh (Sony Group Corp.)
• Inventors: Schmitz, Christoph, Schmidt, Hans-Werner, Yasuda, Akio, Thelakkat, Mukundan, Nelles, Gabrielle
• Primary Examiner(s): DIAMOND, ALAN D
• Application Number:
  US09/989,848
• Publication Number:
  US 20020117201A1
• Time in Patent Office: 846 Days
• Field of Search: 136/263, 136/252, 136/256, 257/43, 257/431, 438/85, 438/98, 438/57
• US Class Current: 136/263
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H10K 2102/103 comprising indium oxides, e.g. ITO
• CPC Class Codes: H10K 30/151 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
• CPC Class Codes: H10K 30/50 Photovoltaic [PV] devices
• CPC Class Codes: H10K 71/164 using vacuum deposition
• CPC Class Codes: H10K 85/311 Phthalocyanine
• CPC Class Codes: H10K 85/621 Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Method for producing a hybrid organic solar cell having the general structure

Substrate+EM/HTM/dye/SOL/EM, or

Substrate+EM/SOL/dye/HTM/EM, or

Substrate+EM/HTM/SOL/EM, in which

EM is the electrode material that may be a transparent conductive oxide (TCO) or metal, with at least one of the EM layer(s) of the cell being a TCO,

HTM is the hole transport material,

SOL is a semiconducting oxide layer,

“dye” is a suitable dye, and the SOL layer is vapor deposited.

Claims

1. Method for the production of a hybrid organic solar cell comprising introducing the semiconducting oxide layer (SOL) by thermal evaporation.

2. Method according to claim 1, comprising deposition and/or vapor-deposition of a layer of lithium fluoride close to either one or both sides of an electrode material interface.

3. Method according to claim 2, wherein said layer of lithium fluoride has a thickness of between about 0.1 Å

to about 50 Å

.

4. Method according to claim 1, comprising increasing a number of surfaces of a number of interfaces of a number of layers by use of structured indium tin oxide, co-evaporation of hole transport material (HTM) and a dye and/or a dye/TiO₂ or co-evaporation of HTM and a dopant.

5. The method according to claim 1, characterised in that a substrate is selected from the group consisting of:

glass, coated glass, polymeric foils, norbornene-based foils, SnO₂-coated metal foils or stainless steal foils.

6. The method according to claim 1, comprising a flexible substrate.

7. The method according to claim 1, comprising an electrode material (EM) selected from the group consisting of indium tin oxide, fluorine doped tin oxide, zinc oxide, doped zinc oxide and metal, and combinations of metals, and Al/Li metal combination, and a Mg/Ag metal combination.

8. The method according to claim 1, comprising an indium tin oxide electrode material.

9. The method according to claim 1, comprising a hole transport material (HTM) selected from the group consisting of phthalocyanine and derivatives thereof with or without a central atom or group of atoms, metal-free and metal containing porphyrins and derivatives thereof, TPD derivatives, triphenylamine and its derivatives, thiophenes, polythiophenes and derivatives thereof, polyanilines and derivatives thereof and hexa-benzocoronene and its derivatives, triphenyldiamine derivatives, aromatic diamine compounds having connected tertiary aromatic amine units of 1,-bis(4-(di-p-tolylamino) phenyl)-cyclohexane, aromatic diamines containing two or more tertiary amines and having two or more fused aromatic rings substituted on the nitrogen atoms, aromatic trimers having a starburst structure derived from triphenylbenzene, aromatic diamines, triphenylamine derivatives whose molecule is sterically asymmetric as a whole, compounds having a plurality of aromatic diamino groups substituted on a pyrenyl group, aromatic diamines having tertiary amine units connected through an ethylene group, aromatic diamines having a styryl structure, starburst aromatic triamines, benzyl-phenyl compounds, compounds having tertiary amine units connected through a fluorene group, triamine compounds, bisdipyridylaminobiphenyl compounds, N,N,N-triphenylamine derivatives, aromatic diamines having a phenoxazine structure, diaminophenylanthridine, carbazole derivatives, hydrazoen compounds, silazane compounds, silanamine derivatives, phosphamine derivatives, quinacridone compounds, stilbene compounds, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivative, polysilane derivatives, and mixtures of two or more of the above compounds and polymers.

10. The method according to claim 1, comprising hole transport material (HTM), wherein said HTM is copper-phthalocyanine (CuPc).

11. The method according to claim 1, characterised in that SOL is selected from the group consisting of TiO2, SnO2, ZnO, Sb2O3, and PbO.

