WO2012028137A2 - Double-sided solar cell - Google Patents

Double-sided solar cell Download PDF

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Publication number
WO2012028137A2
WO2012028137A2 PCT/DE2011/001622 DE2011001622W WO2012028137A2 WO 2012028137 A2 WO2012028137 A2 WO 2012028137A2 DE 2011001622 W DE2011001622 W DE 2011001622W WO 2012028137 A2 WO2012028137 A2 WO 2012028137A2
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Prior art keywords
metal oxide
layer
solar cell
oxide nanorods
contact
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PCT/DE2011/001622
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German (de)
French (fr)
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WO2012028137A3 (en
Inventor
Lie CHEN
Yang Tang
Martha Ch. Lux-Steiner
Lorenz AÉ
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Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh
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Publication of WO2012028137A2 publication Critical patent/WO2012028137A2/en
Publication of WO2012028137A3 publication Critical patent/WO2012028137A3/en

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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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    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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    • H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
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    • H01L31/074—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a heterojunction with an element of Group IV of the Periodic System, e.g. ITO/Si, GaAs/Si or CdTe/Si solar cells
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    • Y02E10/541—CuInSe2 material PV cells
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Definitions

  • the invention relates to a two-sided solar cell, at least comprising a transparent substrate, on which a TCO layer is arranged as the first contact, on which there is an active layer, which is provided with a further TCO layer as a second contact.
  • Such a two-sided solar cell is described in GB 2 405 030 A.
  • a TCO layer Adjacent to a pn junction, on the one side, a TCO layer is arranged as a front contact, which is arranged on a transparent substrate. On the other side of the pn junction another TCO layer is arranged, which forms the back contact.
  • this solar cell can also be irradiated from the back with light. The two-sided irradiation of light improves the efficiency of the solar cell.
  • the reflectivity at the interface TCO layer / absorber layer is still very high.
  • Applied Physics Letters 93, 053113 (208) reports on the investigation of ZnO nanorod device arrangements with a well-defined morphology as a substrate for solar cells with extremely thin absorber layer (eta solar cells).
  • the ZnO nanorods are covered with ln 2 S3 as the absorber material, on which CuSCN is then located as a hole conductor.
  • nanostructures such as .alpha. are used to improve charge transport in the photoelectrode z. ZnO nanorods and filaments and TiO 2 nanotubes.
  • Appl. Phys. Lett. 96, 073115 (2010) describes a hybrid photoanode in which ZnO nanofibers act as a direct pathway for fast electron transport and ZnO nanoparticles fill in the voids between the filaments, forming a larger surface area for sufficient dye adsorption.
  • ZnO nanostructures are described as efficient antireflection layers.
  • the ZnO nanostructures are needle-shaped, ie they have a tip. By defined parameters when growing the nanorods their length and shape becomes influenced their peak, which is to reduce the reflection.
  • the ZnO nanorods are applied, for example, on silicon, between them is air.
  • WO 2009/116018 A2-both in substrate and in superstrate arrangement-a first transparent conductive layer of this layer has protruding structures of the material of the first-mentioned layer.
  • An Si absorber layer is deposited thereon in accordance with the structure.
  • the object of the invention is now to provide a further two-sided solar cell, which has an improved compared to the prior art or at least comparable efficiency, but less
  • Metal oxide nanorods are arranged with tapered cross section in the direction of the second contact, wherein the base of the metal oxide nanorods with the larger cross section is applied directly to the first contact, and the active layer completely covers the height of the metal oxide nanorods.
  • the nanorods in the active layer By arranging the nanorods in the active layer, the latter is textured, which allows a finely adjustable change in the refractive index of the active layer over its thickness, reduces the unwanted reflection at the TCO layer / active layer interface, and improves the efficiency. The result is a so-called sub-wavelength structure. With this arrangement - in comparison to the prior art - absorber material is saved.
  • the hitherto customary buffer layer between the conductive transparent layer and the active layer which in one
  • the arrangement according to the invention also enables the two-sided irradiation of light into the solar cell.
  • it is intended to form the metal oxide nanorods of ZnO or T1O2 or MgO or ZnMgO.
  • a further embodiment provides for forming the conductive transparent layer and the further transparent layer from one of the following materials FTO or ITO or AZO. Both contact materials should have one
  • the active layer is formed of Si or a chalcogenide semiconductor material (such as CdTe, CIGS) or an organic material. This may be a p-Si layer or a pn junction forming p and n-Si layer.
  • the cross section of the nanorods which tapers in the direction of the metal contact, can change continuously or stepwise.
  • the nanorods have a length of a few hundred nm to a few ⁇ , a Diameter of several tens nm to several hundred nm and a distance from each other from 50 to 2,000 nm.
  • metal oxide nanorods that there is an additional seed layer for the application of the metal oxide nanorods on the conductive transparent layer, by which the growth of the metal oxide nanorods is supported.
