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WO2010059240A1 - Couches de modification interfaciale dopées pour l’amélioration de la stabilité de cellules solaires organiques à hétérojonction - Google Patents

Couches de modification interfaciale dopées pour l’amélioration de la stabilité de cellules solaires organiques à hétérojonction Download PDF

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Publication number
WO2010059240A1
WO2010059240A1 PCT/US2009/006236 US2009006236W WO2010059240A1 WO 2010059240 A1 WO2010059240 A1 WO 2010059240A1 US 2009006236 W US2009006236 W US 2009006236W WO 2010059240 A1 WO2010059240 A1 WO 2010059240A1
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Prior art keywords
active layer
anode
layer
interfacial modification
dopant
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PCT/US2009/006236
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English (en)
Inventor
Jessica Benson-Smith
Christopher T. Brown
Bal Mukund Dhar
Shijun Jia
Darin W. Laird
Christine L. Mcguiness
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Plextronics, Inc.
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Publication of WO2010059240A1 publication Critical patent/WO2010059240A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • OCV organic photovoltaic
  • Solar cell devices are described herein with particular importance being attributed to the compositions of an interfacial modification layer and an active layer, as well as methods of making and using same.
  • one embodiment provides a device comprising: at least one anode; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and one n-type material; at least one interfacial modification layer disposed on the active layer, wherein the interfacial modification layer comprises at least one dopant and at least one organic semiconductor; and at least one cathode disposed on the interfacial modification layer, wherein the dopant and the active layer are adapted to provide the device with a power conversion efficiency of at least 4 %.
  • Another embodiment provides a device comprising: at least one anode, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one interfacial modification layer disposed on the active layer, wherein the interfacial modification layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the interfacial modification layer.
  • Another embodiment provides a device comprising: at least one anode, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one ⁇ -ty ⁇ e material and at least one n-type material, at least one interfacial modification layer disposed on the active layer, wherein the interfacial modification layer comprises at least one dopant and at least one organic semiconductor, and at least one cathode disposed on the interfacial modification layer, wherein the dopant and the active layer are adapted to provide the device with a lifetime that is at least about 25% longer than an analogous device that does not contain the interfacial modification layer.
  • Another embodiment is a device comprising: at least one anode; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one interfacial modification layer disposed on the active layer, wherein the interfacial modification layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the interfacial modification layer, wherein the metal and the fullerene are adapted to provide the device with a power conversion efficiency of at least 4 %.
  • Other embodiments comprise methods of making and using these embodiments, as well as compositions and substructures of these embodiments, including coated substrates, for example.
  • Other embodiments include modules which are devices comprising solar cell or organic photovoltaic devices. The modules can generate electrical power and currents.
  • Additional embodiments include, for example: A device comprising: at least one substrate; at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and one n-type material; at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one dopant and at least one organic semiconductor; and at least one cathode disposed on the optical spacer layer, wherein the dopant and the active layer are adapted to provide the device with a power conversion efficiency of at least 4 %.
  • the interfacial modification layer can be in many embodiments also an optical spacer layer.
  • the substrate is transparent.
  • the anode comprises a transparent conductor.
  • the anode comprises a transparent conductive metal-metal oxide.
  • the anode comprises indium tin oxide, SnO, ZnO, or NiO( X) TiO 2 .
  • the device further comprises a hole transport layer between the anode and the active layer.
  • the hole transport layer comprises a semi -conducting organic polymer.
  • the semi-conducting organic polymer comprises PEDOT:PSS, regioregular polythiophene, 3-,4-alkoxysubstituted polythiophene, sulfonated polythiophene, arylaminobenzene materials, polyarylaminoketones, or combination thereof.
  • the p-type material comprises poly (3-hexylthiophene-2,5-diyl) (P3HT), polyphenylene vinyl ene (PPV), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures thereof.
  • the n-type material is selected from the group consisting of [6,6]- phenyl-C ⁇ i -butyric acid methyl ester (PCBM) and indenyl-substituted fullerenes.
  • the p-type material comprises P3HT and the n-type material is selected from the group consisting of PCBM and indenyl-substituted fullerenes.
  • the p-type material and n-type material of the active layer are present in a ratio of from about 1 n-type to about 1 to about 2 p-type, based on weight.
  • the dopant comprises a metal.
  • the dopant is selected from the group consisting of alkali metals, alkali earth metals, transition metals, rare earth metals, and metal oxides. In one embodiment, the dopant is selected from the group consisting of cesium, barium, magnesium, molybdenum oxide, tungsten oxide, chromium, silver, gold, lithium, calcium, and ytterbium. In one embodiment, the dopant comprises an organic material. In one embodiment, the dopant is selected from the group consisting of TTF, Pyronin B, BEDT-TTF, and cobaltocene.
  • the organic semiconductor is selected from the group consisting of Bathophenanthroline(4,7-Diphenyl-l,10- phenanthroline) ("BPhen”), 2,9-dimethyl-4,7-diphenyl-l,10-phenantrolene ("BCP”), Tris-(8- hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9-yl)-biphenyl (“CBP”), Bis-(2-methyl- 8-quinolinolato)-4-(phenylphenolato)-aluminum-(III) (“BAIq”), TPBI, 4,4',4"-Tris(carbazol-9- yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4-biphenylyl)-l,3,4-oxadiazole (“PBD”), 2,2'-(l,3- Phenylene)bis[5-[4-(l,
  • the optical spacer layer comprises ytterbium and BPhen. In one embodiment, the optical spacer layer comprises about 5 wt.% to about 30 wt. % dopant. In one embodiment, the optical spacer layer is about 1 nm to about 30 ran thick. In one embodiment, the active layer is about 150 nm to about 250 nm thick. In one embodiment, the cathode comprises aluminum. In one embodiment, the device further comprising a hole transport layer, and wherein the substrate is transparent, the anode comprises indium tin oxide, the active layer comprises P3HT and indenyl-derivitized fullerene, the optical spacer comprises BPhen and ytterbium, and the cathode comprises aluminum.
  • Another embodiment provides a device comprising: at least one substrate, at least one anode disposed on the substrate, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer.
  • the substrate is transparent.
  • the anode comprises a transparent conductor.
  • the anode comprises a transparent conductive metal-metal oxide.
  • the anode comprises indium tin oxide, SnO, ZnO, or NiO (X ) TiO 2 .
  • the device further comprises a hole transport layer between the anode and the active layer.
  • the hole transport layer comprises a semi-conducting organic polymer.
  • the semi-conducting organic polymer comprises PEDOT:PSS, regioregular polythiophene, 3-,4-alkoxysubstituted polythiophene, sulfonated polythiophene, arylaminobenzene materials, polyarylaminoketones, or combination thereof.
  • the conjugated polymer comprises poly (3-hexylthiophene-2,5- diyl) (P3HT), polyphenylene vinylene (PPV), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures thereof.
  • the fullerene is selected from the group consisting of [6,6]-phenyl-C 6 i-butyric acid methyl ester (PCBM) and indenyl-substituted fullerenes.
  • the conjugated polymer comprises P3HT and the fullerene is selected from the group consisting of PCBM and indenyl-substituted fullerenes.
  • the conjugated polymer and fullerene are present in a ratio of from about 1 conjugated polymer to about 1 to about 2 fullerenes, based on weight.
  • the optical spacer layer metal comprises ytterbium.
