PHOTOVOLTAIC DEVICES FABRICATED BY GROWTH FROM POROUS TEMPLATE

• US 20050121068A1
• Filed: 05/21/2003
• Published: 06/09/2005
• Est. Priority Date: 06/22/2002
• Status: Active Grant

• Current Assignee: Aeris Capital Sustainable IP, Ltd.
• Original Assignee: Nanosolar Incorporated
• Inventors: Petritsch, Klus, Yu, Dong, Pichler, Karl, Roscheisen, Martin R., Sager, Brian M., Fidanza, Jacqueline
• Granted Patent: US 6,946,597 B2
• Time in Patent Office: Days
• US Class Current: 136/252
• CPC Class Codes: H10K 30/10 comprising heterojunctions between organic semiconductors and inorganic semiconductors
• CPC Class Codes: H10K 30/15 Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 photo-electrochemical devices comprising a liquid electrolyte or a solid electrolyte H01G9/20
• CPC Class Codes: H10K 30/30 comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
• CPC Class Codes: H10K 30/50 Photovoltaic [PV] devices
• CPC Class Codes: H10K 30/87 Light-trapping means
• CPC Class Codes: H10K 85/113 Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
• CPC Class Codes: H10K 85/1135 Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
• 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

Photovoltaic devices, such as solar cells, and methods for their manufacture are disclosed. A device may be characterized by an architecture where two more materials having different electron affinities are regularly arrayed such that their presence alternates within distances of between about 1 nm and about 100 nm. The materials are present in a matrix based on a porous template with an array of template pores. The porous template is formed by anodizing a layer of metal. A photovoltaic device may include such a porous template disposed between a base electrode and a transparent conducting electrode. A first charge-transfer material fills the template pores, A second (complementary) charge-transfer material fills additional space not occupied by the first charge-transfer material.

Claims

1. A solar cell device, comprising two or more materials having different electron affinities, the solar cell device being characterized by an architecture

wherein the two materials are regularly arrayed and wherein the presence of the two or more materials alternates within distances of between about 1 nm and about 100 nm,

wherein the two materials are present in a matrix having a porous template with an array of template pores, wherein the porous template has been made by anodizing a layer of metal,

wherein one of the materials in the matrix is an organic material that can absorb light in the bulk of the organic material;

and

wherein the two or more materials are disposed between a base electrode and a transparent conducting electrode.

2. A photovoltaic device, comprising:

a porous template of anodized metal having an array of template pores;

a first charge-transfer material that substantially fills the template pores, a second charge transfer material that fills additional space not occupied by the first charge-transfer material, wherein the first charge-transfer material has complementary charge-transfer characteristics with respect to the porous template;

a base electrode; and

a transparent conducting electrode (TCE),

wherein the first and second charge-transfer materials are disposed between the base electrode and the TCE.

3. The device of claim 2 wherein at least one of the first and second charge-transfer materials is an organic material that can absorb light in the bulk of the organic material.

4. The device of claim 2 wherein the template pores are between about 2 nm and about 500 nm in diameter, or between about 40 nm and about 100 nm in diameter or between about 10 nm and about 30 nm in diameter.

5. The device of claim 2 wherein the template pores are spaced apart by an average distance of between about 10 nm to about 500 nm center-to-center, or between about 30 nm and about 50 nm center-to center.

6. The device of claim 2 wherein an average wall thickness between neighboring template pores is less than about 5 nm, or less than about 20 nm, or between about 5 nm and about 40 nm.

7. The device of claim 2 wherein the template pores are present in the porous template with a pore density between about 10¹² and about 3×

10¹⁵ pores per square meter.

8. The device of claim 2 wherein the template pores have an average wall thickness of between about 0.5 nm and about 20 nm.

9. The device of claim 2 wherein the porous template is made from the second charge transfer material.

10. The device of claim 9 wherein the template pores stop short of penetrating all the way through the porous template.

11. The device of claim 2 wherein the porous template has been formed by anodizing a layer of metal.

12. The device of claim 11 wherein the metal is aluminum or titanium, whereby the porous template is made of alumina or titania.