  • An additional layer may be located on the TCO layer for the first contact as a template for the application of the metal oxide nanorods.
  • This can be formed, for example, of anodic aluminum oxide (AAO) or a structured photoresist and on the one hand affects the density of the metal oxide nanorods to be applied and, on the other hand, their vertical alignment during growth.
  • AAO anodic aluminum oxide
  • a structured photoresist on the one hand affects the density of the metal oxide nanorods to be applied and, on the other hand, their vertical alignment during growth.
  • next embodiments relate to further optional layers which, by virtue of their special function, are intended to bring about a further improvement in the effect of the active layer comprising metal oxide nanorods according to the invention.
  • an insulating layer is disposed between metal oxide nanorods and active layer formed of, for example, anodic aluminum oxide (AAO) or Al 2 O 3 or a patterned photoresist or MgO, exposing the tip of the metal oxide nanorods.
  • AAO anodic aluminum oxide
  • Al 2 O 3 Al 2 O 3
  • MgO patterned photoresist
  • a passivation layer for example Al 2 O 3 , arranged between metal oxide nanorods and active layer is intended to passivate the surface states of the metal oxide nanorods.
  • the same result can be achieved with a plasma treatment of the grown metal oxide nanorods.
  • Metal oxide nanorods form a Schottky contact.
  • a functional layer is provided, for example, the metal oxide nanorods arranged in a CIGS absorber are covered with a Mo-NaF layer.
  • the nanorods can be applied by known methods according to the prior art. Examples are the following
  • Fig. 1 a SEM image of a ZnO-Nanstäbchen arrangement on a ZnO-AI surface in cross section;
  • Fig. 2 a schematic representation of the invention
  • WO 2009/103286 A2 produced, wherein the production of nanostructured ZnO with a high internal quantum efficiency (IQE) without additional annealing step takes place.
  • IQE internal quantum efficiency
  • FIG. 1 An arrangement of ZnO nanorods in cross-section shown in FIG. 1 serves as the basis for the production of the superstrate solar cell arrangement according to the invention in cross section, as shown in FIG.
  • a conductive transparent layer as the first contact 2 here ZnO: AI with a thickness of 800 nm, arranged.
  • ZnO nanorods 3 with a length of 400 nm, which were produced as described above.
  • These ZnO nanorods 3 have a cross section tapering in the direction of the second contact 5 (from 300 nm to 40 nm).
  • the ZnO nanorods 3 are completely filled with a Si
  • the back contact 5 is formed of AZO with a thickness of 800 nm.
  • the reflection index of the textured Si absorber layer 4 in this superstrate arrangement changes from about 2 at the interface ZnO: Al layer 2 and Si absorber layer 4 to approximately 3.2 at the interface Si absorber layer 4 and second contact 5.
  • a two-sided solar cell according to the invention can be used in a tandem arrangement and in a stacked structure for solar cells.

Abstract

In the case of a double-sided solar cell, which has at least a transparent substrate (1) on which a TCO layer is arranged as first contact (2), on which there is located an active layer (4) which is provided with a further TCO layer as second contact (5), metal oxide nanorods (3) having a cross section tapering in the direction of the second contact (5) are arranged according to the invention in the active layer (4), wherein the base area of the metal oxide nanorods (3) with the larger cross section rests directly against the first contact (2) and the active layer (4) covers the entire height of the metal oxide nanorods (3), wherein the tips of the metal oxide nanorods (3) form point contacts.

Description

Bezeichnung  description
Zweiseitige Solarzelle Two-sided solar cell
Beschreibung description
Die Erfindung betrifft eine zweiseitige Solarzelle, mindestens aufweisend ein transparentes Substrat, auf dem eine TCO-Schicht als erster Kontakt angeordnet ist, auf der sich eine aktive Schicht befindet, die mit einer weiteren TCO-Schicht als zweiter Kontakt versehen ist. The invention relates to a two-sided solar cell, at least comprising a transparent substrate, on which a TCO layer is arranged as the first contact, on which there is an active layer, which is provided with a further TCO layer as a second contact.
Eine derartige zweiseitige Solarzelle ist in GB 2 405 030 A beschrieben. Such a two-sided solar cell is described in GB 2 405 030 A.
Einem pn-Übergang benachbart ist auf der einen Seite eine TCO-Schicht als Frontkontakt angeordnet, der auf einem transparenten Substrat angeordnet ist. Auf der anderen Seite des pn-Übergangs ist eine weitere TCO-Schicht angeordnet, die den Rückkontakt bildet. Damit kann diese Solarzelle auch von der Rückseite mit Licht bestrahlt werden. Das beidseitige Einstrahlen von Licht verbessert den Wirkungsgrad der Solarzelle. Die Reflektivität an der Grenzfläche TCO-Schicht/Absorberschicht ist hierbei aber noch sehr hoch. Adjacent to a pn junction, on the one side, a TCO layer is arranged as a front contact, which is arranged on a transparent substrate. On the other side of the pn junction another TCO layer is arranged, which forms the back contact. Thus, this solar cell can also be irradiated from the back with light. The two-sided irradiation of light improves the efficiency of the solar cell. The reflectivity at the interface TCO layer / absorber layer is still very high.
