ES2350222B1 - TIO2 NANOCRISTALINE GIVEN WITH NITROGEN FOR PHOTOVOLTAIC APPLICATIONS. - Google Patents
TIO2 NANOCRISTALINE GIVEN WITH NITROGEN FOR PHOTOVOLTAIC APPLICATIONS. Download PDFInfo
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- ES2350222B1 ES2350222B1 ES200930194A ES200930194A ES2350222B1 ES 2350222 B1 ES2350222 B1 ES 2350222B1 ES 200930194 A ES200930194 A ES 200930194A ES 200930194 A ES200930194 A ES 200930194A ES 2350222 B1 ES2350222 B1 ES 2350222B1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 claims description 11
- 229920001940 conductive polymer Polymers 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000004549 pulsed laser deposition Methods 0.000 claims description 7
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 6
- 210000004027 cell Anatomy 0.000 description 45
- 239000012298 atmosphere Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 239000002070 nanowire Substances 0.000 description 2
- -1 nitrogen ions Chemical class 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004904 UV filter Substances 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000004754 hybrid cell Anatomy 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010397 one-hybrid screening Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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Abstract
TiO_{2} nanocristalino dopado con nitrógeno para aplicaciones fotovoltaicas.TiO 2 nitrogen-doped nanocrystalline for photovoltaic applications.
La presente invención describe un procedimiento de obtención de un TiO_{2} nanocristalino dopado con nitrógeno mediante la técnica de láser pulsado, que confiere a dicho nanocristalino unas propiedades que lo hacen idóneo para utilizar en dispositivos fotovoltaicos, especialmente en células solares, ya sean éstas de tipo Gratzel, híbridas u orgánicas.The present invention describes a process to obtain a nano-crystalline TiO2 nitrogen doped with nitrogen by the pulsed laser technique, which confers on said nanocrystalline properties that make it ideal for use in photovoltaic devices, especially in solar cells, already whether they are Gratzel, hybrid or organic.
Description
TiO_{2} nanocristalino dopado con nitrógeno para aplicaciones fotovoltaicas.TiO 2 nitrogen-doped nanocrystalline for photovoltaic applications.
La presente invención se refiere a un TiO_{2} dopado con nitrógeno, que presenta una estructura 100% tipo rutilo, su procedimiento de obtención y su uso en la fabricación de un dispositivo fotovoltaico.The present invention relates to a TiO2 doped with nitrogen, which has a 100% rutile structure, its procedure for obtaining and its use in the manufacture of a photovoltaic device
El óxido de titanio dopado con nitrógeno (N-TiO_{2}), es un material altamente utilizado en fotocatálisis, agente antibacteriano, etc.Nitrogen oxide doped with nitrogen (N-TiO 2), is a material highly used in photocatalysis, antibacterial agent, etc.
En el documento CN 101279250 A describe la aplicación de un fotocatalizador a base de TiO_{2} dopado con nitrógeno cuyo dopaje le permite la absorción de longitudes de onda en el espectro visible y en el infrarrojo. En otro documento CN 101026200 A se describe un procedimiento de preparación de películas de TiO_{2} dopado con nitrógeno controlado por amoniaco y un dispositivo de reacción a alta presión. En el documento CN 101026024 A se revela un buen conductor de TiO_{2} dopado con nitrógeno en polvo y su procedimiento de preparación.In CN 101279250 A describes the application of a TiO_ {2} based photocatalyst doped with nitrogen whose doping allows the absorption of wavelengths in the visible spectrum and in the infrared. In another CN document 101026200 A describes a film preparation procedure of TiO2 doped with ammonia-controlled nitrogen and a high pressure reaction device. In document CN 101026024 A good TiO2 conductor doped with nitrogen is revealed in powder and its preparation procedure.
En el mercado se encuentra el uso del N-TiO_{2} en dispositivos para fotocatálisis (ventanas con autolimpiado, desodorante de vehículos de Toyota, etc.) o relacionados.In the market is the use of N-TiO_ {2} in devices for photocatalysis (self-cleaning windows, Toyota vehicle deodorant, etc.) or related.
