ES2720596T3 - Subcélula para su utilización en una célula solar multiunión - Google Patents

Subcélula para su utilización en una célula solar multiunión Download PDF

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ES2720596T3
ES2720596T3 ES10849171T ES10849171T ES2720596T3 ES 2720596 T3 ES2720596 T3 ES 2720596T3 ES 10849171 T ES10849171 T ES 10849171T ES 10849171 T ES10849171 T ES 10849171T ES 2720596 T3 ES2720596 T3 ES 2720596T3
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subcell
gaas
solar cell
layer
zsbz
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Rebecca Elizabeth Jones
Homan Bernard Yuen
Ting Liu
Pranob Misra
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Solar Junction Corp
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Solar Junction Corp
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    • 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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    • H01L31/03046—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP
    • H01L31/03048—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP comprising a nitride compounds, e.g. InGaN
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    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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Abstract

Subcélula para su utilización en una célula solar multiunión, que comprende: una capa Ga1-xInxNyAs1-y-zSbz (220), en la que los valores de contenido para x, y, y z se encuentran en los rangos de composición siguientes: 0,07 <= x <= 0,18, 0,025 <= y <= 0,04 y 0,001 <= z <= 0,03; un emisor (26), un campo en superficie delantero opcional (28) y un campo en superficie trasero opcional (30); donde la capa Ga1-xInxNyAs1-y-zSbz (220) se empareja reticularmente de forma sustancial a un sustrato GaAs o a un sustrato Ge; donde la capa Ga1-xInxNyAs1-y-zSbz (220) presenta una banda prohibida en el rango de 0,9 - 1,1 eV; donde, cuando se expone a una iluminación de 1 sol AM 1.5D, la subcélula presenta una tensión en circuito abierto superior a 0,30 V; y una corriente de cortocircuito superior a 13 mA/cm cuando se expone a una iluminación de 1 sol AM1.5D con un filtro que bloquea toda la luz por encima de la banda prohibida GaAs.

Description

DESCRIPCIÓN
Subcélula para su utilización en una célula solar multiunión
REFERENCIAS CRUZADAS A SOLICITUDES RELACIONADAS
[0001] NO APLICABLE
DECLARACIÓN SOBRE DERECHOS DE INVENCIONES OBTENIDAS MEDIANTE INVESTIGACIÓN O DESARROLLO FINANCIADOS POR EL GOBIERNO FEDERAL
[0002] NO APLICABLE
REFERENCIA A UN APÉNDICE DE "LISTA DE SECUENCIAS", TABLA O LISTA DE PROGRAMA INFORMÁTICO PRESENTADOS EN UN DISCO COMPACTO
[0003] NO APLICABLE
ESTADO DE LA TÉCNICA
[0004] La presente invención se refiere a una subcélula para su utilización en células solares multiunión y, en particular, a células solares de alta eficiencia formadas por aleaciones semiconductoras III-V.
[0005] Se sabe que las células solares multiunión obtenidas principalmente a partir de aleaciones semiconductoras III-V producen eficiencias de células solares que sobrepasan las eficiencias de otros tipos de materiales fotovoltaicos. Dichas aleaciones son combinaciones de elementos extraídos de las columnas III y V de la tabla periódica estándar, que de ahora en adelante serán identificados por su símbolo, nombre y abreviatura químicos estándar. (Los expertos en la materia pueden identificar su clase de propiedades semiconductoras por clase sin referencia específica a su columna). Las altas eficiencias de estas células solares hacen que sean atractivas para los sistemas fotovoltaicos de concentración terrestre y los sistemas pensados para funcionar en el espacio exterior. Se ha informado de células solares multiunión con eficiencias que superan un 40 % en concentraciones equivalentes a varios cientos de soles. Los dispositivos de más alta eficiencia conocidos presentan tres subcélulas, consistiendo cada una de las subcélulas en una unión p-n funcional y otras capas, tales como capas de campo en superficie delanteras y traseras. Estas subcélulas se conectan a través de uniones túnel y las capas dominantes, bien se emparejan mediante una estructura reticular con el sustrato subyacente, bien se hacen crecer sobre capas metamórficas. Los dispositivos y diseños con emparejamiento mediante estructura reticular son deseables, puesto que han demostrado ser fiables y porque utilizan menos material semiconductor que las células solares metamórficas, que requieren capas buffer relativamente gruesas para adaptarse a las diferencias en los parámetros de red de los diversos materiales. Tal y como se expone más detalladamente en la solicitud de patente estadounidense n.° 12/217818, titulada "GaInNAsSb Solar Cells Grown by Molecular Beam Epitaxy," incorporándose dicha solicitud como referencia en la presente memoria, una capa hecha a partir de material GaInNAsSb para crear una tercera unión que presenta una banda prohibida de aproximadamente 1,0 eV ofrece un enfoque alentador para mejorar la eficiencia de las células multiunión. No obstante, deben tenerse en cuenta mejoras en la célula descrita en dicha solicitud.