  • the organic semiconductor is selected from the group consisting of Bathophenanthroline(4,7-Diphenyl-l,10-phenanthroline) ("BPhen”), 2,9- dimethyl-4,7-diphenyl-l , 10-phenantrolene ("BCP”), Tris-(8-hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9-yl)-bi ⁇ henyl (“CBP”), Bis-(2-methyl-8-quinolinolato)-4- (phenylphenolato)-aluminum-(III) (“BAIq”), TPBI, 4,4',4"-Tris(carbazol-9-yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4-biphenylyl)-l,3,4-oxadiazole (“PBD”), 2,2'-(l,3-Phenylene)bis[5-[4- (l,l-di
  • the optical spacer layer comprises ytterbium and BPhen. In one embodiment, the optical spacer layer comprises about 5 wt.% to about 30 wt. % metal.
  • the optical spacer layer is about 1 nm to about 30 nm thick. In one embodiment, the active layer is about 150 nm to about 250 nm thick. In one embodiment, the cathode comprises aluminum. In one embodiment, the device further comprises a hole transport layer, wherein the substrate is transparent, the anode comprises indium tin oxide, the active layer comprises P3HT and indenyl- substituted fullerene, the optical spacer comprises BPhen and ytterbium, and the cathode comprises aluminum. In one embodiment, the optical spacer layer organic semiconductor has a HOMO value lower in energy than the HOMO value of the active layer conjugated polymer.
  • Another embodiment provides a device comprising: at least one substrate, at least one anode disposed on the substrate, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and at least one n-type material, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one dopant and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the dopant and the active layer are adapted to provide the device with a lifetime that is at least about 25% longer than an analogous device that does not contain the optical spacer.
  • the substrate is transparent.
  • the anode comprises a transparent conductor.
  • the anode comprises a transparent conductive metal-metal oxide.
  • the anode comprises indium tin oxide, SnO, ZnO, or NiO( X ) TiO 2 .
  • the device further comprises a hole transport layer between the anode and the active layer.
  • the hole transport layer comprises a semi-conducting organic polymer.
  • the semi-conducting organic polymer comprises PEDOT:PSS, regioregular polythiophene, 3-,4-alkoxysubstituted polythiophene, sulfonated polythiophene, arylaminobenzene materials, polyarylaminoketones, or combination thereof.
  • the p-type material comprises poly (3-hexylthiophene-2,5-diyl) (P3HT), polyphenylene vinylene (PPV), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures thereof.
  • the n-type material is selected from the group consisting of [6,6]- phenyl-C ⁇ i -butyric acid methyl ester (PCBM) and indenyl-substituted fullerenes.
  • the p-type material comprises P3HT and the n-type material is selected from the group consisting of PCBM and indenyl-substituted fullerenes.
  • the p-type material and n-type material of the active layer are present in a ratio of from about 1 n-type to about 1 to about 2 p-type, based on weight.
  • the dopant comprises a metal.
  • the dopant is selected from the group consisting of alkali metals, alkali earth metals, transition metals, rare earth metals, and metal oxides. In one embodiment, the dopant is selected from the group consisting of cesium, barium, magnesium, molybdenum oxide, tungsten oxide, chromium, silver, gold, lithium, calcium, and ytterbium. In one embodiment, the dopant comprises an organic material. In one embodiment, the dopant is selected from the group consisting of TTF, Pyronin B, BEDT-TTF, and cobaltocene.
  • the organic semiconductor is selected from the group consisting of Bathophenanthroline(4,7-Diphenyl- 1 , 10-phenanthroline) ("BPhen”), 2,9-dimethyl-4,7-diphenyl- 1,10-phenantrolene ("BCP”), Tris-(8-hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9- yl)-biphenyl (“CBP”), Bis-(2-methyl-8-quinolinolato)-4-(phenylphenolato)-aluminum-(III) (“BAIq”), TPBI, 4,4 1 ,4"-Tris(carbazol-9-yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4- biphenylyl)-l,3,4-oxadiazole (“PBD”), 2,2'-(l,3-Phenylene)bis[5-[4-(l,l- dimethyl
  • the optical spacer layer comprises ytterbium and BPhen. In one embodiment, the optical spacer layer comprises about 5 wt.% to about 30 wt. % dopant. In one embodiment, the optical spacer layer is about 1 nm to about 30 nm thick. In one embodiment, the active layer is about 150 nm to about 250 nm thick. In one embodiment, the cathode comprises aluminum. In one embodiment, the device further comprises a hole transport layer, wherein the substrate is transparent, the anode comprises indium tin oxide, the active layer comprises P3HT and indenyl- substituted fullerene, the optical spacer comprises BPhen and ytterbium, and the cathode comprises aluminum.
  • Another embodiment provides a device comprising: at least one substrate, at least one anode disposed on the substrate, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the metal and the fullerene are adapted to provide the device with a lifetime that is at least about 25% longer than an analogous device that does not contain the optical spacer.
  • the substrate is transparent.
  • the anode comprises a transparent conductor.
  • the anode comprises a transparent conductive metal-metal oxide.
  • the anode comprises indium tin oxide, SnO, ZnO, or NiO( X ) TiO 2 .
  • the device further comprises a hole transport layer between the anode and the active layer.
  • the hole transport layer comprises a semi-conducting organic polymer.
  • the semi-conducting organic polymer comprises PEDOT:PSS, regioregular polythiophene, 3-,4-alkoxysubstituted polythiophene, sulfonated polythiophene, arylaminobenzene materials, polyarylaminoketones, or combination thereof.
  • the conjugated polymer comprises poly (3-hexylthiophene-2,5- diyl) (P3HT), polyphenylene vinyl ene (PPV), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures thereof.
  • the fullerene is selected from the group consisting of [6,6]-phenyl-C6i -butyric acid methyl ester (PCBM) and indenyl-substituted fullerenes.
  • the conjugated polymer comprises P3HT and the fullerene is selected from the group consisting of PCBM and indenyl-substituted fullerenes.
  • the conjugated polymer and fullerene are present in a ratio of from about 1 conjugated polymer to about 1 to about 2 fullerenes, based on weight.
  • the optical spacer layer metal comprises ytterbium.
  • the organic semiconductor is selected from the group consisting of Bathophenanthroline(4,7-Diphenyl-l,10-phenanthroline) ("BPhen”), 2,9- dimethyl-4,7-diphenyl- 1 , 10-phenantrolene ("BCP”), Tris-(8-hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9-yl)-biphenyl (“CBP”), Bis-(2-methyl-8-quinolinolato)-4- (phenylphenolato)-aluminum-(III) (“BAIq”), TPBI, 4,4',4"-Tris(carbazol-9-yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4-biphenylyl)-l,3,4-oxadiazole (“PBD”), 2,2'-(l,3-Phenylene)bis[5-[4- (l,l-dimethyl
  • the optical spacer layer comprises ytterbium and BPhen. In one embodiment, the optical spacer layer comprises about 5 wt.% to about 30 wt. % metal. In one embodiment, the optical spacer layer is about 1 nm to about 30 nm thick. In one embodiment, the active layer is about 150 nm to about 250 nm thick. In one embodiment, the cathode comprises aluminum. In one embodiment, the device further comprises a hole transport layer, wherein the substrate is transparent, the anode comprises indium tin oxide, the active layer comprises P3HT and indenyl- substituted fullerene, the optical spacer comprises BPhen and ytterbium, and the cathode comprises aluminum. In one embodiment, the optical spacer layer organic semiconductor has a HOMO value lower in energy than the HOMO value of the active layer conjugated polymer.
  • Another embodiment provides a device comprising: at least one substrate; at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and one n-type material; at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one dopant and at least one organic semiconductor; and at least one cathode disposed on the optical spacer layer, wherein the dopant and the active layer are adapted to provide the device with a normalized power output greater that about 80% of initial power for at least about 25 hours.