Además, se conoce la aplicación del N-TiO_{2} en células solares (T. Ma, et al. "High-efficiency dye-sensitized solar cell based on a nitrogen-doped nanostructured titania electrode". Nano Letters, 2005 Dec; 5 (12), 2543-2547) y la aplicación del N-TiO_{2} en células solares obtenido por un procedimiento de sol-gel, obteniéndose un cristal de N-TiO_{2} cuya estructura presenta una mezcla de las fases anatasa, brookita y rutilo (T. Lopez-Luke, et al. "Nitrogen-doped and CdSe Quantum-Dot-Sensitized Nanocrystalline TiO_{2} Films for Solar Energy Conversión Applications". J. Phys. Chem. C, 2008, 112, 4, 1282-1292).In addition, the application of N-TiO2 in solar cells is known ( T. Ma, et al . " High-efficiency dye-sensitized solar cell based on a nitrogen-doped nanostructured titania electrode ". Nano Letters, 2005 Dec; 5 (12), 2543-2547 ) and the application of N-TiO2 in solar cells obtained by a sol-gel process, obtaining a crystal of N-TiO2 whose structure presents a mixture of anatase phases , brookita and rutile ( T. Lopez-Luke, et al . " Nitrogen-doped and CdSe Quantum-Dot-Sensitized Nanocrystalline TiO_2 Films for Solar Energy Conversion Applications ". J. Phys. Chem. C, 2008, 112, 4, 1282-1292 ).
Un dispositivo fotovoltaico híbrido se caracteriza por la utilización de óxidos semiconductores inorgánicos (TiO_{2}, ZnO, Nb_{2}O_{5}, CeO_{2}, SnO_{2}, etc.) en contacto directo con semiconductores orgánicos (colorantes, polímeros, electrolitos). Los mejores ejemplos de este tipo de células solares son las conocidas células solares tipo Gratzel o de óxido de titanio sensitivizado ("dye-sensitized solar cell" o DSC), las células solares poliméricas híbridas ("hybrid solar cells" o HSC) o las células solares tipo Gratzel en estado sólido ("solid state dye-sensitized solar cell" o ss-DSC). Dentro de los semiconductores inorgánicos utilizados (TiO_{2}, ZnO, Nb_{2}O_{5}, CeO_{2}, SnO_{2}, CeO_{2}-TiO_{2}, etc.) el más aplicado, debido a sus altas prestaciones, es el TiO_{2} utilizado en su estructura anatasa que presenta mayor fotoactividad. Sin embargo, algunas variaciones utilizando mezclas de TiO_{2} en sus estructuras anatasa y rutilo también pueden ser utilizadas. El procedimiento de síntesis más utilizado para la obtención de los óxidos semiconductores son las técnicas por sol-gel o síntesis hidrotermal.A hybrid photovoltaic device is characterized by the use of inorganic semiconductor oxides (TiO2, ZnO, Nb2O5, CeO2, SnO2, etc.) in direct contact with organic semiconductors ( dyes, polymers, electrolytes). The best examples of this type of solar cells are known solar type cells Gratzel or titanium oxide sensitivizado ( "dye-sensitized solar cell" or DSC), hybrid polymer solar cells ( "solar hybrid cells" or HSC) or Gratzel solar cells in solid state (" solid state dye-sensitized solar cell " or ss-DSC). Within the inorganic semiconductors used (TiO2, ZnO, Nb2O5, CeO2, SnO2, CeO2-TiO2, etc.) the most applied, Due to its high performance, it is the TiO_2 used in its anatase structure that has greater photoactivity. However, some variations using mixtures of TiO2 in its anatase and rutile structures can also be used. The most commonly used synthesis procedure for obtaining semiconductor oxides is sol-gel or hydrothermal synthesis techniques.
Recientemente, se demostró que los dispositivos fotovoltaicos híbridos, formados por interfases óxido/polímero, presentan un mecanismo de intercambio de oxígeno con la atmósfera necesario para su correcto funcionamiento como transportadores de carga (electrones). Sin embargo, es este mismo oxígeno el responsable de la degradación de los semiconductores orgánicos (colorantes, polímeros, etc.) con el tiempo, limitando así la vida útil del dispositivo. La situación ideal sería entonces la encapsulación del dispositivo en atmósfera inerte para evitar la degradación del semiconductor orgánico, pero la presencia de atmósferas inertes elimina el oxígeno requerido por el óxido semiconductor para funcionar como transportador de cargas. Este mecanismo de actuación es un problema importante para mantener la estabilidad del material orgánico y para poder utilizar estos dispositivos fotovoltaicos en aplicaciones bajo atmósferas inertes como en equipos espaciales (satélites, sondas espaciales, etc.).Recently, it was shown that the devices hybrid photovoltaic, formed by oxide / polymer interfaces, they have an oxygen exchange mechanism with the atmosphere necessary for its proper functioning as conveyors of charge (electrons). However, it is this same oxygen the responsible for the degradation of organic semiconductors (dyes, polymers, etc.) over time, thus limiting life Useful device. The ideal situation would then be the encapsulation of the device in an inert atmosphere to avoid degradation of the organic semiconductor, but the presence of inert atmospheres eliminates the oxygen required by the oxide semiconductor to function as a load conveyor. This mechanism of action is an important problem to maintain the stability of the organic material and to be able to use these photovoltaic devices in applications under inert atmospheres as in space equipment (satellites, space probes, etc.).