13. The device of claim 11 wherein the porous template is made of titania (TiO₂), silica (SiO₂), zinc oxide (ZnO₂), zirconium oxide, lanthanum oxide, niobium oxide, tungsten oxide, tin oxide, indium oxide, indium tin oxide (ITO), strontium oxide, vanadium oxide, molybdenum oxide, calcium/titanium oxide, or blends of two or more such materials.

14. The device of claim 2 wherein the first charge-transfer material includes, a metal, a transparent conductive oxide, indium tin oxide (ITO), fluorinated tin oxide (F:

SnO_x), a conductive oxide, TiO₂, an organic material, PEDOT, a doped fullerene, or doped C₆₀.

15. The device of claim 2 wherein at least one of the first and second charge-transfer materials includes a material chosen from the group of poly(phenylene) and derivatives thereof, poly(phenylene vinylene) and derivatives thereof, poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene (MEH-PPV), poly(para-phenylene vinylene) (PPV), PPV copolymers, poly(thiophene) and derivatives thereof, regioregular poly(3-octylthiophene-2,5,-diyl), regiorandom poly(3-octylthiophene-2,5,-diyl), poly(3-hexylthiophene) (P3HT), regioregular poly(3-hexylthiophene-2,5-diyl), regiorandom poly(3-hexylthiophene-2,5-diyl), poly(thienylenevinylene) and derivatives thereof, poly(isothianaphthene) and derivatives thereof, tetra-hydro-thiophene precursors and derivatives thereof, organometallic polymers, polymers containing perylene units, poly(squaraines) and their derivatives, discotic liquid crystals. polyfluorenes, polyfluorene copolymers, polyfluorene-based copolymers and blends, co-polymerized and/or blended with charge transporting and/or light-absorbing compounds, tri-phenyl-amines and derivatives, fused thiophene rings and derivatives, and hetero-atom ring compounds with or without substituents.

16. The device of claim 2, wherein at least one of the first and second charge-transfer materials is a pigment or dye chosen from the group of organic pigments or dyes, azo-dyes having azo chromofores (—

N═

N—

) linking aromatic groups, phthalocyanines including metal-free phthalocyanine (HPc), perylenes, naphthalocyanines, squaraines, merocyanines and their respective derivatives, poly(silanes), poly(germinates), 2,9-Di(pent-3-yl)-anthra[2,1,9-def;

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10-tetrone, and 2,9-Bis-(1-hexyl-hept-1-yl)-anthra[2,1,9-def;

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10-tetrone.

17. The device of claim 2 further comprising, an interfacial layer disposed between the first and second charge-transfer materials.

18. The device of claim 17 wherein the interfacial layer includes one or more materials chosen from the group of fullerenes, doped fullerenes, functionalized fullerenes, doped functionalized fullerenes, azafullerenes, polymerized fullerenes (doped or undoped), functionalized polymerized fullerenes (doped or undoped), carbon nanotubes, dyes, ruthenium dyes, pigments, organic monomers, oligomers, and polymers, tetra-hydro-thiophene precursor polymers and derivatives thereof, and poly-phenylene-vinylene and derivatives thereof, and conjugated polymers.

19. The device of claim 17 wherein the interfacial layer includes one or more chemicals that can covalently attach to the first charge-transfer material and change a surface energy of the first charge transfer material, one or more chemicals that can covalently attach to the first charge-transfer material and change bonding of the first charge transfer material, one or more chemicals that can covalently attach to the first charge-transfer material and change trap-states of the first charge transfer material one or more chemicals that can attach to dangling-bonds at an exposed surface of the first charge-transfer material, one or more chemicals that can introduce a dipole layer that may increase the efficiency for charge extraction, and/or one or more chemicals that can reduce detrimental charge recombination.

20. The device of claim 2 wherein a surface of the first charge-transfer material is functionalized with one or more silylating agents.

