EP1261990A1 - Flexible metal substrate for cis solar cells, and method for producing the same - Google Patents

Flexible metal substrate for cis solar cells, and method for producing the same

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Publication number
EP1261990A1
EP1261990A1 EP01911618A EP01911618A EP1261990A1 EP 1261990 A1 EP1261990 A1 EP 1261990A1 EP 01911618 A EP01911618 A EP 01911618A EP 01911618 A EP01911618 A EP 01911618A EP 1261990 A1 EP1261990 A1 EP 1261990A1
Authority
EP
European Patent Office
Prior art keywords
nickel
copper foil
layer
molybdenum
tungsten
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01911618A
Other languages
German (de)
French (fr)
Inventor
Klaus Kalberlah
Thomas Hoffmann
Klaus Jacobs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CIS Solartechnik GmbH and Co KG
Original Assignee
CIS Solartechnik GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10005680A external-priority patent/DE10005680B4/en
Priority claimed from DE10006823A external-priority patent/DE10006823C2/en
Application filed by CIS Solartechnik GmbH and Co KG filed Critical CIS Solartechnik GmbH and Co KG
Publication of EP1261990A1 publication Critical patent/EP1261990A1/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L31/036—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 characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—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 characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • H01L31/03928—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 characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L31/0256—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 characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L31/036—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 characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a flexible metallic substrate for CIS solar cells and methods for the production thereof.
  • Thin-film solar modules represent the latest state of development.
  • layers of high-purity silicon, cadmium telluride or copper indium selenide / sulfur (abbreviated to CIS) of less than 1 ⁇ m thickness are usually vapor-deposited onto glass.
  • the CIS technology is particularly interesting because of its environmental compatibility and the lack of degradation (declining effectiveness due to aging).
  • the CIS layer is usually deposited on glass, which was usually only sputter-coated with molybdenum.
  • rolled copper tape is problematic in that it absorbs a number of contaminants through the smelting process. Although it is subjected to electrolytic refining, the purities of 99.99% which can be achieved must be regarded as "heavily contaminated" in the sense of solar semiconductor technology. Although oxygen-free qualities are available, they still contain an undetermined number of others, in the sense of Semiconductor technology with no minor additions.
  • the copper strip must be annealed during the rolling process after each rolling pass. Licher further contamination of the copper surface. Thinly rolled copper strip is therefore once relatively expensive and, secondly, contains impurities which prove to be disruptive when a CIS layer is applied.
  • a fundamental disadvantage of copper is also that the thermal expansion coefficient of the crystalline CIS layer is so different from that of the copper strip that it is easy to crack in the CIS during the heat treatment that is required after the application of the CIS layer. Layer comes, with which every photovoltaic function is destroyed.
  • molybdenum foil has about four times the price of copper tape. Its use, probably because of the impurities it contains, has not gone beyond laboratory tests.
  • Plastic films for CIS deposition have also become known.
  • the selection of sufficiently high-temperature-resistant materials causes considerable effort.
  • such foils naturally have to be made electrically conductive by ITO / TCO layers, which is usually done by vacuum deposition, which increases the costs considerably.
  • Chromium-nickel steel foil which has also already been proposed, is also unsuitable, since it tends to absorb hydrogen, which forms bubbles on the surface of the foil, which lead to “pin holes” when the CIS layer is deposited , which makes it easier to apply later transparent cover layer leads to short circuits, which make the solar cell unusable.
  • the invention has for its object to provide a metallic substrate for a flexible, ribbon-shaped solar cell and method for its production, which allow the galvanic application of the CIS layer and thus do not require vacuum technology with which the diffusion of ions of the substrate into the CIS layer is prevented, however.
  • the substrate should be insensitive to mechanical (bending of the cell) and thermal influences on the solar cell.
  • a ribbon-shaped copper foil is then used as the carrier material.
  • the substrate is created by applying a layer structure to the carrier material from a base layer made of chromium, nickel or nickel-iron and a contact layer made from molybdenum, tungsten or palladium or a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy or only from a contact layer made of a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy.
  • the layer sequence can be generated in the specified order by galvanic deposition.
  • the layer of molybdenum, tungsten or palladium or a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy takes over the "mediation" between the very different thermal expansion coefficients of copper / nickel and CIS, while nickel or nickel Iron significantly increases the strength of the layer composite and represents a diffusion barrier against copper ions has a very low coefficient of thermal expansion similar to that of the CIS layer, on the other hand it has a high modulus of elasticity, which is able to absorb the stresses between the layers below and above it with different expansion.
  • a layer of tungsten behaves similarly, ie it shows high elasticity at low thermal expansion.
  • the layer structure thus represents a suitable substrate that can only be produced using the strip galvano-chemical process and that despite the high costs of molybdenum, tungsten and palladium or the nickel-molybdenum, nickel-tungsten or nickel -Palladium alloy is inexpensive overall because of the low layer thicknesses.
  • Copper foil has the advantage that it is flexible and cheaper than other metal foils.
  • the conductivity, which is also good, is not of great importance, since photovoltaically generated current has a low current density.
  • Copper alloys which have a lower conductivity but have other advantages can therefore also be used.
  • the heat resistance of pure copper is very low, so that without further measures, mechanical stresses during the subsequent annealing process can damage the thin CIS layer.
  • copper ions are extremely mobile, so that they would migrate into the CIS layer in an uncontrolled amount during the tempering process, but also at the temperature of use of the solar cells.
  • the thermal expansion coefficient of copper is so different from that of the crystalline CIS layer that under the influence of temperature, crack formation in the thin, overlying CIS absorber layer can be expected, which in turn nullifies any photovoltaic function.
  • a chromium, nickel or nickel-iron base layer is first applied, which serves as a diffusion barrier, as an adjustment with regard to the coefficient of expansion and as an adhesive layer for the subsequent layers.
  • the nickel-iron layer is known as the so-called KOVAR or INVAR alloy. Chromium, nickel or nickel-iron can be applied by electroplating.
  • the subsequent contact layer consists of molybdenum, palladium or tungsten or a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy, which can also be applied by electroplating.