  • the substrate is transparent.
  • the anode comprises a transparent conductor.
  • the anode comprises a transparent conductive metal-metal oxide.
  • the anode comprises indium tin oxide, SnO, ZnO, or NiO (X ) TiO 2 .
  • the device further comprises a hole transport layer between the anode and the active layer.
  • the hole transport layer comprises a semi-conducting organic polymer.
  • the semi-conducting organic polymer comprises PEDOT:PSS, regioregular polythiophene, 3-,4-alkoxysubstituted polythiophene, sulfonated polythiophene, arylaminobenzene materials, polyarylaminoketones, or combination thereof.
  • the p-type material comprises poly (3-hexylthiophene-2,5-diyl) (P3HT), polyphenylene vinylene (PPV), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures thereof.
  • the n-type material is selected from the group consisting of [6,6]- phenyl-C ⁇ i -butyric acid methyl ester (PCBM) and indenyl-substituted fullerenes.
  • the p-type material comprises P3HT and the n-type material is selected from the group consisting of PCBM and indenyl-substituted fullerenes.
  • the p-type material and n-type material of the active layer are present in a ratio of from about 1 n-type to about 1 to about 2 p-type, based on weight.
  • the dopant comprises a metal.
  • the dopant is selected from the group consisting of alkali metals, alkali earth metals, transition metals, rare earth metals, and metal oxides. In one embodiment, the dopant is selected from the group consisting of cesium, barium, magnesium, molybdenum oxide, tungsten oxide, chromium, silver, gold, lithium, calcium, and ytterbium. In one embodiment, the dopant comprises an organic material. In one embodiment, the dopant is selected from the group consisting of TTF, Pyronin B, BEDT-TTF, and cobaltocene.
  • the organic semiconductor is selected from the group consisting of Bathophenanthroline(4,7-Diphenyl-l,10- phenanthroline) ("BPhen”), 2,9-dimethyl-4,7-diphenyl-l,10-phenantrolene ("BCP”), Tris-(8- hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9-yl)-biphenyl (“CBP”), Bis-(2-methyl- 8-quinolinolato)-4-(phenylphenolato)-aluminum-(III) (“BAIq”), TPBI, 4,4',4"-Tris(carbazol-9- yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4-biphenylyl)-l,3,4-oxadiazole (“PBD”), 2,2'-(l,3- Phenylene)bis[5-[4-(l,
  • the optical spacer layer comprises ytterbium and BPhen. In one embodiment, the optical spacer layer comprises about 5 wt.% to about 30 wt. % dopant. In one embodiment, the optical spacer layer is about 1 run to about 30 ran thick. In one embodiment, the active layer is about 150 run to about 250 run thick. In one embodiment, the cathode comprises aluminum. In one embodiment, the device further comprises a hole transport layer, wherein the substrate is transparent, the anode comprises indium tin oxide, the active layer comprises P3HT and indenyl-substituted fullerene, the optical spacer comprises BPhen and ytterbium, and the cathode comprises aluminum.
  • Another embodiment provides a device comprising: at least one substrate, at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the metal and the fullerene are adapted to provide the device with a power conversion efficiency of at least 4 %.
  • the substrate is transparent.
  • the anode comprises a transparent conductor.
  • the anode comprises a transparent conductive metal-metal oxide.
  • the anode comprises indium tin oxide, SnO, ZnO, or NiO (X ) TiO 2 .
  • the device further comprises a hole transport layer between the anode and the active layer.
  • the hole transport layer comprises a semi-conducting organic polymer.
  • the semi-conducting organic polymer comprises PEDOTPSS, regioregular polythiophene, 3-,4-alkoxysubstituted polythiophene, sulfonated polythiophene, arylaminobenzene materials, polyarylaminoketones, or combination thereof.
  • the conjugated polymer comprises poly (3-hexylthiophene-2,5- diyl) (P3HT), polyphenylene vinylene (PPV), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures thereof.
  • the fullerene is selected from the group consisting of [6,6]-phenyl-C 6 i-butyric acid methyl ester (PCBM) and indenyl-substituted fullerenes.
  • the conjugated polymer comprises P3HT and the fullerene is selected from the group consisting of PCBM and indenyl-substituted fullerenes.
  • the conjugated polymer and fullerene are present in a ratio of from about 1 conjugated polymer to about 1 to about 2 fullerenes, based on weight.
  • the optical spacer layer metal comprises ytterbium.
  • the organic semiconductor is selected from the group consisting of Bathophenanthroline(4,7-Diphenyl- 1 ,10-phenanthroline) ("BPhen”), 2,9- dimethyl-4,7-diphenyl- 1 , 10-phenantrolene ("BCP”), Tris-(8-hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9-yl)-biphenyl (“CBP”), Bis-(2-methyl-8-quinolinolato)-4- (phenylphenolato)-aluminum-(III) (“BAIq”), TPBI, 4,4',4"-Tris(carbazol-9-yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4-biphenylyl)-l,3,4-oxadiazole (“PBD”), 2,2'-(l,3-Phenylene)bis[5-[4- (l,l-di
  • the optical spacer layer comprises ytterbium and BPhen. In one embodiment, the optical spacer layer comprises about 5 wt.% to about 30 wt. % metal. In one embodiment, the optical spacer layer is about 1 run to about 30 nm thick. In one embodiment, the active layer is about 150 nm to about 250 nm thick. In one embodiment, the cathode comprises aluminum. In one embodiment, the device further comprises a hole transport layer, wherein the substrate is transparent, the anode comprises indium tin oxide, the active layer comprises P3HT and indenyl- substituted fullerene, the optical spacer comprises BPhen and ytterbium, and the cathode comprises aluminum. In one embodiment, the optical spacer layer organic semiconductor has a HOMO value lower in energy than the HOMO value of the active layer conjugated polymer.
  • Another embodiment provides a device comprising: at least one substrate, at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the metal and the fullerene are adapted to provide the device with a normalized power output greater that about 80% of initial power for at least about 25 hours.
  • the substrate is transparent.
  • the anode comprises a transparent conductor.
  • the anode comprises a transparent conductive metal-metal oxide.
  • the anode comprises indium tin oxide, SnO, ZnO, or NiO(X) TiO 2 .
  • the device further comprises a hole transport layer between the anode and the active layer.
  • the hole transport layer comprises a semi-conducting organic polymer.
  • the semi-conducting organic polymer comprises PEDOT:PSS, regioregular polythiophene, 3-,4-alkoxysubstituted polythiophene, sulfonated polythiophene, arylaminobenzene materials, polyarylaminoketones, or combination thereof.
  • the conjugated polymer comprises poly (3-hexylthiophene-2,5-diyl) (P3HT), polyphenylene vinylene (PPV), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures thereof.
  • P3HT poly (3-hexylthiophene-2,5-diyl)
  • PV polyphenylene vinylene
  • substituted polythiophenes substituted polycarbazoles
  • copolymer comprising at least one dithieno[3,2-b:2',3'-d]pyrrole (DTP) repeat unit
  • DTP dithieno[3,2-b:2',3'-d]pyrrole
  • the fullerene is selected from the group consisting of [6,6]-phenyl-C 6 i-butyric acid methyl ester (PCBM) and indenyl-substituted fullerenes.
  • the conjugated polymer comprises P3HT and the fullerene is selected from the group consisting of PCBM and indenyl- substituted fullerenes.
  • the conjugated polymer and fullerene are present in a ratio of from about 1 conjugated polymer to about 1 to about 2 fullerenes, based on weight.
  • the optical spacer layer metal comprises ytterbium.