In Applied Physics Letters 93, 053113 (208) wird über die Untersuchung von ZnO-Nanostäbchen-Anordnungen mit einer gut definierten Morphologie als Substrat für Solarzellen mit extrem dünner Absorberschicht (eta-Solarzellen) berichtet. Dabei sind die ZnO-Nanostäbchen mit ln2S3 als Absorbermaterial bedeckt, auf dem sich dann CuSCN als Löcherleiter befindet. Applied Physics Letters 93, 053113 (208) reports on the investigation of ZnO nanorod device arrangements with a well-defined morphology as a substrate for solar cells with extremely thin absorber layer (eta solar cells). In this case, the ZnO nanorods are covered with ln 2 S3 as the absorber material, on which CuSCN is then located as a hole conductor.
Eine verbesserte Lichteinkopplung in Silizium-Dünnschichtsolarzellen durch texturiertes ZnO wird in FVS Themen 2000, S. 97 ff. beschrieben. Durch die Texturierung wird der optische Lichtweg und die Absorption erhöht, was insbesondere bei einer Superstrat-Solarzelle neben der Transparenz und hohen Leitfähigkeit der TCO-Schicht notwendig ist. Die texturierte Oberfläche der mittels Sputterverfahren hergestellten ZnO-Schichten wird in einem nasschemischen Ätzschritt erzeugt. An improved light coupling in silicon thin-film solar cells by textured ZnO is described in FVS Themen 2000, p. 97 ff. The texturing increases the optical light path and the absorption, which is necessary in particular for a superstrate solar cell in addition to the transparency and high conductivity of the TCO layer. The textured surface the sputtered ZnO layers are produced in a wet chemical etching step.
In den seit 1991 bekannten farbstoffsensitivierten Solarzellen, bei denen ein transparentes, leitfähiges Oxid, dessen Bandlücke zu groß ist, um sichtbares Licht zu absorbieren, durch einen im sichtbaren Wellenlängenbereich absorbierenden Farbstoff sensitiviert wird, werden zur Verbesserung des Ladungstransportes in der Photoelektrode Nanostrukturen verwendet, wie z. B. ZnO-Nanostäbchen und -Fäden sowie TiO2-Nanoröhrchen. In Appl. Phys. Lett. 96, 073115 (2010) wird eine hybride Photoanode beschrieben, bei der ZnO-Nanofäden als direkter Pfad für einen schnellen Elektronentransport dienen und ZnO-Nanoteilchen die Leerräume zwischen den Fäden ausfüllen, wodurch eine größere Oberfläche für eine ausreichende Farbstoff-Adsorption gebildet wird. In The 2nd Joint International Conference on Sustainable Energy and Environment (SEE 2006)" 21-23 November 2006, Bangkok, Thailand, B-024 (O) wird eine farbstoffsensitivierte Solarzelle basierend auf ZnO-Nanostäbchen-Arrays - ohne Nanopartikel - beschrieben. Dabei sind die ZnO-Nanostäbchen mit hexagonalem Querschnitt sehr dicht senkrecht auf ein fluordotiertes SnO2-Substrat aufgewachsen. Mit größer werdender Länge der ZnO-Nanostäbchen vergrößert sich die Oberfläche, mehr Farbstoff wird adsorbiert und der Wirkungsgrad der Solarzelle wird erhöht. Die in In dye-sensitized solar cells known since 1991 in which a transparent conductive oxide whose bandgap is too large to absorb visible light is sensitized by a dye absorbing in the visible wavelength range, nanostructures such as .alpha. Are used to improve charge transport in the photoelectrode z. ZnO nanorods and filaments and TiO 2 nanotubes. In Appl. Phys. Lett. 96, 073115 (2010) describes a hybrid photoanode in which ZnO nanofibers act as a direct pathway for fast electron transport and ZnO nanoparticles fill in the voids between the filaments, forming a larger surface area for sufficient dye adsorption. 21-23 November 2006, Bangkok, Thailand, B-024 (O) describes a dye-sensitized solar cell based on ZnO nanorod arrays - without nanoparticles - in The 2nd Joint International Conference on Sustainable Energy and Environment (SEE 2006) For example, the ZnO nanorods with a hexagonal cross-section are grown very close to a fluorine-doped SnO 2 substrate, and as the length of the ZnO nanorods increases, the surface area increases, more dye is adsorbed, and the efficiency of the solar cell is increased
International Journal of Photoenergy, Volume 2010, Article ID 497095 beschriebene Anordnung weist keine TCO-Schicht auf, auf der die ZnO- Nanostäbchen aufgewachsen sind. Vielmehr sind diese nun direkt auf einem ZnO-Film abgeschieden. Damit sollen die Nachteile verringert werden, die durch die Bildung der Grenzflächen zwischen Nanostäbchen und TCO- Schicht entstehen. International Journal of Photoenergy, Volume 2010, Article ID 497095 has no TCO layer on which the ZnO nanorods are grown. Rather, these are now deposited directly on a ZnO film. This is intended to reduce the disadvantages caused by the formation of interfaces between the nanorod and the TCO layer.