[0006] La eficiencia más alta conocida, las células solares con estructura reticular normalmente incluyen una pila monolítica de tres uniones p-n funcionales o subcélulas, que se hacen crecer de manera epitaxial en un sustrato de germanio (Ge). La subcélula superior se ha obtenido a partir de (Al)GaInP, la intermedia a partir de (In)GaAs y la unión inferior incluía el sustrato Ge. (La nomenclatura anterior para una aleación III-V, en la que se muestra un elemento constituyente entre paréntesis, indica una condición de variabilidad donde dicho elemento particular puede ser cero). Esta estructura no es óptima en términos de eficiencia, ya que la unión inferior puede generar aproximadamente el doble de corriente de cortocircuito que las dos uniones superiores, tal y como se expone en J.F. Geisz et al., "Inverted GaInP / (In)GaAs / InGaAs triple-junction solar cells with low-stress metamorphic bottom junctions," Actas del 33° congreso IEEE PVSC Photovoltaics Specialists, 2008. Esta capacidad de corriente adicional se desperdicia, puesto que la corriente neta debe ser uniforme a través de la pila completa, una característica de diseño conocida como coincidencia de corriente.
[0007] En la exposición de la solicitud de patente estadounidense n.° 12/217,818 mencionada anteriormente, se demostró que un material que está sustancialmente emparejado reticularmente a Ge O GaAs con una banda prohibida de alrededor de 1,0 eV podría utilizarse para crear una célula solar de triple unión con eficiencias superiores a las de la estructura descrita anteriormente mediante la sustitución de la unión Ge inferior con una unión hecha de un material diferente que produce una tensión superior.
[0008] Además, se ha propuesto que la utilización de este material de 1 eV pueda considerarse como una cuarta unión para aprovechar la parte completa del espectro que se encuentra entre 0,7 eV (la banda prohibida del germanio) y 1,1 eV (el extremo superior del rango de bandas prohibidas de la capa de ~ 1 eV). Véase, por ejemplo, S. R. Kurtz, D. Myers y J. M. Olson, "Projected Performance of Three and Four-Junction Devices Using GaAs and GalnP," congreso 26° IEEE Photovoltaics Specialists, 1997, pp. 875-878. Ga1-xInxNyAs1-y ha sido identificado como dicho material de 1 eV, pero no se han alcanzado corrientes lo suficientemente altas como para emparejarse con las demás subcélulas; véase, por ejemplo, A. J. Ptak et al., Journal of Applied Physics 98 (2005) 094501. Esto ha sido atribuido a bajas distancias de difusión de los portadores minoritarios, que evitan la recogida eficaz de fotoportadores. El diseño de las subcélulas solares compuestas por galio, indio, nitrógeno, arsénico y diversas concentraciones de antimonio (GaInNAsSb) se ha investigado con el resultado expuesto de que el antimonio es útil en la disminución de la rugosidad de superficie y que permite el crecimiento con unas temperaturas de sustrato superiores en los casos en que el recocido no es necesario, pero los investigadores informaron de que el antimonio, incluso en concentraciones pequeñas es fundamental que se evite ya que es perjudicial para el rendimiento adecuado del dispositivo. Véase Ptak et al., "Effects of temperature, nitrogen ion, and antimony on wide depletion width GaInNAs," Journal of Vacuum Science Technology B 25(3) mayo/junio de 2007 pp. 955-959. Los dispositivos analizados en dicho artículo presentan corrientes de cortocircuito demasiado bajas para integrarse en células solares multiunión. Sin embargo, se sabe que Ga1-xlnxNyAs1-y-zSbz con un 0,05^x^0,07, 0,01^y^0,02 y 0,02^z^0,06 pueden utilizarse para producir un material con estructura reticular con una banda prohibida de aproximadamente 1 eV que puede proporcionar suficiente corriente como para integrarse en una célula solar multiunión. Sin embargo, las tensiones generadas por las subcélulas que contienen este material no han sobrepasado 0,30 V con 1 sol de iluminación. Véase D. B. Jackrel et al., Journal of Applied Physics 101 (114916) 2007. Por lo tanto, una célula solar de tripe unión con este material como subcélula inferior solamente ha resultado ser una pequeña mejora sobre una célula solar de triple unión análoga con una subcélula inferior de Ge, que produce una tensión en circuito abierto de aproximadamente 0,25 V. Véase H. Cotal et al., Energy and Environmental Science 2 (174) 2009. Se necesita un material que se empareje reticularmente a Ge y GaAs con una banda prohibida de alrededor de 1 eV que produce una tensión en circuito abierto superior a 0,30 V y suficiente corriente como para emparejar las subcélulas (Al)InGaP y (In)GaAs. Dicho material también sería ventajoso como subcélula en células solares de alta eficiencia con 4 o más uniones. En R. Kudrawiec, Applied Physics Letters 88, 221113 (2006), se ha aplicado la espectroscopia de electrorreflectancia sin contacto (CER, por sus siglas en inglés) para analizar las transiciones ópticas en un único pozo cuántico (QW, por sus siglas en inglés) de Ga0.gIn0.1N0.027As0.g73-xSbx/GaAs con un contenido de antimonio de entre un 0 % y un 5,4 %.