  • the organic semiconductor is selected from the group consisting of Bathophenanthroline(4,7- Diphenyl- 1 , 10-phenanthroline) ("BPhen”), 2,9-dimethyl-4,7-diphenyl- 1 , 10-phenantrolene ("BCP”), Tris-(8-hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9-yl)-biphenyl (“CBP”), Bis-(2-methyl-8-quinolinolato)-4-(phenylphenolato)-aluminum-(III) (“BAIq”), TPBI, 4,4',4"-Tris(carbazol-9-yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4-biphenylyl)-l,3,4- oxadiazole (“PBD”), 2,2'-(l,3-Phenylene)bis[5-[4-(l,l-di
  • the optical spacer layer comprises ytterbium and BPhen. In one embodiment, the optical spacer layer comprises about 5 wt.% to about 30 wt. % metal, hi one embodiment, the optical spacer layer is about 1 nm to about 30 nm thick. In one embodiment, the active layer is about 150 nm to about 250 nm thick. In one embodiment, the cathode comprises aluminum. In one embodiment, the device further comprises a hole transport layer, and wherein the substrate is transparent, the anode comprises indium tin oxide, the active layer comprises P3HT and indenyl-substituted fullerene, the optical spacer comprises BPhen and ytterbium, and the cathode comprises aluminum. In one embodiment, the optical spacer layer organic semiconductor has a HOMO value lower in energy than the HOMO value of the active layer conjugated polymer.
  • Another embodiment provides a method of using a device comprising: obtaining the device comprising: at least one substrate; at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and one n-type material; at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one dopant and at least one organic semiconductor; and at least one cathode disposed on the optical spacer layer, wherein the dopant and the active layer are adapted to provide the device with a power conversion efficiency of at least 4 %, and exposing the device to light.
  • Another embodiment provides a method of using a device comprising: obtaining the device comprising: at least one substrate, at least one anode disposed on the substrate, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, and exposing the device to light.
  • Another embodiment provides a method of using a device comprising: obtaining the device comprising: at least one substrate, at least one anode disposed on the substrate, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and at least one n-type material, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one dopant and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the dopant and the active layer are adapted to provide the device with a lifetime that is at least about 25% longer than an analogous device that does not contain the optical spacer, and exposing the device to light.
  • Another embodiment provides a method of using a device comprising: obtaining the device comprising: at least one substrate, at least one anode disposed on the substrate, at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the metal and the fullerene are adapted to provide the device with a lifetime that is at least about 25% longer than an analogous device that does not contain the optical spacer, and exposing the device to light.
  • Another embodiment provides a method of using a device comprising: obtaining the device comprising: at least one substrate; at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and one n-type material; at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one dopant and at least one organic semiconductor; and at least one cathode disposed on the optical spacer layer, wherein the dopant and the active layer are adapted to provide the device with a normalized power output greater that about 80% of initial power for at least about 25 hours, and exposing the device to light.
  • Another embodiment provides a method of using a device comprising: obtaining the device comprising: at least one substrate, at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the metal and the fullerene are adapted to provide the device with a power conversion efficiency of at least 4 %, and exposing the device to light.
  • Another embodiment provides a method of using a device comprising: obtaining the device comprising: at least one substrate, at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one conjugated polymer and at least one fullerene, wherein the fullerene comprises an indenyl-substituted fullerene, at least one optical spacer layer disposed on the active layer, wherein the optical spacer layer comprises at least one metal, which is an inner transition metal, and at least one organic semiconductor, and at least one cathode disposed on the optical spacer layer, wherein the metal and the fullerene are adapted to provide the device with a normalized power output greater that about 80% of initial power for at least about 25 hours, and exposing the device to light.
  • Another embodiment provides a device comprising: at least one substrate; at least one anode disposed on the substrate; at least one organic photovoltaic device active layer disposed on the anode, wherein the active layer comprises at least one p-type material and one n-type material; at least one spacer layer disposed on the active layer, wherein the spacer layer comprises at least one dopant and at least one organic semiconductor; and at least one cathode disposed on the layer, wherein the dopant and the active layer are adapted to provide the device with a power conversion efficiency of at least 4 %.
  • the devices described herein can be adapted to other OPV device structures including, for example, inverted solar cell devices.
  • At least one advantage is excellent efficiency including power conversion efficiency.
  • At least one advantage is excellent lifetime and stability, including testing under harsh humidity, temperature, and time conditions.
  • At least one advantage is excellent efficiency including power conversion efficiency combined with excellent lifetime and stability.
  • FIG. 1 shows a schematic of one embodiment of a solar cell device of the present application.
  • FIG. 2 shows device lifetime data for A) a solar cell device without an interfacial modification layer, and B) a solar cell device including an interfacial modification layer of the present application.
  • FIG. 3 shows structures of molecules that can be included in the interfacial modification layer of devices of the present application.
  • FIG. 4A shows burn-in data for OPV modules containing Li:BPhen, YbrBPhen, and Yb:TBPI in the OS and PV2000 in the active layer, evaluated under conditions of 85 °C/85% R.H. with 0.4
  • Sun Xe lamp intensity (“QSun) and ambient conditions with 1 Sun Xe lamp intensity.
  • FIG. 4B shows burn-in data for OPV modules containing Li:BPhen, Yb:BPhen, and Yb:TBPI in the OS and PVlOOO in the active layer, evaluated under conditions of 85 °C/85% R.H. with 0.4
  • Sun Xe lamp intensity (“QSun) and ambient conditions with 1 Sun Xe lamp intensity.
  • FIG. 5 shows burn-in data for OPV modules containing Ca and Li:BPhen in the OS and PVlOOO and PV2000 in the active layer, evaluated under conditions of 85 °C/85% R.H. with 0.4 Sun Xe lamp intensity ("QSun”) and ambient conditions with 1 Sun Xe lamp intensity.
  • QSun Sun Xe lamp intensity
  • FIG 6 A shows a TEM image of an OPV module active layer (with P3HT), Ca layer, and Al layer.
  • FIG 6B shows XPS depth profiles of the Al, Ca, and carbon layers of the module of Fig. 6A.
  • FIG 6C shows XPS depth profiles for various sulfur moieties in the active layer of the module of
  • FIG 7A shows a TEM image of an OPV module active layer (with P3HT), Yb:BPhen layer, and
  • FIG 7B shows XPS depth profiles of the Al, Yb:BPhen, and carbon layers of the module of
  • FIG 7C shows XPS depth profiles for various sulfur moieties in the active layer of the module of Fig. 7A.
  • FIG 8 shows the modules of Example 6. DETAILED DESCRIPTION
  • the present application has a variety of embodiments but generally relates to the use of an organic semiconductor doped with a metal or organic material to form an interfacial modification layer (IML).
  • the IML also could be called or function as an optical spacer ("OS") layer, where the IML or OS is disposed on an active layer including a p- type material and an n-type material.
  • An OS is an IML when the OS is at the interface.
  • an electron transport layer including an organic semiconductor, such as, for example, TPBI or 4,7-diphenyl-l,10-phenanthroline (“BPhen”) doped with a metal, e.g.
  • TPBI:Yb, or BPhen:Li, or BPhen:Yb etc. when disposed between the active layer and the cathode of a device, such as a bulk heterojunction solar cell or small molecule solar cell, can effectively increase the absorption in the active layer of the device, thereby improving device efficiency.
  • a device such as a bulk heterojunction solar cell or small molecule solar cell
  • the layer X When a layer X is disposed on an object such as another layer, the layer X can be directly contacting the object, or an intermediate material can be disposed between the layer X and the object.