In Nano Lett., Vol. 8, No. 5, 2008, 1501 -1505 sind ZnO-Nanostrukturen als effiziente Antireflexionsschichten beschrieben. Die ZnO-Nanostrukturen sind nadeiförmig ausgebildet, d.h. sie weisen eine Spitze auf. Durch definierte Parameter beim Wachsen der Nanostäbchen wird ihre Länge und die Form ihrer Spitze beeinflusst, wodurch die Reflexion verringert werden soll. Die ZnO-Nanostäbchen sind beispielsweise auf Silizium aufgebracht, zwischen ihnen befindet sich Luft. Bei der in WO 2009/116018 A2 beschriebenen photovoltaischen Zelle - sowohl in Substrat- als auch in Superstrat-Anordnung - weist eine erste transparente leitende Schicht aus dieser Schicht hervorstehende Strukturen aus dem Material der erstgenannten Schicht auf. Eine Si-Absorberschicht ist darauf strukturkonform abgeschieden. In Nano Lett., Vol. 8, no. 5, 2008, 1501-1505, ZnO nanostructures are described as efficient antireflection layers. The ZnO nanostructures are needle-shaped, ie they have a tip. By defined parameters when growing the nanorods their length and shape becomes influenced their peak, which is to reduce the reflection. The ZnO nanorods are applied, for example, on silicon, between them is air. In the photovoltaic cell described in WO 2009/116018 A2-both in substrate and in superstrate arrangement-a first transparent conductive layer of this layer has protruding structures of the material of the first-mentioned layer. An Si absorber layer is deposited thereon in accordance with the structure.
In US 2009/0242029 A1 ist ein photovoltaisches Bauelement in In US 2009/0242029 A1 is a photovoltaic device in
Substratanordnung beschrieben, bei dem die Absorberschicht aus Substrate arrangement described in which the absorber layer of
Halbleitermaterial der Gruppe ll-VI und/oder die Grenzflächenschicht zwischen Absorber- und Fensterschicht Nanopartikel oder gesinterte Semiconductor material of group II-VI and / or the interface layer between absorber and window layer nanoparticles or sintered
Nanopartikel enthält. Die Nanopartikel können verschieden geformt sein, beispielsweise kugelförmig, als Nanofäden oder -Stäbchen, und aus unterschiedlichen Materialien, wie z. B. Materialien der Gruppen M-Vl oder NINA bestehen. Aufgabe der Erfindung ist es nun, eine weitere zweiseitige Solarzelle anzugeben, die einen im Vergleich zum Stand der Technik verbesserten bzw. mindestens vergleichbaren Wirkungsgrad aufweist, aber weniger Contains nanoparticles. The nanoparticles can be shaped differently, for example spherically, as nanofilaments or rods, and made of different materials, such as. B. materials of groups M-Vl or NINA exist. The object of the invention is now to provide a further two-sided solar cell, which has an improved compared to the prior art or at least comparable efficiency, but less
Absorbermate rial benötigt und weniger aufwändig in der Herstellung ist. Erfindungsgemäß wird diese Aufgabe in einer zweiseitigen Solarzelle der eingangs genannten Art dadurch gelöst, dass in der aktiven Schicht Absorbermate rial needed and less expensive to manufacture. According to the invention this object is achieved in a two-sided solar cell of the type mentioned in that in the active layer
Metalloxid-Nanostäbe mit in Richtung zweiten Kontakt sich verjüngendem Querschnitt angeordnet sind, wobei die Grundfläche der Metalloxid- Nanostäbe mit dem größeren Querschnitt direkt am ersten Kontakt anliegt, und die aktive Schicht die Metalloxid-Nanostäbe in ihrer Höhe vollständig bedeckt. Durch die Anordnung der Nanostäbe in der aktiven Schicht wird diese texturiert, wodurch eine fein einstellbare Änderung des Brechungsindex der aktiven Schicht über ihre Dicke ermöglicht, die unerwünschte Reflexion an der Grenzfläche TCO-Schicht/aktive Schicht verringert und der Wirkungsgrad verbessert wird. Es entsteht eine so genannte Subwellenlängen-Struktur. Mit dieser Anordnung wird - im Vergleich zum Stand der Technik - Absorbermaterial eingespart. Die bisher übliche Pufferschicht zwischen der leitenden transparenten Schicht und der aktiven Schicht, die in einer Metal oxide nanorods are arranged with tapered cross section in the direction of the second contact, wherein the base of the metal oxide nanorods with the larger cross section is applied directly to the first contact, and the active layer completely covers the height of the metal oxide nanorods. By arranging the nanorods in the active layer, the latter is textured, which allows a finely adjustable change in the refractive index of the active layer over its thickness, reduces the unwanted reflection at the TCO layer / active layer interface, and improves the efficiency. The result is a so-called sub-wavelength structure. With this arrangement - in comparison to the prior art - absorber material is saved. The hitherto customary buffer layer between the conductive transparent layer and the active layer, which in one