En un primer aspecto, la presente invención se refiere a un procedimiento de obtención de TiO_{2} nanocristalino dopado con nitrógeno en la fase 100% rutilo que comprende:In a first aspect, the present invention is refers to a procedure for obtaining nanocrystalline TiO2 doped with nitrogen in the 100% rutile phase comprising:
- a)to)
- deposición por láser pulsado (pulse láser deposition o PLD) de TiO_{2} sobre un electrodo sustrato transparente y conductor tipo óxido de estaño dopado con flúor (flúor tin oxide o FTO), donde dicho sustrato se encuentra a una temperatura de entre 400ºC y 600ºC,Pulsed laser deposition ( pulse laser deposition or PLD) of TiO 2 on a transparent substrate electrode and fluorine-doped tin oxide conductor ( fluorine tin oxide or FTO), where said substrate is at a temperature between 400 ° C and 600 ° C,
- b)b)
- adición de una mezcla de gas oxígeno-nitrógeno sobre el material obtenido en el paso anterior, donde la relación de presiones parciales de dichos gases es X:Y, siendo X+Y un valor constante de entre 1 y 15 Pa.adding a gas mixture oxygen-nitrogen on the material obtained in the previous step, where the ratio of partial pressures of said gases is X: Y, with X + Y being a constant value between 1 and 15 Pa.
El TiO_{2} nanocristalino dopado con nitrógeno (N-TiO_{2}) es un óxido semiconductor inorgánico cuya estructura cristalina presenta unas dimensiones del orden de 10 nm y en el que se han introducido iones de nitrógeno. El TiO_{2} se encuentra en la naturaleza en forma de minerales con estructura rutilo, anatasa, brookita o mezcla de las mismas. El TiO_{2} en la fase cristalina tipo rutilo presenta la mejor respuesta fotovoltaica al trabajar bajo condiciones de atmósfera inerte (estabilidad de la J_{sc}). Por tanto, es imprescindible la síntesis del material en su estructura rutilo, pues la estructura anatasa o mezcla de anatasa y/o rutilo y/o brookita no presenta las propiedades deseadas. Este comportamiento puede deberse a que la fase rutilo presenta mayor resistencia interna en comparación a la fase anatasa, lo que evita que el TiO_{2} se comporte como un conductor casi metálico al doparse y durante la extracción de oxígeno que se lleva a cabo en atmósferas inertes.The nitrogen-doped nanocrystalline TiO2 (N-TiO2) is an inorganic semiconductor oxide whose crystalline structure has dimensions of the order of 10 nm and in which nitrogen ions have been introduced. TiO_ {2} It is found in nature in the form of minerals with structure rutile, anatase, brookita or mixture thereof. The TiO_ {2} in the Rutile type crystalline phase presents the best photovoltaic response when working under conditions of inert atmosphere (stability of the J_ {sc}). Therefore, the synthesis of the material in its rutile structure, because the anatase structure or anatase mixture and / or rutile and / or brookita does not have the desired properties. This behavior may be due to the greater rutile phase internal resistance compared to the anatase phase, which prevents that TiO_ {2} behaves like an almost metallic conductor to doping and during the extraction of oxygen that is carried out in inert atmospheres.
La utilización de la técnica de deposición por láser pulsado (PLD) ha dado como resultado un material TiO_{2} con mejores prestaciones (menor pérdida de fotoactividad bajo irradiación continuada). Mediante la técnica PLD se consigue la deposición en forma de capa delgada del TiO_{2} sobre el sustrato deseado en el interior de una cámara.The use of deposition technique by Pulsed laser (PLD) has resulted in a TiO2 material with better performance (less loss of low photoactivity continued irradiation). The PLD technique achieves the Thin layer deposition of TiO2 on the substrate desired inside a camera.
Preferiblemente, en el procedimiento descrito anteriormente, el electrodo sustrato transparente y conductor de la etapa a) se encuentra a una temperatura de 500ºC.Preferably, in the procedure described previously, the transparent and conductive substrate electrode of the step a) is at a temperature of 500 ° C.
Preferiblemente, en el procedimiento anterior, la deposición por láser pulsado se realiza, a una energía de entre 200 a 600 mJ y a una frecuencia de entre 1 y 20 Hz. Más preferiblemente, la deposición por láser pulsado se realiza a una energía de 400 mJ y a una frecuencia de 10 Hz.Preferably, in the above procedure, Pulsed laser deposition is performed at an energy between 200 to 600 mJ and at a frequency between 1 and 20 Hz. More preferably, pulsed laser deposition is performed at a 400 mJ energy and at a frequency of 10 Hz.
Preferiblemente, en el procedimiento descrito anteriormente, X+Y es 10 Pa.Preferably, in the procedure described Previously, X + Y is 10 Pa.