  • Another variant is the sole deposition of a nickel-palladium, nickel-molybdenum or nickel-tungsten alloy on the copper foil, which also serves as a diffusion barrier and as a mediation layer for the CIS layer.
  • the electroplating of a molybdenum layer is little known so far, but it is possible as an alloy deposit together with nickel, just like nickel-palladium or nickel-tungsten.
  • Layers of palladium, nickel-palladium, or tungsten or tungsten-palladium are in themselves a diffusion barrier against copper, but the expensive noble metals can be applied galvanically in a lower layer thickness and with better adhesion and without contamination of the baths by copper, if at least a thin layer of nickel is previously deposited on the copper foil.
  • Molybdenum is not able to act as a diffusion barrier for copper and therefore requires a nickel layer with a certain minimum thickness as a base.
  • the direct contact of a pure nickel layer with the CIS layer must be avoided because this would form CIS-nickel complexes, ie pure CIS would no longer be available for the crystalline structure.
  • the copper foil should have a surface roughness that is as low as possible, but in order to maximize the later light absorption, the surface area can be increased by bulges being introduced during the manufacturing process. As a result, the light absorption and thus the total output is increased in the case of diffuse radiation impinging on the solar cell.
  • the CIS layer can then be galvanically applied to the carrier material with the substrate layers in a known manner, so that no vacuum systems are required.
  • the CIS layer is then activated in a heat treatment process. Copper foil produced by electrolytic deposition is advantageously used as the carrier material.
  • Electrolytically deposited copper foil which has traditionally been used exclusively for the manufacture of printed circuit boards, has a number of advantages which have hitherto not been used in other applications or which are not in demand there and which prove to be relevant here.
  • Electrolytically deposited copper foil is namely produced with a certain roughness for the production of printed circuit boards.
  • Rolled copper strip also has a certain roughness. Such roughness is advantageous for further processing, namely for bonding, but would be disadvantageous for solar cells.
  • Electrolytically deposited copper foil on the other hand, can also be produced with very little roughness, which is a great advantage for solar cells.
  • the copper foil is produced as an endless strip by deposition from an electrolytic bath. Components can be added to the bath, the deposits of which in the copper foil increase the tensile strength and / or temperature resistance and / or reduce the coefficient of expansion of the copper foil, for example nickel. Additionally or alternatively, the copper foil can be provided with further metallic layers after the first deposition process by further galvanic treatment.
  • Suitable bath additives for simultaneous deposition are e.g. B. those that a deposition of nickel, zinc, tin and. effect.
  • Nickel in particular causes the tensile strength of the copper foil to increase, which would otherwise be lost in the subsequent heat treatment processes. Copper foil with a certain nickel content then has the effect that the following base layer can be made much thinner and adheres better.
  • a subsequent layer build-up by galvanic deposition can be, for example, copper foil / nickel or copper foil / (nickel iron).
  • electrolytically deposited copper foil for the construction of flexible CIS solar cells has various advantages.
  • the foil can also be produced in a high degree of purity, which, however, did not play a role for the previous application in printed circuit board manufacture and was not used there.
  • the price for electrodeposited, thin copper foils is no higher than for comparable rolled copper strips.
  • the copper foil In contrast to copper foil, which is used for the printed circuit board industry, the copper foil is manufactured with a low surface roughness. To maximize the later light absorption, the surface area can be increased by bulging during the deposition without any additional manufacturing effort. The dimension of these bulges is macroscopic. Such, e.g. B. hemispherical bulges in the order of about 2 mm can be realized by appropriate design of the separation drum. As a result, the light absorption and thus the cell Efficiency increased. In addition, the bulges reduce the longitudinal expansion of the copper under the influence of temperature and thus represent a desirable adaptation to the behavior of the CIS layer (avoidance of cracking).
  • the CIS layer can then also be galvanically applied to the carrier material in a known manner, so that overall there is a galvanic process and no vacuum systems are required within a band process of solar cell production.
  • Fig. 3 shows a third example of a layer structure with a nickel-palladium alloy
  • Fig. 4 schematically shows a system for depositing a copper foil from an electrolytic bath
  • Fig. 5 shows the copper foil thus deposited in cross section.
  • the flexible substrate consists of an electrodeposited copper foil 1 to which a nickel layer 3 and then a nickel-molybdenum layer 4 have been applied galvanochemically. Since molybdenum is not a particularly good diffusion barrier for copper ions, a relatively thick nickel layer, approximately 2 ⁇ m thick, must be applied in this case. Nickel then takes on the function of a diffusion barrier and at the same time increases the heat resistance of the copper foil 1. Finally, a CIS layer 5 can also be applied galvanically to the nickel-molybdenum layer 4 in a conventional manner.
  • an electrodeposited copper foil 1 is again used, onto which a nickel layer 2 was also electrodeposited, but here only with a thickness of approximately 0.2 ⁇ m.
  • a layer 6 made of nickel-palladium or nickel-tungsten follows. Palladium and tungsten represent better diffusion barriers than molybdenum, so that the nickel layer 2 is required here alone to promote adhesion.
  • the CIS layer follows again in a known manner.
  • a third variant is shown in FIG.
  • a nickel (20) -alladium (80) alloy layer 7 of medium thickness was applied to a copper foil 1 alone, as is available as a standard product in strip electroplating.
  • the CIS layer is then applied to this.
  • the 4 consists of a drum 8, which is rotatably mounted in a basin 9, in which an electrolyte 10 is located.
  • the drum 8 forms the cathode, the basin 9 the anode.
  • the basin 9 is provided with an inlet 11 for the electrolyte 10, while an outlet 12 at which the basin 9 enclosing container 15 is provided.
  • copper is deposited on the drum 8, which can be lifted off the drum 8 as a copper foil 13 with a width of approximately 35 mm and a thickness of approximately 0.2 mm and wound onto a reel 14 ,
  • a suitable nickel salt can be mixed into the electrolyte in such a concentration that the copper foil 13 is formed with an alloy composition of the desired type.
  • the otherwise greatly reduced tensile strength of the copper foil 13 is increased by the nickel content in the subsequent heat treatment.
  • the copper foil 13 has hemispherical bulges 19 which increase the light absorption in a finished solar module.
  • the photovoltaically effective CIS layer 20 is later applied to the convex side 16 of these bulges, which is kept as smooth as possible.