Superstrat-Anordnung die Reflexion zwischen der TCO-Schicht und der aktiven Schicht verringern soll, ist damit nicht mehr notwendig. Die Spitzen der sich in der aktiven Schicht befindlichen Metalloxid-Nanostäbe bilden Punktkontakte. Diese sind eng benachbart zu dem Bereich der Anordnung, in dem die Ladungsträger generiert werden, wodurch der Ladungstransport verbessert wird. Die erfindungsgemäße Anordnung ermöglicht ebenfalls die beidseitige Einstrahlung von Licht in die Solarzelle. Superstrate arrangement to reduce the reflection between the TCO layer and the active layer, so that is no longer necessary. The tips of the metal oxide nanorods in the active layer form point contacts. These are closely adjacent to the region of the array in which the charge carriers are generated, thereby improving charge transport. The arrangement according to the invention also enables the two-sided irradiation of light into the solar cell.
In einer Ausführungsform ist vorgesehen, die Metalloxid-Nanostäbe aus ZnO oder T1O2 oder MgO oder ZnMgO auszubilden. In one embodiment, it is intended to form the metal oxide nanorods of ZnO or T1O2 or MgO or ZnMgO.
Eine weitere Ausführungsform sieht vor, die leitende transparente Schicht und die weitere transparente Schicht aus einem der folgenden Materialien FTO oder ITO oder AZO zu bilden. Beide Kontaktmaterialien sollten einen A further embodiment provides for forming the conductive transparent layer and the further transparent layer from one of the following materials FTO or ITO or AZO. Both contact materials should have one
Widerstand von etwa 10 Ω bis einige 10 Ω aufweisen. Resistance of about 10 Ω to some 10 Ω have.
In einer anderen Ausführungsform ist die aktive Schicht aus Si oder einem Chalkogenidhalbleitermateial (wie z. B. CdTe, CIGS) oder einem organischen Material gebildet. Dabei kann es sich um eine p-Si-Schicht oder einen pn- Übergang bildende p- und n-Si-Schicht handeln. In another embodiment, the active layer is formed of Si or a chalcogenide semiconductor material (such as CdTe, CIGS) or an organic material. This may be a p-Si layer or a pn junction forming p and n-Si layer.
Je nach Anwendung kann sich der in Richtung Metallkontakt verjüngende Querschnitt der Nanostäbe kontinuierlich oder stufenförmig verändern. Die Nanostäbe weisen eine Länge von einigen Hundert nm bis einige μιη, einen Durchmesser von einigen Zehn nm bis einige Hundert nm und einen Abstand zueinander von 50 bis 2.000 nm auf. Depending on the application, the cross section of the nanorods, which tapers in the direction of the metal contact, can change continuously or stepwise. The nanorods have a length of a few hundred nm to a few μιη, a Diameter of several tens nm to several hundred nm and a distance from each other from 50 to 2,000 nm.
Weiterhin ist bei der Anordnung von Metalloxid-Nanostäben vorgesehen, dass sich auf der leitenden transparenten Schicht eine zusätzliche Keimschicht für das Aufbringen der Metalloxid-Nanostäbe befindet, durch die das Wachstum der Metalloxid-Nanostäbe unterstützt wird. Furthermore, it is provided in the arrangement of metal oxide nanorods that there is an additional seed layer for the application of the metal oxide nanorods on the conductive transparent layer, by which the growth of the metal oxide nanorods is supported.
Auf der TCO-Schicht für den ersten Kontakt kann sich eine zusätzliche Schicht als Template für das Aufbringen der Metalloxoid-Nanostäbe befinden. Diese kann beispielsweise aus anodischem Aluminiumoxid (AAO) oder einem strukturierten Photolack gebildet sein und beeinfiusst einerseits die Dichte der aufzubringenden Metalloxid-Nanostäbe und andererseits ihre senkrechte Ausrichtung während des Aufwachsens. An additional layer may be located on the TCO layer for the first contact as a template for the application of the metal oxide nanorods. This can be formed, for example, of anodic aluminum oxide (AAO) or a structured photoresist and on the one hand affects the density of the metal oxide nanorods to be applied and, on the other hand, their vertical alignment during growth.