12. The method according to claim 1, characterised in that SOL is TiO2.

13. The method according to claim 1, characterised in that a dye is selected from the group consisting of di- or monosubstituted perylenes, perylene anhydride, perylene dianhydrides, perylene imides, perylene diimides, perylene imidazoles, perylene diimidazoles and derivatives thereof, terrylene, quinacridone, anthraquinone, red dyes, titanylphthalocyanine, porphines and porphyrines and derivatives thereof, polyfluorenes and derivatives thereof and azo-dyes.

14. The method according to claim 1, characterised in that a dye layer is deposited in a thickness of about 5 to about 65 nm and the SOL is deposited in a thickness of about 5 to about 50 nm.

15. The method according to claim 1, characterised in that said hybrid organic solar cell comprises more than one dye.

16. The method according to claim 1, characterised in that said hybrid organic cell comprises hole transport material that is doped.

17. The method according to claim 1, wherein the substrate is a polymeric foil selected from the group consisting of foils made from PET, PEN and PI.

18. The method according to claim 1, comprising an electrode material selected from the group consisting of Au, Al, Ca, and Mg.

19. The method according to claim 1, comprising hole transport material selected from the group consisting of TDATAs, TTABs, TDABs, N-carbazoles and derivatives of N-carbazoles.

20. The method according to claim 1, comprising a hole transport material selected from the group consisting of aromatic diamines containing two or more tertiary amines and having two or more fused aromatic rings substituted on the nitrogen atoms, wherein said aromatic rings are 4,4-bis[(N-1-naphthyl)-N-phenylamino]-biphenyl.

21. The method according to claim 1, comprising hole transport material selected from the group consisting of N,N′

-diphenyl-N,N′

-bis(3-methyphenyl)-(1,1′

-biphenyl)-4,4′

diamine, and α

,α

, α

′

,α

′

-tetramethyl-α

,α

′

-bis(4-di-p-tolylaminophenyl)-p-xylene.

22. The method according to claim 1, comprising hole transport material selected from the group consisting of 4-di-p-tolylamino-stilbene and 4-(di-p-tolylamino)-4′

-[4-di-p-tolylamino)-styryl]stilbene.

23. The method according to claim 1, comprising hole transport material selected from the group consisting of polyvinyl carbazole and polysilanes, polyphosphazenes, polyamides, polyvinyl triphenylamine, polymers having a triphenylamine skeleton, polymers having triphenylamine units connected through a methylene group and polymethacrylates containing aromatic amine.

24. The method according to claim 1, comprising hole transport material having an average molecular weight of at least 1000.

25. The method according to claim 1, comprising hole transport material having an average molecular weight of at least 5000.

26. Method for the production of a hybrid organic solar cell having the general structure Substrate+EM/HTM/dye/SOL/EM, or Substrate+EM/SOL/dye/HTM/EM, or Substrate+EM/HTM/SOL/EM, wherein EM is the electrode material, selected from the group consisting of a transparent conductive oxide (TCO) and metal, with at least one of the EM layer(s) of the cell being a TCO, HTM is the hole transport material, SOL is a semiconducting oxide layer, and dye is a suited dye, comprising physical vapor-deposition of the SOL of the hybrid organic solar cell.

27. Method for the production of a hybrid organic solar cell according to claim 26, comprising vapor-deposition of at least one other layer of the hybrid organic solar cell in addition to the SOL layer.

28. The method according to claim 26, comprising deposition and/or vapor-deposition of a layer of lithium fluoride close to the EM interfaces either on one side or both sides.

29. The method according to claim 26, comprising increasing the surfaces of the interfaces of the layers by use of structured ITO, co-evaporation of HTM and dye and/or dye/TiO₂ or co-evaporation of HTM and a dopant.

30. The method according to claim 26, characterised in that the substrate is selected from the group consisting of glass, coated glass, polymeric foils, SnO₂-coated metal foils and stainless steel foils.

31. The method according to claim 26, characterised in that the substrate is flexible.

32. The method according to claim 26, characterised in that EM is selected from the group consisting of indium tin oxide, fluorine doped tin oxide, zinc oxide, doped zinc oxide, metal, combinations of metals, an AL/Li metal combination, and a Mg/Ag metal combination.