  • the other, concave side 21, however, can have a certain roughness.
  • the convex side 16 has only a slight roughness due to the polished surface of the drum 8.
  • a special edge design e.g. B. for subdivision of the carrier material into individual solar cells, can be provided, which can be introduced in the manufacturing process.
  • a bent edge strip 18 is used to support a next solar cell, while on the other edge side, which is contacted with an edge strip 18 of a next solar cell, curved contact points 17 are provided to improve the contact.
  • the edge strip serves to limit the actual cell area coated with the CIS layer 20. Except for the contact points 17, it can be coated with an insulating material.

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Abstract

Substrates known in the art for use in flexible CIS solar cells have a series of drawbacks. The aim of the invention is to overcome these drawbacks. To this end, the substrate is characterized by a layer structure that comprises a chromium, nickel or nickel-iron base layer and a molybdenum, tungsten or palladium contact layer, or a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy contact layer, or only a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy contact layer disposed on a strip-shaped copper film. The layer structure is produced by a galvanic method. Advantageously, a galvanically deposited copper strip is used as the substrate material for the CIS solar cells.

Description

Flexibles metallisches Substrat für CIS - Solarzellen undFlexible metallic substrate for CIS solar cells and
Verfahren zu seiner HerstellungProcess for its manufacture
Beschreibungdescription
Die Erfindung betrif ft ein flexibles metallisches Substrat für CIS-Solarzellen und Verfahren zu dessen Herstellung .The invention relates to a flexible metallic substrate for CIS solar cells and methods for the production thereof.
In dem Bemühen, Strom aus Sonnenlicht ohne Umweltbelastung zu erzeugen mit Kosten, die in der selben Größenordnung wie die Erzeugungskosten bei der Nutzung fossiler Energieträger liegen, werden große Anstrengungen zur Entwicklung kosten- günstiger Solarzellen gemacht . Dabei stellen Dünnschichtsolarmodule den jüngsten Entwicklungsstand dar. Hierbei werden Schichten aus hochreinem Silizium, Kadmium-Tellurid oder Kupfer-Indium-Selenid/Schwefel (abgekürzt CIS) von weniger als 1 μm Dicke, üblicherweise mit Hilfe von Vakuumtechniken, auf Glas aufgedampft .In an effort to generate electricity from sunlight without environmental pollution with costs that are in the same order of magnitude as the production costs for the use of fossil fuels, great efforts are being made to develop inexpensive solar cells. Thin-film solar modules represent the latest state of development. Here layers of high-purity silicon, cadmium telluride or copper indium selenide / sulfur (abbreviated to CIS) of less than 1 μm thickness are usually vapor-deposited onto glass.
Unter den drei genannten Dünnschicht-Technologien ist die CIS-Technologie wegen ihrer Umweltverträglichkeit und dem Fehlen von Degradation (nachlassende Wirksamkeit durch Al- tern) besonders interessant. Die CIS-Schicht wird üblicherweise auf Glas, das zumeist erst im Sputterverfahren mit Molybdän beschichtet wurde, abgeschieden.Among the three thin-film technologies mentioned, the CIS technology is particularly interesting because of its environmental compatibility and the lack of degradation (declining effectiveness due to aging). The CIS layer is usually deposited on glass, which was usually only sputter-coated with molybdenum.
Es sind wegen der Nachteile von Glas als Substrat jedoch verschiedene Anstrengungen unternommen worden, um auch flexible Materialien einsetzen zu können. In der Überlegung, daß die Verwendung von Kupfer als Trägermaterial das elektrochemische Abscheiden der CIS-Schicht erlauben würde und Kupfer selbst Bestandteil der CIS-Schicht ist, wurde mit der DE-A 196 34 580 vorgeschlagen, ein Kupferband als Trägermaterial zu verwenden. Zunächst wird auf dem Kupferband Indium elektrochemisch abgeschieden. In einem zweiten Schritt wird das Band aufgeheizt und auf die aufgeheizte Indium-Schicht in der Dampfphase vorliegendes Selen oder Schwefel aufgebracht, wobei Kupfer in die Indiumschicht eindiffundieren und dort zusammen mit dem Selen/Schwefel die CIS-Schicht bilden soll. Das Verfahren erfordert eine genaue Einhaltung des Temperaturbereiches und der Prozeßzeiten bei der Selenisierung bzw. Sulfudisierung. Außerdem bildet sich an der Oberfläche Kupferselenid bzw. Kupfersulfid, das die Reinheit der CIS-Schicht stören würde und deshalb ätztech- nisch wieder entfernt werden muß. Schließlich kann nicht ausgeschlossen werden, daß im Verlauf der Zeit weiteres Kupfer in die CIS-Schicht eindiffundiert und die für den photo- voltaischen Effekt nötige Zusammensetzung ändert und somit die Funktion der Solarzelle zunehmend vermindert. Aufgrund der Nutzung der Kupferunterlage für den gleichzeitigen Aufbau der CIS-Schicht ist hier keine Diffusionssperre vorhanden.However, because of the disadvantages of glass as a substrate, various efforts have been made to also be able to use flexible materials. In consideration of the fact that the use of copper as a carrier material would allow the CIS layer to be deposited electrochemically and that copper itself is part of the CIS layer, DE-A 196 34 580 proposed using a copper tape as a carrier material. First, indium is electrochemically deposited on the copper strip. In a second step, the strip is heated and selenium or sulfur present in the vapor phase is applied to the heated indium layer, with copper diffusing into the indium layer and forming the CIS layer there together with the selenium / sulfur. The process requires precise observance of the temperature range and the process times for selenization or sulfudization. In addition, copper selenide or copper sulfide forms on the surface, which would disturb the purity of the CIS layer and therefore has to be removed by etching. Finally, it cannot be ruled out that further copper will diffuse into the CIS layer in the course of time and change the composition necessary for the photovoltaic effect and thus increasingly reduce the function of the solar cell. Due to the use of the copper base for the simultaneous build-up of the CIS layer, there is no diffusion barrier here.