Preferiblemente, en el procedimiento descrito anteriormente la relación de presiones parciales de la mezcla de gas oxígeno-nitrógeno se selecciona entre 4:6, 3:7 ó 2:8. Más preferiblemente, la relación de presiones parciales es 2:8.Preferably, in the procedure described previously the ratio of partial pressures of the gas mixture oxygen-nitrogen is selected from 4: 6, 3: 7 or 2: 8 More preferably, the partial pressure ratio is 2: 8
En un segundo aspecto, la presente invención se refiere a un TiO_{2} nanocristalino dopado con nitrógeno obtenible por el procedimiento descrito anteriormente.In a second aspect, the present invention is refers to a nano-crystalline TiO2 doped with nitrogen obtainable by the procedure described above.
En un tercer aspecto, la presente invención se refiere a un dispositivo fotovoltaico que comprende el TiO_{2} nanocristalino dopado con nitrógeno anteriormente descrito, un polímero conductor y un contraelectrodo metálico.In a third aspect, the present invention is refers to a photovoltaic device comprising the TiO2 nitrogen-doped nanocrystalline described above, a conductive polymer and a metallic counter electrode.
En una realización preferida, en dicho dispositivo fotovoltaico el polímero conductor se selecciona entre P3HT (poli(3-hexiltiofeno)), PCBM (ester metílico de ácido fenil-C61-butírico), MEH-PPV (poli[2-metoxi-5-(2'-etil-hexiloxi)-1,4-fenilenovinileno]) o mezclas de los mismos. Y más preferiblemente, el polímero conductor es MEH-PPV.In a preferred embodiment, in said photovoltaic device the conductive polymer is selected from P3HT (poly (3-hexylthiophene)), PCBM (ester acid methyl phenyl-C61-butyric), MEH-PPV (poly [2-methoxy-5- (2'-ethyl-hexyloxy) -1,4-phenylenevinylene]) or mixtures thereof. And more preferably, the polymer Driver is MEH-PPV.
En otra realización preferida, en dicho dispositivo fotovoltaico el contraelectrodo metálico se selecciona entre Ag, Au, Pt, Ca o Al. Y más preferiblemente, el contraelectrodo metálico es Ag.In another preferred embodiment, in said photovoltaic device the metal counter electrode is selected between Ag, Au, Pt, Ca or Al. And more preferably, the counter electrode metallic is Ag.
El dispositivo fotovoltaico objeto de la presente invención se compone de dos capas delgadas, el N-TiO_{2} y un polímero conductor (preferiblemente MEH-PPV), ensamblados entre dos electrodos colectores de corriente, el FTO transparente y un electrodo de Ag evaporado. El grosor de la capa de N-TiO_{2} es de aproximadamente 400 nm, mientras que la del polímero conductor es de 100 nm. Esta configuración se ha utilizado para análisis de laboratorio donde se requiere que, para efectos prácticos, el tiempo de vida de la célula solar sea suficientemente corto para llevarse a cabo en el laboratorio, pero capaz de ser comparado con dispositivos fotovoltaicos similares. Por lo tanto, una configuración óptima sería aquella en la que el N-TiO_{2} se utilizara de forma nanoestructurada (nanopartículas, nanocables, etc.) con una mayor área de superficie.The photovoltaic device object of the The present invention is composed of two thin layers, the N-TiO2 and a conductive polymer (preferably MEH-PPV), assembled between two electrodes current collectors, the transparent FTO and an Ag electrode evaporated. The thickness of the N-TiO 2 layer is approximately 400 nm, while that of the conductive polymer is 100 nm This configuration has been used for analysis of laboratory where time is required for practical purposes of solar cell life is short enough to carry out in the lab, but able to be compared to devices Similar photovoltaic Therefore, an optimal configuration would be one in which the N-TiO_ {2} was used Nanostructured (nanoparticles, nanowires, etc.) with a Greater surface area.
En un cuarto aspecto, la presente invención se refiere al uso del TiO_{2} dopado con nitrógeno anteriormente descrito para la fabricación de un dispositivo fotovoltaico.In a fourth aspect, the present invention is refers to the use of TiO2 doped with nitrogen previously described for the manufacture of a photovoltaic device.
Como se ha descrito anteriormente, el
dispositivo fotovoltaico presenta, preferiblemente, una
configuración TOC/
N-TiO_{2}/MEH-PPV/Ag, donde TOC
(Transparent Conducting Oxide) es un electrodo substrato
transparente y conductor, N-TiO_{2} es el
TiO_{2} nanocristalino dopado con nitrógeno,
MEH-PPV es un polímero conductor y Ag actúa como un
contraelectrodo metálico. El objetivo es poder trabajar con el
dispositivo fotovoltaico objeto de la presente invención en
atmósferas inertes para así mejorar la vida útil de la célula solar
donde éste se utiliza.As described above, the photovoltaic device preferably has a TOC / configuration.