  • OCVs Organic Photovoltaic Devices
  • a photovoltaic cell can be an electrochemical device that converts electromagnetic radiation to electrical energy.
  • OPVs also known as organic solar cells, are described in, for example, U.S. Provisional Patent Application No. 61/090,464 and U.S. Non-Provisional Patent Application No. 11/743,587 (Plextronics), both of which are hereby incorporated by reference in their entirety.
  • Various architectures for OPVs are known; elements typically include electrodes, e.g., an anode and a cathode, an active layer, and a substrate to support the larger structure. So- called inverted devices can be made.
  • an HTL, interfacial modification, or optical spacer layer, and one or more conditioning layers may also be used in an OPV.
  • FIG. 1 An example of a solar cell device is shown in Figure 1.
  • the value of such a device is that it may be used to directly convert solar radiation into usable energy without the generation of chemical waste products or a dependence on petroleum-or coal-based energy.
  • This "clean" and renewable energy can be used to charge batteries or operate electronic devices. It offers advantages to electrical applications which are electrically driven by an electrical distribution grid, either as a replacement for a battery or as means to restore the charge on a battery which is then used to power a device. Finally, it can be used to supplement power supply on the electrical distribution grid or to replace power supply from the electrical distribution grid.
  • Electrodes including anodes and cathodes, are known in the art for photovoltaic devices, and known electrode materials can be used to fabricate electrodes in embodiments of the present application.
  • transparent conductive oxide, metal-metal oxide, sulfide material, metal, and combinations of metals can be used. Transparency can be adapted for a particular application.
  • the anode may commonly comprise metals, such as, for example, gold, silver, and the like, carbon nanorubes (single or multiwalled), transparent conducting oxides such as, for example, indium tin oxide ("ITO"), SnO, ZnO, and NiO( X) TiO 2 , and transparent conducting oxides such as, for example, ITO, SnO, ZnO, and NiO (X) TiO 2 comprising additional metal components.
  • the anode can be ITO including ITO supported on a substrate. Substrates can be rigid or flexible.
  • the substrate can be, for example, glass, quartz, plastics such as, for example, PTFE, polysiloxanes, thermoplastics such as, for example, PET, PEN, and the like, metals such as, for example, aluminum, gold, and silver, metal foils, metal oxides, such as, for example, TiOx and ZnOx, and semiconductors, such as, for example, silicon.
  • the cathode may desirably comprise a metal, such as, for example, aluminum, calcium, or mixtures of aluminum and calcium.
  • the p-type material can be called the primary light harvesting component or layer. This material absorbs a photon of a particular energy and generates a state in which an electron is promoted to an excited energy state, leaving a positive charge or "hole” in the ground state energy levels. As known in the art, this is called exciton formation. The exciton diffuses to a junction between p-type and n-type material, creating a charge separation or dissociation of the exciton. The electron and "hole” charges are conducted through the n-type and p-type materials respectively to the electrodes, resulting in the flow of electric current out of the OPV.
  • the p-type material can be an organic material including a polymeric material, although other types of p-type material are known in the art.
  • the p-type material can comprise a conjugated polymer or a conducting polymer comprising a polymer backbone having a series of conjugated double bonds.
  • the p-type material can be, for example, a homopolymer or a copolymer, including a block copolymer, a random copolymer, or a terpolymer.
  • Examples of p-type materials include polythiophene, polypyrrole, polyaniline, polyfluorene, polyphenylene, polyphenylene vinylene, and derivatives, copolymers, and mixtures thereof.
  • the p-type material can comprise, for example, a conjugated polymer soluble or dispersible in organic solvent or water.
  • the p-type semiconductor can comprise conjugated polymers including, for example, including poly-phenylenevinylene (“PPV”) poly (3-hexyl)thiophene (“P3HT”), substituted polythiophenes, substituted polycarbazoles, copolymer comprising at least one dithieno[3,2- b:2',3'-d]pyrrole (DTP) repeat unit, or mixtures or blends of these materials.
  • Low band gap and donor acceptor polymers can be used as p-type materials. For materials comprising DTP and related components, see, for example, US provisional application 61/029,255 filed February 15, 2008.
  • the n-type component can comprise materials with a strong electron affinity including, for example, carbon fullerenes, such as, for example, indenyl-substituted fullerenes, titanium dioxide, cadmium selenium, polymers, and small molecules that are specifically designed to exhibit n-type behavior.
  • the n-type material may commonly include fullerene derivatives, such as, for example, those described in U.S. Non-Provisional Application No. 1 1/743,587, which is hereby incorporated by reference in its entirety.
  • the active layers comprise commercially available inks, such as, for example, PV2000 and PVlOOO (Plextronics, Pittsburgh, PA).
  • the aforementioned inks are typically formulated from a mixture of n-type and p-type materials, and are commonly dissolved in an organic solvent, such as, for example, dichlorobenzene, chlorobenzene, toluene, xylenes, and blends of solvents such as, for example, toluene/xylene, nitrobenzene/ toluene, etc.
  • the n- and p-type materials can be mixed in a ratio of, for example, from about 0.1 to 4.0 (p-type) to about 1 (n-type) based on a weight, from about 1.1 to about 3.0 (p-type) to about 1 (n-type), or from about 1 to about 1.5 (p-type) to about 1 (n-type).
  • the amount of each type of material or the ratio between the two types of components can be varied for the particular application.
  • Total solids for formulations for active layers of the present application are commonly about 1 wt.% to about 3 wt.%.
  • Photovoltaic cells can optionally include a hole transport layer ("HTL"), where the HTL is disposed between the anode and the active layer.
  • HTL hole transport layer
  • the optional HTL can be added using, for example, spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method.
  • the HTL can be, for example, PEDOT, PEDOT/PSS or TBD, or NPB, or Plexcore OC (Plextronics, Pittsburgh, PA).
  • IML Interfacial Modification Layer
  • One layer can be a spacer layer or an interfacial modification layer.
  • the interfacial modification layer can comprise at least one material that is an organic, semiconducting compound, and at least one dopant which can be an organic compound or an alkali metal, alkali earth metal, rare earth metal, or metal oxide.
  • the organic semiconductor material of the present application is desirably hole blocking, meaning that, although not limited by theory, it can have a HOMO value lower in energy than that of the HOMO of the hole transporting material in the OPV active layer.
  • the active layer comprises P3HT
  • the HOMO of the organic material in the IML can be approximately -5.2 eV or less.
  • organic semiconductor materials suitable for the OS layer of the present application include, for example, Bathophenanthroline(4,7-Diphenyl-l,10- phenanthroline) ("BPhen”), 2,9-dimethyl-4,7-diphenyl-l,10- ⁇ henantrolene (“BCP”), Tris-(8- hydroxyquinolino)aluminum (“Alq3”), 4,4'-Bis(carbazol-9-yl)-biphenyl (“CBP”), Bis-(2-methyl- 8-quinolinolato)-4-(phenylphenolato)-aluminum-(III) (“BAIq”), 1 ,3,5-tris(2-N- phenylbenzimidazolyl) benzene (“TPBI”), 4,4',4"-Tris(carbazol-9-yl)-triphenylamine (“TCTA”), 2-Phenyl-5-(4-biphenylyl)-l,3,4-ox
  • Metals that can be suitable dopants for the organic semiconductor can include, for example, alkali metals, alkali earth metals, transition metals, rare earth metals, and metal oxides.
  • Particularly suitable dopant metals and metal oxides may include, for example, cesium, barium, magnesium, molybdenum, cobalt, molybdenum oxide, tungsten oxide, chromium, silver, gold, lithium, calcium, and ytterbium.