Die Verwendung von gewalztem Kupferband ist insofern proble- matisch, als daß dieses durch den Verhüttungsprozeß ein Reihe von Verunreinigungen aufnimmt. Zwar wird es einer elektrolytischen Raffination unterzogen, die erzielbaren Reinheiten von 99,99 % müssen jedoch im Sinn der solaren Halbleitertechnologie als „stark verunreinigt" gelten. Es sind zwar Sauerstoffreie Qualitäten lieferbar, sie enthalten jedoch noch eine nicht bestimmbare Anzahl anderer, im Sinne der Halbleitertechnologie nicht geringfügiger Beimengungen. Außerdem muß das Kupferband während des Walzprozesses nach jedem Walzgang zwischengeglüht werden. Hierbei entstehen mög- licherweise weitere Verunreinigungen der Kupferoberfläche . Dünn gewalztes Kupferband ist also einmal relativ teuer und enthält zum zweiten Verunreinigungen, die sich beim Aufbringen einer CIS-Schicht als störend erweisen.The use of rolled copper tape is problematic in that it absorbs a number of contaminants through the smelting process. Although it is subjected to electrolytic refining, the purities of 99.99% which can be achieved must be regarded as "heavily contaminated" in the sense of solar semiconductor technology. Although oxygen-free qualities are available, they still contain an undetermined number of others, in the sense of Semiconductor technology with no minor additions. In addition, the copper strip must be annealed during the rolling process after each rolling pass. Licher further contamination of the copper surface. Thinly rolled copper strip is therefore once relatively expensive and, secondly, contains impurities which prove to be disruptive when a CIS layer is applied.
Ein grundsätzlicher Nachteil von Kupfer ist darüber hinaus, daß der thermische Ausdehnungskoeffizient der kristallinen CIS-Schicht von dem des Kupferbandes derart verschieden ist, daß es bei der Wärmebehandlung, der nach dem Aufbringen der CIS-Schicht erforderlich ist, leicht zur Rißbildung in der CIS-Schicht kommt, womit jede photovoltaische Funktion zunichte gemacht wird.A fundamental disadvantage of copper is also that the thermal expansion coefficient of the crystalline CIS layer is so different from that of the copper strip that it is easy to crack in the CIS during the heat treatment that is required after the application of the CIS layer. Layer comes, with which every photovoltaic function is destroyed.
Es wurde auch bereits vorgeschlagen, die CIS-Schicht auf eine handelsübliche flexible Molybdänfolie aufzubringen, wie sie beispielsweise für Durchführungen von elektrischen Anschlüssen in Halogenlampen verwendet wird. Molybdänfolie hat jedoch den etwa vierfachen Preis von Kupferband. Seine Verwendung ist, vermutlich wegen der darin enthaltenen Verunreinigungen, nicht über Laborversuche hinausgekommen.It has also already been proposed to apply the CIS layer to a commercially available flexible molybdenum foil, such as is used, for example, for making electrical connections in halogen lamps. However, molybdenum foil has about four times the price of copper tape. Its use, probably because of the impurities it contains, has not gone beyond laboratory tests.
Ebenfalls bekannt geworden sind Kunststoff-Folien zur CIS- Abscheidung. Die Auswahl genügend hochtemperaturfester Materialien bereitet jedoch erhebliche Mühe. Außerdem müssen derartige Folien naturgemäß erst durch ITO/TCO-Schichten e- lektrisch leitfähig gemacht werden, was üblicherweise wiederum durch Aufdampfen im Vakuum geschieht, das die Kosten erheblich steigen läßt .Plastic films for CIS deposition have also become known. However, the selection of sufficiently high-temperature-resistant materials causes considerable effort. In addition, such foils naturally have to be made electrically conductive by ITO / TCO layers, which is usually done by vacuum deposition, which increases the costs considerably.
Chrom-Nickel-Stahl-Folie, die auch bereits vorgeschlagen wurde, eignet sich ebenfalls wenig, da es dazu neigt, Wasserstoff aufzunehmen, das auf der Folienoberfläche Bläschen bildet, die bei der Abscheidung der CIS-Schicht zu „pin ho- les" führen, wodurch es beim späteren Aufbringen einer transparenten Deckschicht zu Kurzschlüssen kommt, welche die Solarzelle unbrauchbar machen.Chromium-nickel steel foil, which has also already been proposed, is also unsuitable, since it tends to absorb hydrogen, which forms bubbles on the surface of the foil, which lead to “pin holes” when the CIS layer is deposited , which makes it easier to apply later transparent cover layer leads to short circuits, which make the solar cell unusable.
Der Erfindung liegt die Aufgabe zugrunde, ein metallisches Substrat für eine flexible, bandförmige Solarzelle und Ver- fahren zu seiner Herstellung anzugeben, die das galvanische Aufbringen der CIS-Schicht erlauben und somit keine Vakuumtechnologie erfordern, mit denen das Eindiffundieren von Ionen des Substrats in die CIS-Schicht jedoch verhindert wird. Das Substrat soll unempfindlich sein gegenüber mechanischen (Biegen der Zelle) und thermischen Einflüssen auf die Solarzelle .The invention has for its object to provide a metallic substrate for a flexible, ribbon-shaped solar cell and method for its production, which allow the galvanic application of the CIS layer and thus do not require vacuum technology with which the diffusion of ions of the substrate into the CIS layer is prevented, however. The substrate should be insensitive to mechanical (bending of the cell) and thermal influences on the solar cell.
Die Aufgabe wird erfindungsgemäß gelöst durch die Merkmale der Ansprüche 1 bis 3 , 6 und 8. Zweckmäßige Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche.The object is achieved according to the invention by the features of claims 1 to 3, 6 and 8. Useful embodiments of the invention are the subject of the dependent claims.
Danach wird als Trägermaterial eine bandförmige Kupferfolie verwendet. Das Substrat entsteht durch Aufbringen eines Schichtaufbaus auf das Trägermaterial aus einer Grundschicht aus Chrom, Nickel oder Nickel-Eisen und einer KontaktSchicht aus Molybdän, Wolfram oder Palladium oder einer Nickel- Molybdän-, Nickel-Wolfram- oder Nickel-Palladium-Legierung oder nur aus einer KontaktSchicht aus einer Nickel-Molybdän- , Nickel-Wolfram oder Nickel-Palladium- Legierung. Die Schichtfolge kann in der angegebenen Reihenfolge durch galvanisches Abscheiden erzeugt werden.A ribbon-shaped copper foil is then used as the carrier material. The substrate is created by applying a layer structure to the carrier material from a base layer made of chromium, nickel or nickel-iron and a contact layer made from molybdenum, tungsten or palladium or a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy or only from a contact layer made of a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy. The layer sequence can be generated in the specified order by galvanic deposition.