Die nächsten Ausführungsformen betreffen weitere optionale Schichten, die durch ihre spezielle Funktion eine weitere Verbesserung der Wirkung der erfindungsgemäß Metalloxid-Nanostäbe aufweisenden aktiven Schicht bewirken sollen. The next embodiments relate to further optional layers which, by virtue of their special function, are intended to bring about a further improvement in the effect of the active layer comprising metal oxide nanorods according to the invention.
So ist eine Isolationsschicht zwischen Metalloxid-Nanostäben und aktiver Schicht angeordnet, die beispielsweise aus anodischem Aluminiumoxid (AAO) oder AI2O3 oder einem strukturierten Photolack oder MgO gebildet ist, wobei die Spitze der Metalloxid-Nanostäbe freigelegt ist. Diese Schicht soll einen Kurzschluss zwischen erstem Kontakt und der aktiven Schicht vermeiden. Thus, an insulating layer is disposed between metal oxide nanorods and active layer formed of, for example, anodic aluminum oxide (AAO) or Al 2 O 3 or a patterned photoresist or MgO, exposing the tip of the metal oxide nanorods. This layer should avoid a short circuit between the first contact and the active layer.
Durch eine zwischen Metalloxid-Nanostäben und aktiver Schicht angeordnete Passivierungsschicht, beispielsweise AI2O3, sollen die Oberflächenzustände der Metalloxid-Nanostäbe passiviert werden. Das gleiche Ergebnis kann mit einer Plasmabehandlung der aufgewachsenen Metalloxid-Nanostäbe erreicht werden. Eine andere zusätzliche zwischen Metalloxid-Nanostäben und aktiver Schicht angeordnete Schicht, eine Pufferschicht, dient der besseren Bandanpassung dieser beiden Schichten, insbesondere wenn die aktive Schicht aus einem Chalkogenidhalbleitermaterial gebildet tst.Diese Schicht kann in Abhängigkeit der Materialien für die Metalloxid-Nanostäbe und die aktive Schicht beispielsweise Al203 oder ZnMgO oder CdS sein. A passivation layer, for example Al 2 O 3 , arranged between metal oxide nanorods and active layer is intended to passivate the surface states of the metal oxide nanorods. The same result can be achieved with a plasma treatment of the grown metal oxide nanorods. Another additional layer disposed between metal oxide nanorods and active layer, a buffer layer, serves for better band matching of these two layers, in particular when the active layer is formed from a chalcogenide semiconductor material. This layer may vary depending on the materials for the metal oxide nanorods and the active Layer be for example Al 2 0 3 or ZnMgO or CdS.
In Abhängigkeit des Materials der aktiven Schicht kann diese mit den Depending on the material of the active layer, this can with the
Metalloxid-Nanostäben einen Schottky-Kontakt bilden. Zur Bildung eines ohmschen Kontakts zwischen Metalloxid-Nanostäben und aktiver Schicht ist eine funktionelle Schicht vorgesehen, beispielsweise sind die in einem CIGS- Absorber angeordneten Metalloxid-Nanostäbe mit einer Mo-NaF-Schicht bedeckt. Metal oxide nanorods form a Schottky contact. To form an ohmic contact between metal oxide nanorods and active layer, a functional layer is provided, for example, the metal oxide nanorods arranged in a CIGS absorber are covered with a Mo-NaF layer.
Selbstverständlich kann eine dieser optional vorgesehenen zusätzlichen Schichten mehrere Funktionen erfüllen. Of course, one of these optionally provided additional layers can fulfill several functions.
Die Nanostäbe können mit den dem Stand der Technik nach bekannten Verfahren aufgebracht werden. Beispielhaft seien hierfür folgende The nanorods can be applied by known methods according to the prior art. Examples are the following
Veröffentlichungen erwähnt: Appl. Phys. Lett. 92, 161906 (2008) und WO 2009/103286 A2 betreffend die elektrochemische Deposition sowie Chem. Mater. 2005, 17, 1001 -1006, wo weitere Möglichkeiten für das Aufwachsen von Nanostäben genannt sind. Publications mentioned: Appl. Phys. Lett. 92, 161906 (2008) and WO 2009/103286 A2 concerning electrochemical deposition and Chem. Mater. 2005, 17, 1001 -1006, where further possibilities for the growth of nanorods are mentioned.
Die Erfindung soll in folgendem Ausführungsbetspiel anhand von Figuren näher beschrieben werden. The invention will be described in more detail in the following Ausführungsbetspiel reference to figures.
Dabei zeigen Show
Fig. 1 : eine SEM-Aufnahme einer ZnO-Nanstäbchen-Anordnung auf einer ZnO-AI-Oberfläche im Querschnitt; Fig. 2: eine schematische Darstellung der erfindungsgemäßen Fig. 1: a SEM image of a ZnO-Nanstäbchen arrangement on a ZnO-AI surface in cross section; Fig. 2: a schematic representation of the invention
Anordnung ebenfalls im Querschnitt.  Arrangement also in cross section.