RESUMEN DE LA INVENCIÓN
[0009] La invención da a conocer una subcélula para su utilización en una célula solar multiunión, una célula solar multiunión y un procedimiento de fabricación de la subcélula según se establece en las reivindicaciones adjuntas.
BREVE DESCRIPCIÓN DE LOS DIBUJOS
[0010]
La figura 1A es un corte transversal esquemático de una célula solar de tres uniones que incorpora la invención
La figura 1B es un corte transversal esquemático de una célula solar de cuatro uniones que incorpora la invención.
La figura 2A es un corte transversal esquemático de una subcélula GaInNAsSb de acuerdo con la invención. La figura 2B es un corte transversal esquemático detallado que ilustra una subcélula GaInNAsSb de ejemplo. La figura 3 es un gráfico que muestra la eficiencia frente a la energía de banda prohibida de subcélulas formadas a partir de diferentes materiales de aleación, para su comparación.
La figura 4 es un gráfico que muestra la corriente de cortocircuito (Jsc) y la tensión en circuito abierto (Voc) de subcélulas formadas a partir de diferentes materiales de aleación, para su comparación.
La figura 5 es un gráfico que muestra la fotocorriente como una función de la tensión para una célula solar de triple unión que incorpora una subcélula de acuerdo con la invención, con iluminación AM1.5D de 1 sol. La figura 6 es un gráfico que muestra la fotocorriente como función de la tensión para una célula solar de triple unión que incorpora una subcélula de acuerdo con la invención, con iluminación AM1.5D equivalente a 523 soles.
La figura 7 es un gráfico de la corriente de cortocircuito (Jsc) y la tensión en circuito abierto (Voc) de subcélulas con Sb bajo, In mejorado y N GaInNAsSb distinguidas por la presión transmitida a la película por el sustrato.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓN
[0011] La figura 1A es un corte transversal esquemático que muestra un ejemplo de una célula solar de triple unión 10 de acuerdo con la invención, que consiste fundamentalmente en una subcélula con Sb bajo, In mejorado y N GaInNAsSb 12 adyacente a Ge, GaAs u otro sustrato compatible de cualquier otra forma 14 con una subcélula superior 16 de (Al)InGaP y una subcélula intermedia 18 con la utilización de (In)GaAs. La unión túnel 20 se encuentra entre las subcélulas 16 y 18, mientras que la unión túnel 22 se encuentra entre las subcélulas 18 y 12. Cada una de las subcélulas 12, 16, 18 comprende diversas capas asociadas, incluidas campo en superficie delanteras y traseras, un emisor y una base. El material de subcélula indicado (p.ej., (In)GaAs) forma la capa de base y puede o puede no formar las otras capas.
[0012] Las subcélulas con Sb bajo, In mejorado y N GaInNAsSb también pueden incorporarse en células solares multiunión con cuatro o más uniones sin desviarse del espíritu y alcance de la invención. En la figura 1B, se muestra una de dichas células solares con cuatro uniones 100 con una subcélula específica con Sb bajo, In mejorado y N GaInNAsSb 12 como tercera unión, así como con una subcélula superior 16 de (Al)InGaP, una segunda subcélula 18 de (In)GaAs y una subcélula inferior 140 de Ge, que también se incorpora en un sustrato de germanio (Ge). Cada una de las subcélulas 16, 18, 12, 140 está separada por respectivas uniones túnel 20, 22, 24, y cada una de las subcélulas 16, 18, 12, 140 puede comprender diversas capas asociadas, incluidas campo en superficie delanteras y traseras opcionales, un emisor y una base. El material de subcélula indicado (p. ej., (In)GaAs) forma la capa de base y puede o puede no formar las otras capas.