Die Schicht aus Molybdän, Wolfram oder Palladium bzw. einer Nickel-Molybdän- , Nickel-Wolfram- oder Nickel-Palladium- Legierung übernimmt die „Vermittlung" zwischen den sehr unterschiedlichen thermischen Ausdehnungskoeffizienten von Kupfer/Nickel und CIS, während Nickel bzw. Nickel-Eisen die Festigkeit des Schichtenverbundes erheblich erhöht und eine Diffusionsbarriere gegenüber Kupferionen darstellt. Molybdän hat einen sehr geringen, der CIS-Schicht ähnlichen thermischen Ausdehnungskoeffizienten, andererseits einen hohen E- lastizitätsmodul, der die Spannungen zwischen den darunter und daruberliegenden Schichten unterschiedlicher Ausdehnung aufzunehmen vermag. Eine Schicht aus Wolfram verhält sich ähnlich, d. h. sie zeigt bei niedriger Wärmeausdehnung eine hohe Elastizität.The layer of molybdenum, tungsten or palladium or a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy takes over the "mediation" between the very different thermal expansion coefficients of copper / nickel and CIS, while nickel or nickel Iron significantly increases the strength of the layer composite and represents a diffusion barrier against copper ions has a very low coefficient of thermal expansion similar to that of the CIS layer, on the other hand it has a high modulus of elasticity, which is able to absorb the stresses between the layers below and above it with different expansion. A layer of tungsten behaves similarly, ie it shows high elasticity at low thermal expansion.
Als Verbundsystem stellt der Schichtenaufbau somit ein ge- eignetes Substrat dar, das ausschließlich im bandgalvanoche- mischen Verfahren herstellbar ist und das trotz der an sich hohen Kosten von Molybdän, Wolfram und Palladium bzw. der Nickel-Molybdän- , Nickel-Wolfram- oder Nickel-Palladium- Legierung wegen der geringen Schichtdicken insgesamt preis- wert ist .As a composite system, the layer structure thus represents a suitable substrate that can only be produced using the strip galvano-chemical process and that despite the high costs of molybdenum, tungsten and palladium or the nickel-molybdenum, nickel-tungsten or nickel -Palladium alloy is inexpensive overall because of the low layer thicknesses.
Als vorteilhaft hat sich erwiesen, die Kupferfolie nach dem Beschichten mit der Grundschicht und/oder KontaktSchicht einer Wärmebehandlung zu unterziehen, bevor die CIS-Schicht aufgebracht wird.It has proven to be advantageous to subject the copper foil to a heat treatment after coating with the base layer and / or contact layer before the CIS layer is applied.
Kupferfolie hat den Vorteil, daß sie flexibel und preiswerter als andere Metallfolien ist. Die außerdem gute Leitfähigkeit ist nicht von allzu großer Bedeutung, da photovol- taisch erzeugter Strom eine geringe Stromdichte besitzt. Es können daher auch Kupferlegierungen, die eine geringere Leitfähigkeit aufweisen, jedoch andere Vorteile besitzen, verwendet werden .Copper foil has the advantage that it is flexible and cheaper than other metal foils. The conductivity, which is also good, is not of great importance, since photovoltaically generated current has a low current density. Copper alloys which have a lower conductivity but have other advantages can therefore also be used.
Kupfer hat an sich allerdings für die Verwendung als Trägermaterial die bereits oben angedeuteten gravierenden Nachteile, die durch die Erfindung jedoch überwunden werden. Erstens ist die Warmfestigkeit von reinem Kupfer sehr gering, so daß ohne eine weitere Maßnahme mechanische Beanspruchungen während des nachfolgenden Temperprozesses zur Beschädigung der dünnen CIS-Schicht führen können. Zweiten sind Kupferionen, wie bereits gesagt, äußerst beweglich, so daß diese bei dem Temperprozeß, aber auch bereits bei der Gebrauchstemperatur der Solarzellen, in unkontrollierter Menge in die CIS-Schicht einwandern würden. Drittens ist der thermische Ausdehnungkoeffizient von Kupfer von dem der kristallinen CIS-Schicht derart verschieden, daß unter Tempera- tureinfluß mit einer Rißbildung in der dünnen, aufliegenden CIS-Absorberschicht zu rechnen ist, welches wiederum jede photovoltaische Funktion zunichte macht.However, copper per se has the serious disadvantages already indicated above for use as a carrier material, which, however, are overcome by the invention. First, the heat resistance of pure copper is very low, so that without further measures, mechanical stresses during the subsequent annealing process can damage the thin CIS layer. Secondly, as already mentioned, copper ions are extremely mobile, so that they would migrate into the CIS layer in an uncontrolled amount during the tempering process, but also at the temperature of use of the solar cells. Thirdly, the thermal expansion coefficient of copper is so different from that of the crystalline CIS layer that under the influence of temperature, crack formation in the thin, overlying CIS absorber layer can be expected, which in turn nullifies any photovoltaic function.
Mit dem erfindungsgemäßen Schichtaufbau wird, wie bereits beschrieben, zunächst eine Chrom, Nickel- oder Nickel-Eisen- Grundschicht aufgebracht, die als Diffusionsbarriere, als Anpassung hinsichtlich des Ausdehnungskoeffizienten und als Haftschicht für die nachfolgenden Schichten dient. Die Nickel-Eisen-Schicht ist als sogenannte KOVAR oder auch INVAR- Legierung bekannt. Chrom, Nickel oder Nickel-Eisen können galvanotechnisch aufgebracht werden. Die nachfolgende Kontaktschicht besteht aus Molybdän, Palladium oder Wolfram bzw. einer Nickel-Molybdän- , Nickel-Wolfram- oder Nickel- Palladium-Legierung, die sich ebenfalls galvanotechnisch aufbringen lassen.With the layer structure according to the invention, as already described, a chromium, nickel or nickel-iron base layer is first applied, which serves as a diffusion barrier, as an adjustment with regard to the coefficient of expansion and as an adhesive layer for the subsequent layers. The nickel-iron layer is known as the so-called KOVAR or INVAR alloy. Chromium, nickel or nickel-iron can be applied by electroplating. The subsequent contact layer consists of molybdenum, palladium or tungsten or a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy, which can also be applied by electroplating.