Die ZnO-Nanostäbchen in der in Fig. 1 gezeigten Aufnahme wurden mittels eines Elektrodepositionsverfahrens - wie bereits in der erwähnten The ZnO nanorods in the photograph shown in Fig. 1 were by means of an electrode position method - as already mentioned in the
WO 2009/103286 A2 beschrieben - erzeugt, wobei die Herstellung von nanostrukturiertem ZnO mit einer hohen inneren Quanteneffizienz (IQE) ohne zusätzlichen Temperschritt erfolgt. Bei diesem Elektrodepositionsverfahren wird eine wässrige Lösung aus einem Zn-Salz, beispielsweise Zn(N03>2, und einem Dotiermittel, beispielsweise HNO3 oder NH4NO3, verwendet. WO 2009/103286 A2 - produced, wherein the production of nanostructured ZnO with a high internal quantum efficiency (IQE) without additional annealing step takes place. In this electro-deposition process, an aqueous solution of a Zn salt, such as Zn (N0 3> 2, and a dopant, for example, HNO 3 or NH 4 NO 3, is used.
Eine in Fig. 1 gezeigte Anordnung von ZnO-Nanostäben im Querschnitt dient als Basis für die Herstellung der erfindungsgemäßen Superstrat-Solarzellen- Anordnung im Querschnitt, wie sie in Fig. 2 gezeigt ist. An arrangement of ZnO nanorods in cross-section shown in FIG. 1 serves as the basis for the production of the superstrate solar cell arrangement according to the invention in cross section, as shown in FIG.
Dabei ist auf einem Glassubstrat 1 eine leitende transparente Schicht als erster Kontakt 2, hier ZnO:AI mit einer Dicke von 800 nm, angeordnet. Auf dieser Schicht 2 befinden sich ZnO-Nanostäbe 3 mit einer Länge von 400 nm, die - wie oben beschrieben - erzeugt wurden. Diese ZnO-Nanostäbe 3 weisen einen sich in Richtung zweiten Kontakt 5 verjüngenden (von 300 nm auf 40 nm) Querschnitt auf. Die ZnO-Nanostäbe 3 sind vollständig mit einer Si-In this case, on a glass substrate 1, a conductive transparent layer as the first contact 2, here ZnO: AI with a thickness of 800 nm, arranged. On this layer 2 there are ZnO nanorods 3 with a length of 400 nm, which were produced as described above. These ZnO nanorods 3 have a cross section tapering in the direction of the second contact 5 (from 300 nm to 40 nm). The ZnO nanorods 3 are completely filled with a Si
Schicht 4 bedeckt, die eine Dicke von 500 nm aufweist. Der Rückkontakt 5 ist aus AZO mit einer Dicke von 800 nm gebildet. Layer 4 covered, which has a thickness of 500 nm. The back contact 5 is formed of AZO with a thickness of 800 nm.
Der Reflexionsindex der texturierten Si-Absorberschicht 4 ändert sich in dieser Superstrat-Anordnung von etwa 2 an der Grenzfläche ZnO:AI-Schicht 2 und Si-Absorberschicht 4 auf ca. 3,2 an der Grenzfläche Si-Absorberschicht 4 und zweiten Kontakt 5. The reflection index of the textured Si absorber layer 4 in this superstrate arrangement changes from about 2 at the interface ZnO: Al layer 2 and Si absorber layer 4 to approximately 3.2 at the interface Si absorber layer 4 and second contact 5.
Eine erfindungsgemäße zweiseitige Solarzelle kann in einer Tandem- Anordnung und in einer Stapelstruktur für Solarzellen Anwendung finden. A two-sided solar cell according to the invention can be used in a tandem arrangement and in a stacked structure for solar cells.

Claims

Patentansprüche claims
1. Zweiseitige Solarzelle, mindestens aufweisend ein transparentes Substrat, auf dem eine TCO-Schicht als erster Kontakt angeordnet ist, auf dem sich eine aktive Schicht befindet, die mit einer weiteren TCO-Schicht als zweiter Kontakt versehen ist, 1. Two-sided solar cell, at least comprising a transparent substrate, on which a TCO layer is arranged as a first contact, on which there is an active layer, which is provided with a further TCO layer as a second contact,
dadurch gekennzeichnet, dass characterized in that
in der aktiven Schicht (4) Metalloxid-Nanostäbe (3) mit in Richtung zweiten Kontakt (5) sich verjüngendem Querschnitt angeordnet sind, wobei die Grundfläche der Metalloxid-Nanostäbe (3) mit dem größeren Querschnitt direkt am ersten Kontakt (2) anliegt, und die aktive Schicht (4) die Metalloxid- Nanostäbe (3) vollständig in ihrer Höhe bedeckt, wobei die Spitzen der Metalloxid-Nanostäbe (3) Punktkontakte bilden. in the active layer (4) metal oxide nanorods (3) are arranged in the direction of the second contact (5) of tapered cross-section, wherein the base of the metal oxide nanorods (3) with the larger cross-section directly against the first contact (2), and the active layer (4) completely covers the height of the metal oxide nanorods (3), the tips of the metal oxide nanorods (3) forming point contacts.