[0013] A modo de ilustración adicional, la figura 2A es un corte transversal esquemático con más detalle de una subcélula GaInNAsSb 12, de acuerdo con la invención. La subcélula con Sb bajo, In mejorado y N GaInNAsSb 12 se caracteriza, por lo tanto, por su utilización de Sb bajo, In mejorado y N GaInNAsSb como capa de base 220 en la subcélula 12. Otros componentes de la subcélula GaInNAsSb 12, incluidos un emisor 26, un campo en superficie delantero 28 y un campo en superficie trasero opcionales 30, son preferiblemente aleaciones III-V, incluyendo, a modo de ejemplo, GaInNAs(Sb), (In)(Al)GaAs, (Al)InGaP o Ge. La base con Sb bajo, In mejorado y N GaInNAsSb 220 puede, bien ser de tipo p o de tipo n, con un emisor 26 del tipo contrario.
[0014] Para determinar el efecto de Sb en el rendimiento de la subcélula con In mejorado y N GaInNAsSb, se investigaron varias subcélulas del tipo (12) de la estructura mostrada en la figura 2B. La figura 2B es un ejemplo representativo de la estructura más general 12 de la figura 2A. Las capas de base 220 sin Sb, con Sb bajo (0,001 < z < 0,03) y con Sb alto (0,03 < z < 0,06) fueron desarrolladas mediante crecimiento epitaxial por haces moleculares y fueron emparejadas reticularmente de forma sustancial a un sustrato GaAs (no mostrado). Estas composiciones de aleación fueron verificadas mediante espectometría de masas de iones secundarios. Las subcélulas 12 fueron sometidas a un recocido térmico, procesado con procesamiento de células solares generalmente conocido y, a continuación, medidas con el espectro AM1.5D (1 sol) por debajo de un filtro que bloqueaba toda la luz por encima de la banda prohibida de GaAs. Este filtro era adecuado porque una subcélula GaInNAsSb 12 está normalmente por debajo de una subcélula (In)GaAs en una pila multiunión (p. ej., figuras 1A y 1B) y, por lo tanto, la luz de energías elevadas no alcanzará la subcélula 12.
[0015] La figura 3 muestra las eficiencias producidas por las subcélulas 12 desarrolladas con diferentes fracciones de Sb como una función de sus bandas prohibidas. Las concentraciones de indio y de nitrógeno eran de rangos entre 0,07 y 0,18, y entre 0,025 y 0,04, respectivamente. Puede observarse que las subcélulas con Sb bajo, In mejorado y N GaInNAsSb (representadas por triángulos) presentan eficiencias de subcélula sistemáticamente más elevadas que las otras dos candidatas (representadas por rombos y cuadrados). Esto se debe a la combinación de capacidades de tensión elevada y de corriente elevada en los dispositivos con Sb bajo, In mejorado y N GaInNAsSb. (Véase la figura 4). Como puede observarse en la figura 4, tanto los dispositivos con concentración baja y elevada de Sb presentan suficiente corriente de cortocircuito para emparejarse con subcélulas (Al)InGaP de alta eficiencia y con subcélulas (In)GaAs (> 13 mA/cm2 con el espectro AM1.5D filtrado) y, por lo tanto, pueden utilizarse en células solares de tres uniones o de cuatro uniones 10, 100 sin reducir la corriente total a través de la célula completa. Este emparejamiento de corriente es esencial para conseguir una eficiencia elevada. Los dispositivos sin Sb presentan eficiencias relativamente elevadas de subcélula debido a sus tensiones elevadas en circuito abierto, pero sus corrientes de cortocircuito son demasiado bajas para las células solares multiunión de alta eficiencia, como se muestra en la figura 4.