Eine weitere Variante ist das alleinige Abscheiden einer Nickel-Palladium-, Nickel-Molybdän oder Nickel-Wolfram- Legierung auf der Kupferfolie, die gleichzeitig als Diffusi- onsbarriere und als Vermittlungschicht für die CIS-Schicht dient . Das galvanotechnische Aufbringen einer Molybdänschicht ist bisher wenig bekannt, ist als Legierungsabscheidung zusammen mit Nickel, ebenso wie Nickel-Palladium oder Nickel-Wolfram aber möglich.Another variant is the sole deposition of a nickel-palladium, nickel-molybdenum or nickel-tungsten alloy on the copper foil, which also serves as a diffusion barrier and as a mediation layer for the CIS layer. The electroplating of a molybdenum layer is little known so far, but it is possible as an alloy deposit together with nickel, just like nickel-palladium or nickel-tungsten.
Schichten aus Palladium, Nickel-Palladium oder Wolfram bzw. Wolfram-Palladium stellen an sich bereits eine Diffusionsbarriere gegen Kupfer dar, die teuren Edelmetalle können jedoch in geringerer Schichtstärke und mit besserer Haftung sowie ohne die Verunreinigung der Bäder durch Kupfer galva- nisch aufgebracht werden, wenn zuvor wenigstens eine dünne Nickelschicht auf die Kupferfolie abgeschieden wird.Layers of palladium, nickel-palladium, or tungsten or tungsten-palladium are in themselves a diffusion barrier against copper, but the expensive noble metals can be applied galvanically in a lower layer thickness and with better adhesion and without contamination of the baths by copper, if at least a thin layer of nickel is previously deposited on the copper foil.
Molybdän ist nicht in der Lage, als Diffusionsbarriere für Kupfer zu wirken und benötigt deshalb eine Nickelschicht mit bestimmter Mindestdicke als Unterlage. Andererseits muß der direkte Kontakt einer reinen Nickelschicht mit der CIS- Schicht vermieden werden, weil sich hierbei CIS-Nickel- Komplexe bilden würden, also reines CIS für den kristallinen Aufbau nicht mehr zur Verfügung stünde.Molybdenum is not able to act as a diffusion barrier for copper and therefore requires a nickel layer with a certain minimum thickness as a base. On the other hand, the direct contact of a pure nickel layer with the CIS layer must be avoided because this would form CIS-nickel complexes, ie pure CIS would no longer be available for the crystalline structure.
Die Kupferfolie soll eine möglichst geringe Oberflächenrauhigkeit aufweisen, kann zur Maximierung der späteren Licht- aufnähme jedoch oberflächenvergrößert sein, indem während des Herstellungsprozesses bereits Auswölbungen eingebracht werden. Hierdurch wird bei diffus auf die Solarzelle auf- treffender Strahlung die Lichtabsorption und damit die Ge- samt1eistung erhöht .The copper foil should have a surface roughness that is as low as possible, but in order to maximize the later light absorption, the surface area can be increased by bulges being introduced during the manufacturing process. As a result, the light absorption and thus the total output is increased in the case of diffuse radiation impinging on the solar cell.
Auf das Trägermaterial mit den Substrat-Schichten kann die CIS-Schicht dann in bekannter Weise galvanisch aufgebracht werden, so daß keine Vakuumanlagen benötigt werden. Die CIS- Schicht wird anschließend in einem Wärmebhandlungsprozeß aktiviert . Vorteilhaft wird als Trägermaterial durch elektrolytisches Abscheiden hergestellte Kupferfolie verwendet.The CIS layer can then be galvanically applied to the carrier material with the substrate layers in a known manner, so that no vacuum systems are required. The CIS layer is then activated in a heat treatment process. Copper foil produced by electrolytic deposition is advantageously used as the carrier material.
Überraschend hat sich gezeigt, daß elektrolytisch abgeschiedene Kupferfolie, die bisher traditionell ausschließlich für die Leiterplattenfertigung benutzt wurde, eine Reihe von bisher bei anderen Anwendungen nicht genutzten bzw. dort nicht gefragten Vorteilen aufweist, die sich hier als relevant erweisen. Elektrolytisch abgeschiedene Kupferfolie wird nämlich für die Leiterplattenfertigung mit bestimmter Rauhigkeit hergestellt. Auch gewalztes Kupferband weist eine bestimmte Rauhigkeit auf. Solche Rauhigkeit ist für die Weiterverarbeitung, nämlich für eine Verklebung, von Vorteil, wäre für Solarzellen allerdings nachteilig. Elektrolytisch abgeschiedene Kupferfolie lässt sich dagegen auch mit sehr geringer Rauhigkeit herstellen, was für Solarzellen von großem Vorteil ist.Surprisingly, it has been shown that electrolytically deposited copper foil, which has traditionally been used exclusively for the manufacture of printed circuit boards, has a number of advantages which have hitherto not been used in other applications or which are not in demand there and which prove to be relevant here. Electrolytically deposited copper foil is namely produced with a certain roughness for the production of printed circuit boards. Rolled copper strip also has a certain roughness. Such roughness is advantageous for further processing, namely for bonding, but would be disadvantageous for solar cells. Electrolytically deposited copper foil, on the other hand, can also be produced with very little roughness, which is a great advantage for solar cells.