N-TiO_2 / MEH-PPV / Ag, where TOC ( Transparent Conducting Oxide ) is a transparent and conductive substrate electrode, N-TiO2 is the nano-crystalline TiO2 nitrogen-doped, MEH-PPV is a Conductive polymer and Ag acts as a metallic counter electrode. The objective is to work with the photovoltaic device object of the present invention in inert atmospheres in order to improve the useful life of the solar cell where it is used.
Y en un último aspecto, la presente invención se refiere al uso de dicho dispositivo fotovoltaico para la fabricación de una célula solar. Preferiblemente, la célula solar es una célula solar tipo Gratzel, una célula solar híbrida o una célula solar orgánica.And in a final aspect, the present invention is refers to the use of said photovoltaic device for manufacturing of a solar cell. Preferably, the solar cell is a cell solar type Gratzel, a hybrid solar cell or a solar cell organic
El N-TiO_{2} obtenible por el procedimiento objeto de la presente invención presenta una buena estabilidad con el tiempo de la célula solar donde se usa el dispositivo fotovoltaico del que forma parte, bajo condiciones de atmósfera inerte (N_{2}, argón, etc.) e irradiación continuada de 1 sol (1000 W/m^{2}, 1,5 A.M.). Los dopajes que se utilizan varían con las condiciones de deposición (presión parcial de oxígeno y nitrógeno).The N-TiO_2 obtainable by the procedure object of the present invention has a good stability over time of the solar cell where the photovoltaic device of which it is part, under conditions of inert atmosphere (N2, argon, etc.) and continuous irradiation of 1 sol (1000 W / m2, 1.5 A.M.). The dopings that are used vary with deposition conditions (partial pressure of oxygen and nitrogen).
Fig. 1. Comparación de las primeras dos horas de vida de células solares híbridas tipo FTO/TiO_{2}/MEH-PPV/Ag analizadas bajo condiciones de irradiación continuada a 1 sol (1.000 W/m^{2}), A.M. 1,5 y en atmósfera inerte. El TiO_{2} utilizado se sintetizo por medio de dos técnicas diferentes: (superior) PLD y (inferior) sol-gel.Fig. 1. Comparison of the first two hours of life of hybrid solar cells type FTO / TiO2 / MEH-PPV / Ag analyzed under conditions of irradiation continued at 1 sol (1,000 W / m2), A.M. 1.5 and in inert atmosphere The TiO2 used was synthesized by means of Two different techniques: (upper) PLD and (lower) sol-gel
Fig. 2. Comparación de células solares híbridas del tipo TCO/TiO_{2}/MEH-PPV/Ag en donde el TiO_{2} se ha utilizado en su fase rutilo (superior) y anatasa (inferior). Análisis llevados a cabo bajo condiciones de irradiación continuada a 1 sol (1.000 W/m^{2}), A.M. 1,5 y en atmósfera inerte.Fig. 2. Comparison of hybrid solar cells of the TCO / TiO_2 / MEH-PPV / Ag type where the TiO2 has been used in its rutile (upper) and anatase phase (lower). Analysis carried out under irradiation conditions continued at 1 sol (1,000 W / m2), A.M. 1.5 and in atmosphere inert.
Fig. 3. Comparación de células solares híbridas del tipo FTO/TiO_{2}/MEH-PPV/Ag utilizando el TiO_{2} y el TiO_{2} dopado con nitrógeno (Relación O:N de 2:8). Análisis llevados a cabo bajo condiciones de irradiación continuada a 1 sol (1.000 W/m^{2}), A.M. 1,5 y en atmósfera inerte.Fig. 3. Comparison of hybrid solar cells of type FTO / TiO_2 / MEH-PPV / Ag using the TiO2 and TiO2 doped with nitrogen (O: N ratio of 2: 8). Analysis carried out under conditions of continuous irradiation at 1 sol (1,000 W / m2), A.M. 1.5 and in an inert atmosphere.