[0016] La figura 4 también confirma que Sb presenta un efecto perjudicial en la tensión, como se había informado previamente para otras composiciones de aleación. No obstante, a diferencia de lo que se había informado previamente para otras composiciones de aleación, la adición de antimonio NO disminuye la corriente de cortocircuito. Las subcélulas de tipo Sb bajo presentan aproximadamente tensiones en circuito abierto unos 100 mV superiores que las subcélulas de tipo Sb alto. Para ilustrar el efecto de esta mejora, se ha descubierto que una célula solar de triple unión 10 con una tensión en circuito abierto de 3,1 V presenta una eficiencia relativa un 3,3 % superior en comparación con una célula idéntica por lo demás con una tensión en circuito abierto de 3,0 V. Por lo tanto, la inclusión de Sb en células solares de GaInNAs(Sb) es necesaria para producir suficiente corriente para una célula solar de alta eficiencia, pero sólo mediante la utilización de Sb bajo (0,1-3 %) pueden alcanzarse tanto tensiones elevadas como corriente elevadas.
[0017] La presión de compresión mejora la tensión en circuito abierto de las subcélulas con Sb bajo, In mejorado y N GaInNAsSb 10, 100. Más específicamente, las capas con Sb bajo, In mejorado y N GaInNAsSb 220 que presentan un parámetro de red más grande que el de un sustrato GaAs o Ge cuando se relajan completamente (<0,5 % más grande) y, por lo tanto, se encuentran bajo presión de compresión cuando se desarrollan pseudomórficamente en esos sustratos. También proporcionan mejor rendimiento de dispositivo que las capas con un parámetro de red completamente relajado y más pequeño (con tensión de rotura).
[0018] La figura 7 muestra la corriente de cortocircuito y la tensión en circuito abierto de subcélulas con Sb bajo, In mejorado y N GaInNAsSb desarrolladas en sustratos de GaAs con presión de compresión (triángulos) y tensión de rotura (rombos). Puede observarse que las subcélulas con presión de compresión presentan constantemente tensiones en circuito abierto superiores que las que tienen tensión de rotura.
[0019] Las subcélulas con Sb bajo, In mejorado y N GaInNAsSb con presión de compresión se han integrado con éxito en células solares multiunión de alta eficiencia. La figura 5 muestra una curva de corriente-tensión de una célula solar de triple unión de la estructura de la figura 1A con iluminación AM1.5D equivalente a 1 sol. La eficiencia de este dispositivo es de un 30,5 %. La figura 6 muestra la curva de corriente-tensión de la célula solar de triple unión con una concentración equivalente a 523 soles, con una eficiencia de un 39,2 %.
[0020] La invención se ha explicado con referencia a modos de realización específicos. Otros modos de realización serán evidentes para los expertos en la materia. Por lo tanto, no se pretende que la invención se limite, con la excepción de cuando lo indiquen las reivindicaciones adjuntas.

Claims (5)

REIVINDICACIONES
1. Subcélula para su utilización en una célula solar multiunión, que comprende:
una capa Ga-iJnxNyAs-i-y-zSbz (220), en la que
los valores de contenido para x, y, y z se encuentran en los rangos de composición siguientes: 0,07 < x < 0,18, 0,025 < y < 0,04 y 0,001 < z < 0,03;
un emisor (26), un campo en superficie delantero opcional (28) y un campo en superficie trasero opcional (30);
donde la capa Ga-iJnxNyAs-i-y-zSbz (220) se empareja reticularmente de forma sustancial a un sustrato GaAs o a un sustrato Ge;
donde la capa Ga-iJnxNyAs-i-y-zSbz (220) presenta una banda prohibida en el rango de 0,9 -1,1 eV; donde, cuando se expone a una iluminación de 1 sol AM 1.5D, la subcélula presenta una tensión en circuito abierto superior a 0,30 V; y
una corriente de cortocircuito superior a 13 mA/cm cuando se expone a una iluminación de 1 sol AM1.5D con un filtro que bloquea toda la luz por encima de la banda prohibida GaAs.
2. Subcélula de acuerdo con la reivindicación 1, donde el parámetro de red de la capa Ga-iJnxNyAs-i-y-zSbz cuando se desarrolla en una capa de sustrato GaAs o Ge es hasta un 0,5 % superior que el parámetro de red de GaAs o Ge, y donde la capa Ga-iJnxNyAs-i-y-zSbz tiene presión por compresión.
3. Célula solar multiunión que incluye la subcélula de la reivindicación 1, donde la subcélula de la reivindicación 1 está dispuesta como primera subcélula en el sustrato GaAs o Ge.
4. Célula solar multiunión de acuerdo con la reivindicación 3, donde la célula solar multiunión es una célula solar de triple unión.
5. Procedimiento de fabricación de la subcélula de la reivindicación 1, que comprende:
el desarrollo de la capa Ga-iJnxNyAs-i-y-zSbz (220) mediante crecimiento epitaxial por haces moleculares y donde la subcélula se somete a un recocido térmico.
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