Die Kupferfolie wird als Endlosband durch Abscheiden aus einem elektrolytischen Bad hergestellt. Es können dem Bad Be- standteile zugesetzt werden, deren Abscheidungen in der Kupferfolie die Zugfestigkeit und/oder Temperaturbeständigkeit erhöhen und/oder den Ausdehnungkoeffizienten der Kupferfolie vermindern, beispielsweise Nickel. Zusätzlich oder alternativ dazu kann die Kupferfolie anschließend an den ersten Ab- scheideprozeß durch weitere galvanische Behandlung mit weiteren metallischen Schichten versehen werden.The copper foil is produced as an endless strip by deposition from an electrolytic bath. Components can be added to the bath, the deposits of which in the copper foil increase the tensile strength and / or temperature resistance and / or reduce the coefficient of expansion of the copper foil, for example nickel. Additionally or alternatively, the copper foil can be provided with further metallic layers after the first deposition process by further galvanic treatment.
Auch ein gleichzeitiges Abscheiden von Substanzen, die gezielt in kleinen Mengen in die CIS-Schicht eindiffundieren sollen ist möglich. Beispielsweise wandert Natrium später bei einer Wärmebehandlung, die zur Aktivierung der CIS- Schicht nötig ist, in gezielter Menge in die CIS-Schicht ein und begünstigt dort in der Art eines Flußmittels die Kristallisation. Geeignete Badzusätze zur gleichzeitigen Abscheidung sind z. B. solche, die ein Abscheiden von Nickel, Zink, Zinn u. ä. bewirken. Insbesondere Nickel bewirkt die Erhöhung der Zugfestigkeit der Kupferfolie, die ansonsten bei den folgenden Wärmebehandlungsprozessen verloren gehen würde. Kupferfolie mit einem gewissen Nickelgehalt hat dann den Effekt, daß die folgende Grundschicht sehr viel dünner ausgeführt werden kann und besser haftet .It is also possible to separate substances that are intended to diffuse into the CIS layer in small quantities. For example, sodium later migrates in a targeted amount into the CIS layer during a heat treatment that is necessary to activate the CIS layer, and favors crystallization there in the manner of a flux. Suitable bath additives for simultaneous deposition are e.g. B. those that a deposition of nickel, zinc, tin and. effect. Nickel in particular causes the tensile strength of the copper foil to increase, which would otherwise be lost in the subsequent heat treatment processes. Copper foil with a certain nickel content then has the effect that the following base layer can be made much thinner and adheres better.
Ein nachfolgender Schichtaufbau durch galvanische Abschei- düng kann beispielsweise die Folge Kupferfolie/Nickel oder Kupferfolie/ (Nickeleisen) sein.A subsequent layer build-up by galvanic deposition can be, for example, copper foil / nickel or copper foil / (nickel iron).
Die Verwendung von elektrolytisch abgeschiedener Kupferfolie für den Aufbau flexibler CIS-Solarzellen hat verschiedenen Vorteile. Neben der angesprochenen Möglichkeit einer gezielten Legierungsbildung ist die Folie auch in großer Reinheit herstellbar, was für die bisherige Anwendung in der Leiterplattenfertigung allerdings kein Rolle spielte und dort nicht genutzt wurde. Der Preis für galvanisch abgeschiedene, dünne Kupferfolien liegt nicht höher als der für vergleichbares gewalztes Kupferband.The use of electrolytically deposited copper foil for the construction of flexible CIS solar cells has various advantages. In addition to the mentioned possibility of targeted alloy formation, the foil can also be produced in a high degree of purity, which, however, did not play a role for the previous application in printed circuit board manufacture and was not used there. The price for electrodeposited, thin copper foils is no higher than for comparable rolled copper strips.
Die Kupferfolie wird im Gegensatz zu Kupferfolie, die für die Leiterplattenindustrie zum Einsatz kommt, mit geringer Oberflächenrauhigkeit hergestellt, kann zur Maximierung der späteren Lichtaufnahme zugleich oberflächenvergrößert sein, indem während des Abscheidens bereits Auswölbungen eingebracht werden, ohne daß dabei herstellungstechnisch ein besonderer Mehraufwand entsteht. Die Dimension dieser Auswöl- bungen ist makroskopisch. Solche, z. B. halbkugligen Auswölbungen in der Größenordnung von ca. 2 mm lassen sich durch entsprechende Gestaltung der Abscheidetrommel realisieren. Hierdurch wird bei diffus auf die Solarzelle auftreffender Strahlung die Lichtabsorption und damit der Zellen- Wirkungsgrad erhöht . Zudem vermindern die Aufwölbungen eine Längenausdehnung des Kupfers unter Temperatureinfluß und stellen somit eine wünschenswerte Anpassung an das Verhalten der CIS-Schicht (Vermeiden von Rißbildung) dar.In contrast to copper foil, which is used for the printed circuit board industry, the copper foil is manufactured with a low surface roughness. To maximize the later light absorption, the surface area can be increased by bulging during the deposition without any additional manufacturing effort. The dimension of these bulges is macroscopic. Such, e.g. B. hemispherical bulges in the order of about 2 mm can be realized by appropriate design of the separation drum. As a result, the light absorption and thus the cell Efficiency increased. In addition, the bulges reduce the longitudinal expansion of the copper under the influence of temperature and thus represent a desirable adaptation to the behavior of the CIS layer (avoidance of cracking).
Schließlich können bei der galvanischen Abscheidung auch noch andere Forderungen bezüglich der Form ohne wesentlichen Mehraufwand realisiert werden, wie beispielsweise Abgrenzungen der eigentlichen Zellenflächen auf der Kupferfolie oder Nocken, die ähnlich den Kontaktflächen eines Relais bei der späteren Verschaltung der Solarzellen zu Solarzellenmodulen für die kontaktierende Stromführung vorteilhaft sind (sogenanntes „Schindeln") .Finally, in the case of galvanic deposition, other requirements regarding the shape can also be met without significant additional effort, such as, for example, delimitation of the actual cell areas on the copper foil or cams, which, similar to the contact areas of a relay, are advantageous for the contacting current supply when the solar cells are later connected to solar cell modules are (so-called "shingles").
Auf das Trägermaterial kann die CIS-Schicht dann in bekann- ter Weise ebenfalls galvanisch aufgebracht werden, so daß insgesamt ein galvanischer Prozeß vorliegt und innerhalb eines Bandprozesses der Solarzellenherstellung keine Vakuumanlagen benötigt werden.The CIS layer can then also be galvanically applied to the carrier material in a known manner, so that overall there is a galvanic process and no vacuum systems are required within a band process of solar cell production.