Fig. 4. Curvas IV obtenidas a diferentes tiempos de irradiación bajo atmósfera de N_{2} obtenidas durante el análisis de las células solares híbridas aplicando TiO_{2} (superior) y N-TiO_{2} (inferior). La mayor diferencia entre ambos dispositivos es el tipo de curva IV que en el caso del TiO_{2} es casi plana después de sólo 5 minutos de análisis, mientras que el N-TiO_{2} mantiene un FF superior al 30%. Análisis llevados a cabo bajo condiciones de irradiación continuada a 1 sol (1.000 W/m^{2}), A.M. 1,5 y en atmósfera inerte.Fig. 4. Curves IV obtained at different times of irradiation under atmosphere of N 2 obtained during the analysis of hybrid solar cells applying TiO2 (upper) and N-TiO2 (lower). The biggest difference between both devices is the type of curve IV that in the TiO_ {2} case is almost flat after only 5 minutes of analysis, while the N-TiO_2 maintains an FF more than 30%. Analysis carried out under conditions of continued irradiation at 1 sol (1,000 W / m2), A.M. 1.5 and in inert atmosphere
Fig. 5. Primeras 50 horas de irradiación continuada en atmósfera de N_{2} y 1.000 W/m^{2}, A.M. 1,5 para la célula solar utilizando el N-TiO_{2}. Se hace especial énfasis en las curvas IV a diferentes tiempos del análisis donde se muestra un factor de llenado (FF) superior al 25%.Fig. 5. First 50 hours of irradiation continued in an atmosphere of N2 and 1,000 W / m2, A.M. 1.5 for the solar cell using the N-TiO2. It does special emphasis on IV curves at different times of analysis where a filling factor (FF) greater than 25% is shown.
Fig. 6. Comparación de la respuesta fotovoltaica de células solares híbridas utilizando el TiO_{2} y el N-TiO_{2} como transportadores de electrones en células solares híbridas. Análisis llevados a cabo bajo condiciones de irradiación continuada a 1 sol (1.000 W/m^{2}) A.M. 1,5 y en atmósfera inerte.Fig. 6. Comparison of the photovoltaic response of hybrid solar cells using TiO2 and the N-TiO2 as electron transporters in hybrid solar cells. Analysis carried out under conditions of irradiation continued at 1 sol (1,000 W / m2) A.M. 1.5 and in inert atmosphere
Fig. 7. Respuesta fotovoltaica de las primeras 50 horas de células solares híbridas utilizando el N-TiO_{2} como transportadores de electrones. Análisis llevados a cabo bajo condiciones de irradiación continuada a 1 sol (1.000 W/m^{2}) A.M. 1,5 y en atmósfera inerte.Fig. 7. Photovoltaic response of the first 50 hours of hybrid solar cells using the N-TiO2 as electron transporters. Analysis carried out under conditions of continuous irradiation at 1 sol (1,000 W / m2) A.M. 1.5 and in an inert atmosphere.
Fig. 8. Diagrama esquemático de una célula solar híbrida en donde se muestra la bicapa N-TiO_{2}/Polímero entre los dos electrodos FTO y Ag.Fig. 8. Schematic diagram of a solar cell hybrid where the bilayer is shown N-TiO2 / Polymer between the two FTO electrodes and Ag.
EjemploExample
La obtención de la fase rutilo depende completamente del sustrato transparente que se utilice. El crecimiento del material sobre sustratos tipo óxido de estaño dopado con indio (Indium Tin Oxide, ITO) dará como resultado un material con estructura anatasa, o mezcla de anatasa-rutilo, mientras que sintetizado sobre un substrato transparente y conductor tipo óxido de estaño dopado con flúor (Fluor Tin Oxide, FTO) da como resultado la obtención del material en su forma rutilo.Obtaining the rutile phase depends completely of the transparent substrate that is used. He material growth on doped tin oxide substrates with indium (Indium Tin Oxide, ITO) will result in a material with anatase structure, or anatase-rutile mixture, while synthesized on a transparent and conductive substrate type fluorine-tinned tin oxide (Fluor Tin Oxide, FTO) gives as result obtaining the material in its rutile form.
Las capas de TiO_{2} se depositan mediante la técnica de depósito por láser pulsado (PLD, pulse láser deposition). El material blanco utilizado fue TiO_{2} sinterizado en forma de pastilla a 1.100ºC durante 4 horas. Se fijó la distancia blanco-sustrato en 50 mm y la deposición por láser pulsado se realizó a una energía de 400 mJ, lo que corresponde a una fluencia de 2 J cm^{-2} en la superficie de los blancos. La frecuencia de repetición de los pulsos láser fue de 10 Hz. La suma de las presiones parciales de la mezcla de gas oxígeno-nitrógeno en el interior de la cámara fue 10 Pa. Se utilizó una temperatura del sustrato de 500ºC.TiO_ {2} layers are deposited by Pulsed laser deposition technique (PLD, press laser deposition). The white material used was TiO2 sintered in the form of tablet at 1,100 ° C for 4 hours. The distance was set 50mm white substrate and laser deposition pulsed was performed at an energy of 400 mJ, which corresponds to a 2 J cm -2 creep on the surface of the targets. The repetition frequency of the laser pulses was 10 Hz. The sum of the partial pressures of the gas mixture oxygen-nitrogen inside the chamber was 10 Pa. A substrate temperature of 500 ° C was used.