2. Zweiseitige Solarzelle nach Anspruch 1 , 2. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
die Metalloxid-Nanostäbe (3) aus ZnO oder T1O2 oder MgO oder ZnMgO gebildet sind. the metal oxide nanorods (3) are formed of ZnO or T1O2 or MgO or ZnMgO.
3. Zweiseitige Solarzelle nach Anspruch 1 , 3. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
die TCO-Schicht für den ersten Kontakt (2) oder den zweiten Kontakt (5) gebildet ist aus einem der folgenden Materialien FTO oder ITO oder AZO. the TCO layer for the first contact (2) or the second contact (5) is formed from one of the following materials FTO or ITO or AZO.
4. Zweiseitige Solarzelle nach Anspruch 1 , 4. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
die aktive Schicht (4) gebildet ist aus Si oder einem the active layer (4) is formed of Si or a
Chalkogenidhalbleitermaterial oder einem organischen Material. Chalcogenide semiconductor material or an organic material.
5. Zweiseitige Solarzelle nach Anspruch 1 , 5. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass der sich in Richtung zweiten Kontakt (5) verjüngende Querschnitt der Metalloxid-Nanostäbe (3) kontinuierlich verändert. characterized in that the continuously tapering cross section of the metal oxide nanorods (3) in the direction of the second contact (5).
6. Zweiseitige Solarzelle nach Anspruch 1 , 6. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
der sich in Richtung zweiten Kontakt (5) verjüngende Querschnitt der Metalloxid-Nanostäbe (3) stufenförmig verändert. the step of tapering in the direction of the second contact (5) cross section of the metal oxide nanorods (3).
7. Zweiseitige Solarzelle nach Anspruch 1 , 7. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
die Metalloxid-Nanostäbe (3) eine Länge von einigen Hundert nm bis einige μηη, einen Durchmesser von einigen Zehn nm bis einige Hundert nm und einen Abstand zueinander von 50 bis 2.000 nm aufweisen. the metal oxide nanorods (3) have a length of a few hundred nm to a few μm, a diameter of several tens nm to several hundreds nm, and a distance from each other of 50 to 2,000 nm.
8. Zweiseitige Solarzelle nach Anspruch 1 und 2, 8. Two-sided solar cell according to claim 1 and 2,
dadurch gekennzeichnet, dass characterized in that
sich auf der TCO-Schicht für den ersten Kontakt (2) eine Keimschicht für das Aufbringen der Metalloxid-Nanostäbe (3) befindet. on the TCO layer for the first contact (2) is a seed layer for the deposition of the metal oxide nanorods (3).
9. Zweiseitige Solarzelle nach Anspruch 1 , 9. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
sich auf der TCO-Schicht für den ersten Kontakt (2) eine zusätzliche Schicht als Template für das Aufbringen der Metalloxid-Nanostäbe (3) befindet. on the TCO layer for the first contact (2) is an additional layer as a template for the application of the metal oxide nanorods (3).
10. Zweiseitige Solarzelle nach Anspruch 1 , 10. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
zwischen Metalloxid-Nanostäben (3) und aktiver Schicht (4) eine between metal oxide nanorods (3) and active layer (4) a
Isolationsschicht angeordnet ist, wobei die Spitze der Metalloxid-Nanostäbe (3) freigelegt ist. Insulation layer is arranged, wherein the tip of the metal oxide nanorods (3) is exposed.
11. Zweiseitige Solarzelle nach Anspruch 1 , 11. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass zwischen Metalloxid-Nanostäben (3) und aktiver Schicht (4) eine characterized in that between metal oxide nanorods (3) and active layer (4) a
Passivierungsschicht angeordnet ist. Passivation layer is arranged.
12. Zweiseitige Solarzelle nach Anspruch 1 , 12. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
zwischen Metalloxid-Nanostäben (3) und aktiver Schicht (4) eine Pufferschicht zur Verbesserung der Bandanpassung dieser beiden Schichten angeordnet ist. between metal oxide nanorods (3) and active layer (4) a buffer layer for improving the band matching of these two layers is arranged.
13. Zweiseitige Solarzelle nach Anspruch 1 , 13. Two-sided solar cell according to claim 1,
dadurch gekennzeichnet, dass characterized in that
zwischen Metalloxid-Nanostäben (3) und aktiver Schicht (4) eine Schicht zur Ausbildung eines ohmschen Kontaktes angeordnet ist. between metal oxide nanorods (3) and active layer (4) a layer for forming an ohmic contact is arranged.
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