  • Organic materials that can be suitable dopants can include, for example, TTF, Pyronin B, BEDT- TTF, and cobaltocene.
  • the metal or organic dopant can be about 1 wt.% to about 60 wt.% of the IML, about 2 wt.% to about 50 wt.% of the IML, about 3 wt.% to about 40 wt.% of the IML, about 4 wt.% to about 30 wt.% of the IML, about 5 wt.% to about 20 wt.% of the IML, or about 6 wt.% to about 10 wt.% of the IML.
  • the IML may be about 1 nm to about 100 nm thick, about 1 nm to about 60 nm thick, about 3 nm to about 30 nm thick, about 5 nm to about 20 nm thick, or about 10 nm to about 15 nm thick.
  • the dopant and the active layer can be adapted to provide the device with properties such as, for example, power conversion efficiency or lifetime, or combinations thereof.
  • properties such as, for example, power conversion efficiency or lifetime, or combinations thereof.
  • the active layer one can select the identity and amounts of the n-type and p-type materials.
  • One can, if desired, consider electronic energy levels including HOMO and LUMO calculations and measurements.
  • One can in some cases also adapt the preparation methods.
  • One can take measurements to determine if the properties are achieved or not, and adapt accordingly based on the results.
  • FIG. 1 shows a schematic of one embodiments of a solar cell device (100) of the present application, including a substrate (102), anode (104), hole transport layer (106), active layer (108), interfacial modification layer (IML) or optical spacer layer (110), and cathode (112).
  • the devices can be made using ITO as an anode material on a substrate.
  • Other anode materials can include, for example, metals such as Au, carbon nanotubes (single or multiwalled), and other transparent conducting oxides.
  • the resistivity of the anode can be maintained below, for example, 15 ⁇ /sq or less, 25 or less, 50 or less, or 100 or less, or 200 or less, or 250 or less.
  • the substrate can be for example glass, plastics (PTFE, polysiloxanes, thermoplastics, PET, PEN and the like), metals (Al, Au, Ag), metal foils, metal oxides, (TiOx, ZnOx) and semiconductors, such as Si.
  • the ITO on the substrate can be cleaned using techniques known in the art prior to device layer deposition.
  • Inverted devices can be also made as known in the art. Modules can be prepared comprising a plurality of OPV devices.
  • HTL hole transport layer
  • the HTL can be for example PEDOT, PEDOT/PSS or TBD, or NPB, or Plexcore HTL (Plextronics, Pittsburgh, PA), or materials described in, for example, US Patent publication 2008/0248313 published October 9, 2008; provisional applications serial nos. 61/044,380 filed April 11, 2008; 61/108,851 filed October 27, 2008; and 61/115,877 filed November 18, 2008 (all assigned to Plextronics).
  • the thickness of the HTL layer can be, for example, from about 10 nm to about 300 run thick, from 30 nm to 60 nm thick, from 60 nm to 100 nm thick, or from 100 nm to 200 nm thick.
  • the HTL layer can be optionally dried/annealed at 110 to 200 0 C for about 1 min to about an hour, optionally in an inert atmosphere. Methods for annealing are known in the art.
  • the active layer can be formulated from a mixture of n-type and p-type materials.
  • the n- and p-type materials can be mixed in a ratio of for example from about 0.1 to 4.0 (p-type) to about 1 (n-type) based on a weight, or from about 1.1 to about 3.0 (p-type) to about 1 (n-type) or from about 1 to about 1.2 (p-type) to about 1 (n-type).
  • the amount of each type of material or the ratio between the two types of components can be varied for the particular application.
  • the active layer may comprise commercially-available inks, such as, for example, PV2000 and PVlOOO (Plextronics, Pittsburgh, PA).
  • the active layer can be deposited by spin casting, slot die coating, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method, on top of the anode, if no HTL is present, or on top of the HTL, if an HTL is present.
  • the active layer film can be optionally annealed at about 40 0 C to about 250 0 C, or from about 150 0 C to about 180 0 C, for about one minute to two hours, or for about 10 minutes to about an hour, in an inert atmosphere.
  • the active layer can further comprise additional ingredients including, for example, surfactants, dispersants, and oxygen and water scavengers.
  • the active layer can comprise multiple layers or be multi-layered.
  • An IML may be included between the active layer and the cathode.
  • the IML deposition comprises the co-evaporation of two materials at a base pressure of about 7 x 10 "7 mbar, such as, for example, BPhen and a metal dopant, e.g., calcium, lithium, ytterbium etc., or BPhen and an organic dopant, e.g., TTF, Pyronin B, BEDT-TTF etc. These materials are commonly deposited such that the final OS film has a metal dopant or organic dopant concentration of about 1 to 40 wt.%, about 5 to 30 wt.%, or about 10 to 20 wt.%.
  • the IML can be, for example, from about 0.5 nm to about 100 nm, from about 0.75 nm to about 60 nm, or from about 1 nm to about 30 nm, thick.
  • a cathode layer can be added to the device, generally using, for example, thermal evaporation of one or more metals.
  • a 10 to 300 nm Al layer can be thermally evaporated onto the IML.
  • the devices can be then encapsulated using a glass cover slip sealed with a UV curable glue, or other epoxy or plastic coatings. Cavity glass with a getter/desiccant may also be used.
  • Performance of OPVs can be determined by measurement of the efficiency of conversion of light energy to electrochemical energy as measured by the quantum efficiency (number of photons effectively used divided by the number of photons absorbed) and by the peak output power generated by the cell (given by the product IppVpp where Ipp is the current and Vpp is the voltage at peak power).
  • Known solar cell parameters can be measured including, for example, Jsc (mA/cm 2 ) and Voc (V) and fill factor (FF) and power conversion efficiency (%, PCE) by methods known in the art.
  • the OPV efficiency can be at least about 4%, or at least about 4.3%, or at least about 4.7%, or at least about 5%, or at least about 5.3%, or at least about 6.0%, or at least about 6.7%, at 1 sun (AMI .5G, 100 mW/cm 2 ).
  • An efficiency range can be for example about 4% to about 8%, or about 4.3% to about 6.7%, or about 5% to about 6.3%.
  • the fill factor for example, can be at least about 0.55, or at least about 0.60, or at least about 0.65, at least about 0.7, at least about 0.75, at least about 0.8, or at least about 0.85.
  • the Voc (V), for example, can be at least about 0.56, or at least about 0.63, or at least about 0.82, or at least about 0.9, or at least about 1.0, or at least about 1.2, or at least about 1.4, or at least about 1.5.
  • the Jsc (mA/cm 2 ), for example, can be at least about 8, or at least about 9.2, or at least about 9.48, or at least about 10, or at least about 1 1, or at least about 12, or at least about 13, or at least about 14, or at least about 15.
  • Oriel Solar Simulators can be used to determine OPV properties including for example FF, Jsc, Voc, and efficiencies.
  • the simulator can be calibrated by methods known in the art including for example calibration with a KG5-S ⁇ reference cell.
  • OPV Lifetime A Xenon lamp (Atlas Specialty Lighting, PE240E-13FM) can be used to generate both the temperature and light.
  • the output designation of ' 1 Suns' is derived from adjusting the intensity of light falling on the devices to be such that a KG-5 cell placed in the same fixture would generate the same current it generates under standard AM 1.5G testing.
  • the devices can be connected to a data acquisition setup where an adjustable DC load maintains them at their maximum power point ("MPP").
  • MPP maximum power point
  • the power output of the cells may be continuously monitored over time.
  • intermittent monitoring of the PV parameters such as Voc, FF, Jsc may also be performed.