Para el crecimiento de las capas dopadas con nitrógeno, la suma de las presiones parciales de la mezcla de gas oxígeno-nitrógeno se mantuvo constante a 10 Pa. La presión parcial de nitrógeno varió entre 0 y 8 Pa mientras que la presión parcial de oxígeno era el valor complementario hasta alcanzar la presión total de 10 Pa.For the growth of doped layers with nitrogen, the sum of the partial pressures of the gas mixture oxygen-nitrogen remained constant at 10 Pa. partial pressure of nitrogen varied between 0 and 8 Pa while the partial oxygen pressure was the complementary value until reach the total pressure of 10 Pa.
La configuración más básica para la fabricación de la célula solar es en una estructura bicapa en donde una capa fina de un semiconductor orgánico, (e.g. polímero conductor), que se selecciona entre P3HT, PCBM, MEH-PPV, etc., o mezclas de los mismos, se deposita por medio de la técnica de spin coating sobre el N-TiO_{2} (ver Figura 8.). A este tipo de células solares se les conoce como células solares híbridas. El N-TiO_{2} en este caso está en forma de capa fina pero se pueden utilizar capas nanoestructuradas del mismo material que permitan una mayor área de superficie como nanopartículas, nanocables, etc. De esta forma el N-TiO_{2} actúa como un material transportador de electrones (ETM).The most basic configuration for manufacturing of the solar cell is in a bilayer structure where a layer fine of an organic semiconductor, (e.g. conductive polymer), which select between P3HT, PCBM, MEH-PPV, etc., or mixtures thereof, is deposited by means of the spin technique coating on the N-TiO2 (see Figure 8.). To this Type of solar cells are known as hybrid solar cells. The N-TiO_ {2} in this case is in the form of a layer fine but nanostructured layers of it can be used material that allow a greater surface area such as nanoparticles, nanowires, etc. In this way the N-TiO_ {2} acts as a carrier material for electrons (ETM).
Por lo tanto, como ETM, el N-TiO_{2} puede ser utilizado no sólo en una célula solar híbrida, sino también puede ser utilizado en una célula solar tipo Gratzel y en una célula solar orgánica. Como capa intermedia en una célula solar orgánica tipo tándem o como capa tamponadora en una célula solar tipo excitón, en las que la absorción del fotón de la luz produce un par electron-hueco llamado excitón. La separación eficiente del excitón en el electrón y el hueco es necesaria para la generación de energía. Esta separación se lleva a cabo en la interfase entre el polímero y el óxido.Therefore, like ETM, the N-TiO_ {2} can be used not only in one hybrid solar cell, but can also be used in a cell solar type Gratzel and in an organic solar cell. As a cape intermediate in a tandem type organic solar cell or as a layer buffer in an exciton solar cell, in which the photon absorption of light produces a pair electron-hole called exciton. The separation Efficient exciton in the electron and the gap is necessary for the energy generation. This separation is carried out in the interface between the polymer and the oxide.
La Figura 3 muestra la ventaja de utilizar el TiO_{2} dopado con nitrógeno en comparación con el TiO_{2} convencional. En ambos casos los materiales fueron sintetizados utilizando la técnica de PLD. En las primeras 13 horas de vida de la célula solar se obtiene una retención de las propiedades fotovoltaicas de hasta un 80% cuando el TiO_{2} es dopado con nitrógeno, mientras que el material no dopado mantiene sólo un 20% de sus propiedades fotovoltaicas iniciales en el mismo período de tiempo (en ambos casos utilizando un filtro UV que corta la longitud de onda UV inferior a 400 nm).Figure 3 shows the advantage of using the TiO2 doped with nitrogen compared to TiO2 conventional. In both cases the materials were synthesized. using the PLD technique. In the first 13 hours of life of the solar cell you get a retention of properties photovoltaic of up to 80% when the TiO_2 is doped with nitrogen, while the undoped material maintains only 20% of its initial photovoltaic properties in the same period of time (in both cases using a UV filter that cuts the length UV wavelength less than 400 nm).