21. The device of claim 2 wherein the template pores have substantially cylindrical, cone, or truncated cone shapes.

22. The device of claim 2 wherein the porous template is between about 50 nm and about 1 micron thick.

23. The device of claim 22 wherein the porous template is between about 100 nm and about 200 nm thick or between about 200 nm and about 600 nm thick.

24. The device of claim 2 wherein the first charge-transfer material is in the form of one or more tubules disposed in the template pores, each tubule having a tubule pore.

25. The device of claim 24 wherein the second charge-transfer material fills the tubule pores.

26. The device of claim 24 wherein the tubule pores have an average diameter between about 1 nm and about 200 nm or between about 1 nm and about 100 nm, or between about 10 nm and about 50 nm, or between about 20 nm and about 40 nm or about 30 nm.

27. The device of claim 2 further comprising an intermediate layer disposed between the porous template and the base electrode.

28. The device of claim 2 further comprising an interfacial layer disposed between the porous template and the first charge-transfer material.

29. The device of claim 28, wherein the interfacial layer includes one or more conductive layers, one or more metal layers, nickel or oxides thereof or gold.

30. A method for making a photovoltaic device, comprising:

anodizing a layer of metal to form a porous template having an array of template pores;

filling the template pores with a first charge-transfer material that is complementary to the porous template.

31. The method of claim 30 wherein the template pores are between about 2 nm and about 500 nm in diameter, or between about 40 nm and about 100 nm in diameter or between about 10 nm and about 30 nm in diameter.

32. The method of claim 30 wherein the template pores are spaced apart by an average distance of between about 10 nm to about 500 nm center-to-center, or between about 30 nm and about 50 nm center-to center.

33. The method of claim 30 wherein an average wall thickness between neighboring pores is less than about 5 nm, or less than about 20 nm, or between about 5 nm and about 40 nm.

34. The method of claim 30 wherein the template pores are present in the porous template with a pore density between about 10¹² and about 3×

10¹⁵ pores per square meter.

35. The method of claim 30 wherein the first charge-transfer material is an organic material that can absorb light in the bulk of the organic material.

36. The method of claim 30 wherein the first charge-transfer material includes a material chosen from the group of poly(phenylene) and derivatives thereof, poly(phenylene vinylene) and derivatives thereof, poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene (MEH-PPV), poly(para-phenylene vinylene) (PPV), PPV copolymers, poly(thiophene) and derivatives thereof, regioregular poly(3-octylthiophene-2,5,-diyl), regiorandom poly(3-octylthiophene-2,5,-diyl), poly(3-hexylthiophene) (P3HT), regioregular Poly(3-hexylthiophene-2,5-diyl), regiorandom poly(3-hexylthiophene-2,5-diyl), poly(thienylenevinylene) and derivatives thereof, poly(isothianaphthene) and derivatives thereof, tetra-hydro-thiophene precursor polymers and derivatives thereof, organometallic polymers, polymers containing perylene units, poly(squaraines) and their derivatives, polyfluorene copolymers and discotic liquid crystals,

or a pigment or dye chosen from the group of organic pigments or dyes, azo-dyes having azo chromofores (—

N═

N—

) linking aromatic groups, phthalocyanines including metal-free phthalocyanine (HPc), perylenes, naphthalocyanines, squaraines, merocyanines and their respective derivatives, poly(silanes), poly(germinates), 2,9-Di(pent-3-yl)-anthra[2,1,9-def;

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10-tetrone, and 2,9-Bis-(1-hexyl-hept-1-yl)-anthra[2,1,9-def;

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10-tetrone.

37. The method of claim 30 wherein the porous template is between about 50 nm and about 1 micron thick.

38. The method of claim 30 wherein the porous template is between about 100 nm and about 200 nm thick or between about 200 nm and about 600 nm thick.

39. The method of claim 30 further comprising, disposing an interfacial layer between the porous template and the first charge-transfer material.