  • OPV lifetime is defined as the amount of time that an OPV device or module diminishes to 80% of its 'stabilized' power output (or power conversion efficiency) normalized by the illumination intensity (lamp variation or decay) under ⁇ 1 Sun Xe-arc Lamp with (or converted to) 50% duty cycle.
  • the lifetime of the device that includes an IML at least removes "burn-in" decay that analogous devices without the OS layer usually have, and is at least about 25% longer than an analogous device that does not contain the IML.
  • the lifetime of the device that includes an IML can be at least about 10% longer, 20% longer, 25% longer, 30% longer, 35% longer, 40% longer, 50% longer, 60% longer, 70% longer, 100% longer, 200% longer, or 500% longer than an analogous device that does not contain the IML.
  • the normalized power output of a device prepared according to the present application may be greater than about 80% of initial power for at least about 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours, 100 hours, 250 hours, 500 hours, 750 hours, 1,000 hours, 2,500 hours, 5,000 hours, 7,500 hours, or 10,000 hours than an analogous device that does not contain the IML.
  • Another important aspect is the combination of good efficiency and long lifetime, particularly long lifetime under rigorous testing conditions of high humidity and high temperature.
  • Example 1 Fabrication of Solar Cell Device Using PVlOOO and PV2000 Inks and BPhen Doped with Lithium
  • ITO coated substrates were purchased from Thin Film Devices ("TFD", Anaheim, CA). These substrates were cleaned in a Class 10,000 clean room by sonicating for 20 min in a soap solution, followed by 20 min of sonication in water, 20 min of sonication in acetone and 20 min of sonication in IPA. Finally the substrates were exposed to UV ozone (300 W) for 10 min. After cleaning, each substrate was then coated with an about 30 nm thick layer of Baytron AI4083 (H. C Stark) by spin coating for 5 seconds at 400 rpm in air, followed by a 1 minute at 6000 rpm. The devices were then annealed on a hot plate at 175°C for 30 min in a N 2 atmosphere glove box.
  • the substrates were then transferred to a dry-box for continued processing.
  • the active layer was then spin-coated on top of the HTL layer using one of the two following ink formulations: PV 2000 or PV 1000. These inks were spin cast onto the substrate for 3 min spin at 350 rpm in a nitrogen atmosphere and resulted in films with thicknesses of ⁇ 200-250 nm.
  • the devices were then annealed on a hot plate at 175 0 C for 30 min in a nitrogen atmosphere. Finally, after annealing, the cathode or the IML followed by the cathode was vapor deposited from a base pressure of ⁇ 7 x 10 "7 .
  • An IML comprising an electron transporting material such as BPhen, TPBI, or BCP (Sigma) and a metal (Li, Yb, or Ca, purchased from Kurt Lesker) were thermally evaporated on the surface of the solar cell device active layer inside a high vacuum chamber ( ⁇ 7 x 10 "7 - 10 '6 mbar) to form a layer (about 3-20 nm) comprising about 10-20 wt.% metal.
  • the rate of deposition of the electron transport material was about 1 A/s.
  • the rate of deposition of the metal ranged from 0.1 A/s to 0.6 A/s.
  • an aluminum cathode layer (200 nm) was deposited on the IML.
  • the device was then encapsulated via a glass cover slip (blanket) encapsulation sealed with EPO-TEK OGl 12-4 UV curable glue.
  • the encapsulated device was cured under UV irradiation (80 mW/cm 2 ) for 4 minutes and tested as follows.
  • the photovoltaic characteristics of devices under white light exposure were measured using a system equipped with a Keithley 2400 source meter and an Oriel 300W Solar Simulator based on a Xe lamp with output intensity of 100 mW/cm 2 (AMI .5G).
  • the light intensity was set using an NREL-certif ⁇ ed Si-KG5 silicon photodiode.
  • Example 1 Devices were prepared as described in Example 1 above were tested using an Oriel Solar Simulator and the voltage was swept from reverse to forward bias. From the resulting current that was measured, the power conversion efficiency of each device was determined. Data for each device are summarized in Table 1.
  • a Xenon lamp (Atlas Specialty Lighting, PE240E- 13FM) was used to generate both the temperature and light.
  • the output designation of ' 1 Suns' is derived from adjusting the intensity of light falling on the devices to be such that a KG-5 cell placed in the same fixture would generate the same current it generates under standard AM 1.5G testing.
  • the devices were connected to a data acquisition setup where an adjustable DC load maintained them at their maximum power point ("MPP"). The power output of the cells was continuously monitored over time.
  • MPP maximum power point
  • the "burn-in” decay - defined as the exponential reduction of initial power - is significantly less for devices with the IML than it is for the control device that does not have an IML.
  • This improvement in "burn-in” range significantly impacts the overall device lifetime which is defined as the reduction of device power to 80% of the initial power ("T80").
  • OPV devices of types A, B, and C were prepared.
  • the general architecture for the various OPV devices was as follows:
  • OPVs were prepared using the following procedure: The OPV devices described herein were fabricated on indium tin oxide ("ITO") surfaces deposited on glass substrates. The ITO surface was pre-patterned to define the pixel area of 0.09 cm 2 . The device substrates were cleaned by ultrasonication in a dilute soap solution for 20 minutes each followed by distilled water washes. This was followed by ultrasonication in isopropanol for 20 minutes and then ultrasonication in acetone for 20 minutes. The substrates were dried under nitrogen flow, after which they were treated in a UV-Ozone chamber operating at 300 W for 20 minutes.
  • ITO indium tin oxide
  • the cleaned substrates were then spin coated with PEDOT:PSS (Baytron 4083) at 6000 rpm in a clean-room hood to a thickness of about 40 nm.
  • the substrates were then baked at 175 0 C for 30 minutes in a glove box with a nitrogen atmosphere.
  • the coating process was done on a spin coater but can be similarly achieved with spray coating, slot die coating, ink-jetting, contact printing or any other deposition method capable of resulting in an HTL film of the desired thickness.
  • the substrates were then coated with an Active Layer.
  • OPV devices made with PV 1000, Al-Al 1 were spin coated (350 rpm) to a thickness of about 230 nm in a clean-room glove box for 6-10 minutes.
  • the ink was spin coated (350 rpm) to a thickness of about 210 nm in a clean-room glove box for 6-10 minutes.
  • the ink was spin coated (300 rpm) to a thickness of about 220 nm in a clean-room glove box for 6-10 minutes.
  • the foil was changed after spinning a few substrates in order to remove excess solvent from the spin coater so that the films were spin coated in a limited amount of solvent vapor.
  • the films were then annealed at 175°C for 30 minutes in a glove box with a nitrogen atmosphere and were allowed to cool slowly on a hot plate to below 120°C.
  • the samples were loaded in an evaporator (Edwards) for overnight pumping to ⁇ 7 x 10 "7 mbar.
  • the samples were coated with the various IML materials, listed in Table 2 above, by physical vapor deposition.
  • BPhen was co-evaporated with Yb in the ratio of 83% BPhen (0.1 nm/sec) to 17% Yb (0.02 nm/sec) at a base pressure of 7 x 10 "7 mbar, to a thickness of 10 nm.
  • the cathode layer a 200 nm layer of Al (0.4 nm/sec) with the base pressure at 5 x 10 "7 Torr, was deposited.
  • the devices thus obtained were encapsulated with a glass cover slip to prevent exposure to ambient conditions by means of a UV-light curing epoxy resin cured at 80 W/cm 2 UV exposure for 4 minutes.