El comportamiento metálico del TiO_{2} dopado en la fase cristalina tipo rutilo se ve reflejado en las curvas IV, utilizadas típicamente para analizar las propiedades de un dispositivo fotovoltaico. Mientras más "cuadrada" sea la curva mayor será el factor de llenado (FF) y mayor la eficiencia de la célula solar donde se utiliza el dispositivo fotovoltaico. Una curva IV-recta indica un comportamiento ohmico, o que el dispositivo fotovoltaico es capaz de transformar lo fotones en corriente y voltaje pero la generación de energía es nula o tiene una eficiencia inaceptable. La Figura 4 refleja lo descrito anteriormente, mostrando las curvas IV de células solares que utilizan el TiO_{2} dopado con nitrógeno y sin dopar (ambos en su fase rutilo). Se puede observar que en el caso del TiO_{2} sin dopar la curva es prácticamente plana (FF < 25%) después de analizar la célula solar en atmósfera inerte durante unas cuantas horas, mientras que en el caso del N-TiO_{2} la curva se mantiene durante muchas horas más. Este comportamiento se atribuye a la extracción de oxígeno (reducción) de la estructura cristalina del TiO_{2} durante los procesos de irradiación continuada en atmósferas inertes.The metallic behavior of the doped TiO_2 in the rutile type crystalline phase it is reflected in curves IV, typically used to analyze the properties of a photovoltaic device The more "square" the curve is the greater the filling factor (FF) and the greater the efficiency of the solar cell where the photovoltaic device is used. A curve IV-straight indicates an ohmic behavior, or that the photovoltaic device is capable of transforming the photons into current and voltage but the power generation is zero or has unacceptable efficiency. Figure 4 reflects the description above, showing the IV curves of solar cells that they use the TiO_2 doped with nitrogen and without doping (both in their rutile phase). It can be seen that in the case of TiO_2 without doping the curve is practically flat (FF <25%) after analyze the solar cell in an inert atmosphere for a few hours, while in the case of N-TiO_ {2} the curve is maintained for many more hours. This behavior is attributed to the extraction of oxygen (reduction) from the structure TiO 2 crystalline during irradiation processes continued in inert atmospheres.
La Figura 5 muestra el comportamiento de las células solares que utilizan el N-TiO_{2} bajo condiciones de irradiación continuada y atmósfera de nitrógeno. Se muestra en cada etapa la correspondiente curva IV. Las curvas IV obtenidas a diferentes etapas del análisis muestran un factor de llenado mayor del 30%. Aun a tiempos de análisis largos la respuesta de la celda solar dopada no presenta un comportamiento ohmico.Figure 5 shows the behavior of the solar cells that use the low N-TiO2 conditions of continuous irradiation and nitrogen atmosphere. Be shows in each stage the corresponding curve IV. IV curves obtained at different stages of the analysis show a factor of filling greater than 30%. Even at long analysis times the answer of the doped solar cell does not exhibit ohmic behavior.
La Figura 6 muestra la comparación de los parámetros de las células solares que utilizan el TiO_{2} y el N-TiO_{2} observados durante las primeras 7 h en funcionamiento. El TiO_{2} sin dopar presenta propiedades fotovoltaicas muy bajas (comportamiento ohmico) en tan solo un par de horas de análisis mientras que el material la célula solar utilizando N-TiO_{2} es claramente superior a su homólogo TiO_{2} sin dopar.Figure 6 shows the comparison of parameters of the solar cells that use the TiO2 and the N-TiO2 observed during the first 7 hours in functioning. TiO_2 without doping has properties Very low photovoltaic (ohmic behavior) in just one pair of hours of analysis while the solar cell material using N-TiO_ {2} is clearly superior to its TiO2 homolog without doping.
La Figura 7 muestra las primeras 50 h de vida de la célula solar utilizando N-TiO_{2}. Observamos que los parámetros como factor de llenado (FF), voltaje (Voc) o densidad de corriente (Jsc) se mantienen razonablemente estables con el tiempo. En algunos casos se incrementan, como en el caso del voltaje, y en otro disminuye un poco, como con la densidad de corriente.Figure 7 shows the first 50 hours of life of the solar cell using N-TiO2. We observe that the parameters such as filling factor (FF), voltage (Voc) or current density (Jsc) remain reasonably stable with time. In some cases they increase, as in the case of voltage, and in another decreases a bit, as with the density of stream.
La Figura 8 muestra esquemáticamente la configuración del dispositivo fotovoltaico de la invención utilizado en una célula solar.Figure 8 schematically shows the configuration of the photovoltaic device of the invention used In a solar cell.
Claims (16)
- a)to)
- deposición por láser pulsado de TiO_{2} sobre un electrodo substrato transparente y conductor tipo óxido de estaño dopado con flúor, donde dicho sustrato se encuentra a una temperatura de entre 400ºC y 600ºC,pulsed laser deposition of TiO2 on a transparent substrate electrode and type conductor fluorine doped tin oxide, where said substrate is found at a temperature between 400ºC and 600ºC,
- b)b)
- adición de una mezcla de gas oxígeno-nitrógeno sobre el material obtenido en la etapa a), donde la relación de presiones parciales de dichos gases es X:Y, siendo X+Y un valor constante de entre 1 y 15 Pa.adding a gas mixture oxygen-nitrogen on the material obtained in the stage a), where the ratio of partial pressures of said gases is X: Y, with X + Y being a constant value between 1 and 15 Pa.
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PCT/ES2010/070339 WO2010133743A1 (en) | 2009-05-21 | 2010-05-20 | Nitrogen-doped nanocrystalline tio2 for photovoltaic applications |
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