33. The method according to claim 26 characterised in that EM is indium tin oxide.

34. The method according to claim 26, characterised in that HTM is selected from the group consisting of phthalocyanine and derivatives thereof (with or without a central atom or group of atoms), metal-free and metal containing porphyrins and derivatives thereof, TPD derivatives, triphenylamine and its derivatives, thiophenes, polythiophenes and derivatives thereof, polyanilines and derivatives thereof and hexa-benzocoronene and its derivatives, triphenyldiamine derivatives, aromatic diamine compounds having connected tertiary aromatic amine units of 1,-bis(4-(di-p-tolylamino)phenyl)-cyclohexane, aromatic diamines containing two or more tertiary amines and having two or more fused aromatic rings substituted on the nitrogen atoms, aromatic trimers having a starburst structure derived from triphenylbenzene, aromatic diamines, triphenylamine derivatives whose molecule is sterically asymmetric as a whole, compounds having a plurality of aromatic diamino groups substituted on a pyrenyl group, aromatic diamines having tertiary amine units connected through an ethylene group, aromatic diamines having a styryl structure, starburst aromatic triamines, benzyl-phenyl compounds, compounds having tertiary amine units connected through a fluorene group, triamine compounds, bisdipyridylaminobiphenyl compounds, N,N,N-triphenylamine derivatives, aromatic diamines having a phenoxazine structure, diaminophenylanthridine, carbazole derivatives, hydrazoen compounds, silazane compounds, silanamine derivatives, phosphamine derivatives, quinacridone compounds, stilbene compounds, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivative;

polysilane derivatives, and mixtures of two or more of the above compounds and polymers.

35. The method according to claim 26, characterised in that HTM is copper-phthalocyanine (CuPc).

36. The method according to claim 26, characterised in that SOL is selected from the group consisting of TiO₂, SnO₂, ZnO, Sb₂O₃, and PbO.

37. The method according to claim 26, characterised in that SOL is TiO₂.

38. The method according to claim 26, characterised in that the dye is selected from the group consisting of di- or monosubstituted perylenes, perylene anhydride, perylene dianhydrides, perylene imides, perylene diimides, perylene imidazoles, perylene diimidazoles and derivatives thereof, terrylene, quinacridone, anthraquinone, red dyes, titanylphthaloeyanine, porphines and porphyrines and derivatives thereof, polyfluorenes and derivatives thereof and azo-dyes.

39. The method according to claim 26, characterised in that the dye layer is deposited in a thickness of about 5 to about 65 nm and the SOL is deposited in a thickness of about 5 to about 50 nm.

40. The method according to claim 26, characterised in that more than one dye is used in one cell.

41. The method according to claim 36 characterised in that the substance of the HTM is doped.

42. The method according to claim 26, characterised in that the substrate is a polymeric foil selected from the group consisting of foils made from PET, PEN and PI.

43. The method according to claim 26, comprising an electrode material selected from the group consisting of Au, Al, Ca, and Mg.

44. The method according to claim 26, comprising hole transport material selected from the group consisting of TDATAs, TTABs, TDABs, N-carbazoles and its derivatives of N-carbazoles.

45. The method according to claim 26, comprising hole transport material selected from the group consisting of aromatic diamines containing two or more tertiary amines and having two or more fused aromatic rings substituted on the nitrogen atoms, wherein said aromatic rings are 4,4-bis[(N-1-naphthyl)-N-phenylamino]-biphenyl.

46. The method according to claim 26, comprising hole transport material selected from the group consisting of N,N′

-diphenyl-N,N′

-bis(3-methyphenyl)-(1,1′

-biphenyl)-4,4′

diamine, and α

, α

, α

′

, α

′

, -tetramethyl-α

, α

′

-bis(4-di-p-tolylaminophenyl)-p-xylene.

47. The method according to claim 26, comprising hole transport material selected from the group consisting of 4-di-p-tolylamino-stilbene and 4-(di-p-tolylamino)-4′

-[4-di-p-tolylamino)-styryl]stilbene.

48. The method according to claim 26, comprising hole transport selected from the group consisting of polyvinyl carbazole and polysilanes, polyphosphazenes, polyamides, polyvinyl triphenylamine, polymers having a triphenylamine skeleton, polymers having triphenylamine units connected through a methylene group and polymethacrylates containing aromatic amine.

49. The method according to claim 26, comprising hole transport material having an average molecular weight of at least 1000.

50. The method according to claim 26, comprising hole transport material having an average molecular weight of at least 5000.

51. A method for improving the efficiency of an organic solar cell, comprising the step of providing thermally evaporated semiconductive oxide layers in the organic solar cell.