  • the OPVs comprised pixels on a glass substrate whose electrodes extended outside the encapsulated area of the device which contain the photoactive portion of the pixels.
  • the typical area of each pixel was 0.09 cm 2 .
  • the photovoltaic characteristics of devices under white light exposure were measured using a system equipped with a Keithley 2400 source meter and an Oriel 300W Solar Simulator based on a Xe lamp with output intensity of 100 mW/cm2 (AM 1.5G).
  • a voltage was applied to the photovoltaic device which was swept from -2 V to 2 V.
  • the resulting photocurrent was measured using the Keithley source meter and an efficiency of the device with reference to the incident light intensity was calculated.
  • Jsc short circuit current density
  • Rs series resistance
  • FF fill factor
  • Table 3 below shows the resulting device parameters from the devices studied.
  • a first set of OPV modules ( Figure 8) was fabricated on glass substrates coated with Cr/Ni/Cr reinforced indium tin oxide ("ITO") having approximately 8-10 ⁇ /D sheet resistance.
  • the devices contained 54 individual pixels that were arranged in 6 columns and 9 rows on a 6 inch x 6 inch glass substrate. The area of each individual pixel was 10 x 20 mm. The nine pixels in a column were connected in series and the six columns were connected in parallel.
  • the device substrates were cleaned by ultrasonication in a dilute detergent solution for 15 minutes followed by distilled water washes. The substrates were dried under nitrogen flow and then treated in a UV-Ozone chamber operating at 300 W for 10 minutes.
  • the cleaned substrates were then spin coated with Plexcore hole transport layer (HTL) at 1000 rpm in a clean-room hood to a thickness of about 60 ran. Note that other methods can be used such as, for example, spray coating, ink jetting, contact printing, and other methods.
  • the substrates were then baked at 175°C for 30 minutes in air.
  • the substrates were then spin-coated with an Active Layer.
  • the active layer (PV 2000 series slot die coating ink) was deposited using an FAS slot die coater in air.
  • the target active layer thickness was 200 nm.
  • the substrates were transferred into a glove box under nitrogen and annealed on a hot plate at 175 0 C for 30 minutes.
  • the individual cells of the module were electrically isolated from each other by ablating off the organic material using an excimer laser. This laser patterning also opened up contacts for the interconnects for the electrical connections of the columns and rows. After the laser ablation step, the samples were transferred to an evaporator for cathode deposition.
  • the samples were coated with either a BPhen:Yb/Al cathode or a Ca/ Al bilayer cathode.
  • the Bphen: Yb layer was an IML of BPhen and Yb, co- deposited to create the desired composition of the OS layer.
  • Yb deposition rates were 0.1, 0.3, or 0.5 A/s. Ratios of Bphen to Yb deposition rates were 1, 5, or 15.
  • the thickness of the BPhen/Yb layers ranged from 5-35 nm.
  • the Al deposition rate was 0.5 nm/sec.
  • the Ca/Al electrodes were deposited at rates of 0.2 nm/sec to 20 nm and 0.5 nm/sec to 80 nm for Ca and Al respectively. All depositions occur at base pressures of 7.5 x 10 "7 mtorr.
  • modules were then encapsulated using an MBraun UV press with a glass cover slip, Saes Dynic getters, and epoxy resin. Up to 20 Saes Dynic getters were placed around the perimeter of the module for encapsulation. The perimeter of a glass cover slip was coated with epoxy resin and pressed onto the glass substrate where it was cured by means of a UV-light at 80 W/cm 2 UV exposure for 80 seconds.
  • Stripe modules were also prepared using these methods but a different substrate.
  • the substrate comprised ten equal sized rectangular ITO stripes on a glass substrate leading to an active area on the device of 98 cm 2 (relatively more active area, higher aperture).
  • Photovoltaic characteristics of the modules prepared in Example 6 under white light exposure were measured using a system equipped with a Keithley 2400 source meter and an Oriel 300W Solar Simulator based on a Xe lamp with output intensity of 100 mW/cm2 (AMI .5G).
  • a voltage was applied to the photovoltaic module which was swept from -10 V to 10 V.
  • the resulting photocurrent was measured using the Keithley source meter and an efficiency of the device with reference to the incident light intensity (PCE) was calculated.
  • Jsc short circuit current density
  • Rs series resistance
  • FF fill factor
  • Example 8 Module Preparation and Stability Testing
  • Modules were fabricated using the method as described in Example 6.
  • Module active layers contained PVlOOO or PV2000.
  • Module IMLs contained Ca, Li:BPhen, Yb:BPhen, or Yb:TPBI.
  • the Stability of the modules was evaluated under two different conditions.
  • the first (“Xe”) was ambient temperature and humidity, subject to continuous exposure to a "1 Sun” intensity Xenon lamp .
  • the second (“QSun”) was 85 °C temperature and 85% relative humidity, subject to continuous exposure to a "0.4 Sun” intensity Xenon lamp.
  • FIG. 4 shows burn-in for modules subjected to the two testing conditions, broken down by active layer and OS layer compositions. Burn-in is the ratio of a module's measured efficiency after 200 hours of testing relative to the initial measured efficiency.
  • the Yb:TPBI IML appears to provide better burn-in than the Li:BPhen OS layer, regardless of environmental conditions or the active layer ink. Burn in of over 50%, of over 60%, of over 70%, or of over 80% can be achieved.
  • Fig.5 shows modules subjected to the "QSun" testing conditions, where the IML comprises Ca or Li:BPhen and the active layer comprises PVlOOO or PV2000.
  • Fig. 6A shows a cross sectional transmission electron microscopy image of a module's active layer, a Ca interfacial layer, and an Al layer, taken before environmental testing.
  • the Ca layer shows voids consistent with oxidation at the Ca-Al interface.
  • Fig. 6B shows the XPS depth profile of the module of Fig. 6A.
  • poly-3-hexylthiophene (P3HT) was the active layer polymer. It can be seen from the high resolution XPS spectra of sulfur 2p region that the sulfur moieties in the P3HT polymer also undergo reaction as a result of the Ca layer deposition.
  • P3HT poly-3-hexylthiophene
  • Fig. 7A-7C show the contrasting results for a module that has a Yb:BPhen interfacial layer.
  • Fig. 7A shows a smooth continuous Yb:BPhen interfacial layer, with none of the oxidation-based voids that had been seen in the Ca layer of Fig. 6A.
  • Fig 7B shows that some interfacial oxidation occurred, but not as severe as that shown in Fig. 6B. The relevant peaks are much smaller.
  • Fig. 7C shows that less reduction of the P3HT sulfurs has occurred, with no formation of a separate sulfide layer (pi 22 is green; p75 is blue; p53 is black; and p22 is red).

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Abstract

L'invention concerne des dispositifs photovoltaïques organiques (OPV) comprenant un semi-conducteur organique dopé avec un dopant métallique ou organique pour former une couche de modification interfaciale, où la couche est disposée sur une couche active comprenant un polymère conjugué et un fullerène. Dans la couche, le semi-conducteur organique peut être BPhen ou TPBI, et le dopant peut être un métal ou un matériau organique. Dans la couche active, le polymère conjugué peut être P3HT et le fullerène peut être PCBM ou un fullerène substitué d'indényle. Cela permet d'atteindre un rendement et une longévité de l'OPV améliorés. De bons résultats d'essai sont obtenus malgré une forte humidité et une température élevée, et des modules peuvent être constitués.
PCT/US2009/006236 2008-11-21 2009-11-20 Couches de modification interfaciale dopées pour l’amélioration de la stabilité de cellules solaires organiques à hétérojonction WO2010059240A1 (fr)

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