40. The method of claim 39 wherein the interfacial layer includes one or more materials chosen from the group of fullerenes, doped fullerenes, functionalized fullerenes, doped functionalized fullerenes, azafullerenes, polymerized fullerenes (doped or undoped), functionalized polymerized fullerenes (doped or undoped), carbon nanotubes, dyes, ruthenium dyes, pigments, organic monomers, oligomers and polymers tetra-hydro-thiophene precursor polymers and derivatives thereof, poly-phenylene-vinylene and derivatives thereof, or, if the interfacial layer is disposed between the porous template and the first charge-transfer material, conductive layers, metal layers, nickel or oxides thereof or gold.

41. The method of claim 30 wherein anodizing a layer of metal to form a porous template includes:

placing an aluminum, aluminum-coated, titanium or titanium-coated substrate in an electrolyte, and applying an anodizing voltage to the substrate to form an alumina or titania film.

42. The method of claim 30, further comprising and incrementally stepping down an anodizing voltage.

43. The method of claim 30, further comprising substantially removing a barrier between the template pores and an underlying layer.

44. The method of claim 30, further comprising widening the template pores.

45. The method of claim 30 wherein the template pores stop short of penetrating all the way through the porous template.

56. The method of claim 30 wherein filling additional space not occupied by the first charge-transfer material includes anodizing the metal layer to form the porous template such that the porous template is made of a material having complementary charge-transfer properties with respect to the first charge-transfer material, whereby the material of the porous template is the second charge-transfer material.

57. The method of claim 30 further comprising disposing an intermediate layer between the layer of metal and an underlying substrate.

58. The method of claim 57 wherein the intermediate layer is configured to act as an anodization-stop layer and/or act as an etch-stop layer.

60. The method of claim 30, further comprising:

filling additional space not occupied by the charge-transfer material with a second charge-transfer material that is complementary to the charge-transfer material.

46. A method for making a photovoltaic device, comprising:

anodizing a layer of metal to form a porous template having an array of template pores;

filling the template pores with a first charge-transfer material; and

filling additional space not occupied by the first charge-transfer material with a second charge-transfer material that is complementary to the first charge-transfer material,

wherein filling the template pores with a first charge-transfer material includes;

partly filling one or more of the template pores with the first charge-transfer material to form one or more tubules wherein the additional space is a tubule pore in each tubule.

47. The method of claim 46 wherein the tubule pores have an average wall thickness of between about 0.5 nm and about 20 nm.

48. The method of claim 46 wherein the tubule pores have an average diameter between about 1 nm and about 200 nm or between about 1 nm and about 100 nm, or between about 10 nm and about 50 nm, or between about 20 nm and about 40 nm or about 30 nm.

49. The method of claim 46 wherein the tubules are formed by depositing a sol-gel into the template pores, followed by air drying then heating.

50. The method of claim 49 further comprising adjusting a deposition temperature of the sol-gel and or a deposition time such that tubules form.

51. The method of claim 50, further comprising adjusting a chemical or physical property of the porous template such that tubules form.

52. The method of claim 46 wherein filling additional space not occupied by the first charge-transfer material includes:

filling the tubule pore of one or more of the tubules with the complementary charge-transfer material.

53. The method of claim 52, further comprising removing the porous template leaving behind structures made of the first and second charge-transfer materials with spaces between the structures.

54. A method for making a photovoltaic device, comprising:

anodizing a layer of metal to form a porous template having an array of template pores;

filling the template pores with a first charge-transfer material; and

filling additional space not occupied by the first charge-transfer material with a second charge-transfer material that is complementary to the first charge-transfer material, wherein filling the template pores with a first charge-transfer material includes completely filling the pores with the first charge-transfer material and removing the porous template leaving behind structures of the first charge-transfer material with spaces between the structures.

55. The method of claim 54 wherein filling additional space not occupied by the first charge-transfer material includes filling the spaces between the structures of the first charge-transfer material with the complementary charge-transfer material.

59. (canceled)