Die Erfindung soll nachstehend anhand von zwei Ausführungs- beispielen noch näher erklärt werden. In den Zeichnungen zeigenThe invention will be explained in more detail below with the aid of two exemplary embodiments. Show in the drawings
Fig. 1 ein Beispiel für einen Schichtaufbau mit Molybdän auf einem flexiblen Trägermaterial,1 shows an example of a layer structure with molybdenum on a flexible carrier material,
Fig. 2 ein zweites Beispiel für einen Schichtaufbau mit Palladium/Wolfram,2 shows a second example of a layer structure with palladium / tungsten,
Fig. 3 ein drittes Beispiel für einen Schichtaufbau mit einer Nickel-Palladium-Legierung, Fig. 4 schematisch eine Anlage zum Abscheiden einer Kupferfolie aus einem elektrolytischen Bad undFig. 3 shows a third example of a layer structure with a nickel-palladium alloy, Fig. 4 schematically shows a system for depositing a copper foil from an electrolytic bath and
Fig. 5 die damit abgeschiedene Kupferfolie im Querschnitt . Gemäß Fig. 1 besteht das flexible Substrat aus einer galvanisch abgeschiedenen Kupferfolie 1, auf die galvanochemisch zunächst eine Nickelschicht 3 und dann eine Nickel- Molybdänschicht 4 aufgebracht wurde. Da Molybdän keine besonders gute Diffusionssperre für Kupferionen darstellt, muß in diesen Fall eine relativ dicke Nickelschicht, ca. in einer Dicke von 2 μm, aufgebracht werden. Nickel übernimmt dann die Funktion einer Diffusionssperre und erhöht gleichzeitig die Warmfestigkeit der Kupferfolie 1. Auf die Nickel- Molybdänschicht 4 kann schließlich in üblicher Weise eben- falls galvanisch eine CIS-Schicht 5 aufgebracht werden.Fig. 5 shows the copper foil thus deposited in cross section. 1, the flexible substrate consists of an electrodeposited copper foil 1 to which a nickel layer 3 and then a nickel-molybdenum layer 4 have been applied galvanochemically. Since molybdenum is not a particularly good diffusion barrier for copper ions, a relatively thick nickel layer, approximately 2 μm thick, must be applied in this case. Nickel then takes on the function of a diffusion barrier and at the same time increases the heat resistance of the copper foil 1. Finally, a CIS layer 5 can also be applied galvanically to the nickel-molybdenum layer 4 in a conventional manner.
Nach dem in Fig. 2 dargestellten Beispiel wird wiederum eine galvanisch abgeschiedene Kupferfolie 1 verwendet, auf die galvanisch zunächst auch eine Nickelschicht 2 abgeschieden wurde, hier allerdings nur mit einer Dicke von ca. 0,2 μm. Erlaubt wird das durch den weiteren Schichtaufbau, nach dem eine Schicht 6 aus Nickel-Palladium oder Nickel-Wolfram folgt. Palladium und Wolfram stellen bessere Diffusionsbarrieren dar als Molybdän, so daß die Nickelschicht 2 hier al- lein zur Haftvermittlung benötigt wird. Schließlich folgt wieder die CIS-Schicht in bekannter Weise.According to the example shown in FIG. 2, an electrodeposited copper foil 1 is again used, onto which a nickel layer 2 was also electrodeposited, but here only with a thickness of approximately 0.2 μm. This is permitted by the further layer structure, after which a layer 6 made of nickel-palladium or nickel-tungsten follows. Palladium and tungsten represent better diffusion barriers than molybdenum, so that the nickel layer 2 is required here alone to promote adhesion. Finally, the CIS layer follows again in a known manner.
In Fig. 3 ist eine dritte Variante gezeigt. Hierbei wurde auf eine Kupferfolie 1 allein eine Nickel (20) -Palladium (80) - Legierungsschicht 7 mittlerer Dicke aufgebracht, wie sie als Standardprodukt in der Bandgalvanik zur Verfügung steht . Auf diese wird dann die CIS-Schicht aufgetragen.A third variant is shown in FIG. In this case, a nickel (20) -alladium (80) alloy layer 7 of medium thickness was applied to a copper foil 1 alone, as is available as a standard product in strip electroplating. The CIS layer is then applied to this.
Eine Elektrolyt-Anlage zur Herstellung von Kupferfolie be- steht gemäß Fig. 4 aus einer Trommel 8, die in einem Becken 9, in dem sich ein Elektrolyt 10 befindet, drehbar gelagert ist. Die Trommel 8 bildet die Kathode, das Becken 9 die Anode. Das Becken 9 ist mit einem Zulauf 11 für den Elektrolyten 10 versehen, während ein Ablauf 12 an dem das Becken 9 umschließenden Behälter 15 vorgesehen ist. Durch Drehen der Trommel 8 bei angelegter Spannung wird Kupfer auf der Trommel 8 abgeschieden, das als Kupferfolie 13 mit ca. 35 mm Breite und in einer Dicke von ca. 0,2 mm von der Trommel 8 abgehoben und auf eine Haspel 14 aufgewickelt werden kann.4 consists of a drum 8, which is rotatably mounted in a basin 9, in which an electrolyte 10 is located. The drum 8 forms the cathode, the basin 9 the anode. The basin 9 is provided with an inlet 11 for the electrolyte 10, while an outlet 12 at which the basin 9 enclosing container 15 is provided. By rotating the drum 8 with applied voltage, copper is deposited on the drum 8, which can be lifted off the drum 8 as a copper foil 13 with a width of approximately 35 mm and a thickness of approximately 0.2 mm and wound onto a reel 14 ,
Dem Elektrolyten kann ein geeignetes Nickelsalz in einer solchen Konzentration beigemischt werden, daß sich die Kupferfolie 13 mit einer LegierungsZusammensetzung gewünschter Art bildet. Durch den Nickelgehalt wird bei der nachfolgen- den Wärmebehandlung die ansonsten stark verminderte Zugfestigkeit der Kupferfolie 13 erhöht.A suitable nickel salt can be mixed into the electrolyte in such a concentration that the copper foil 13 is formed with an alloy composition of the desired type. The otherwise greatly reduced tensile strength of the copper foil 13 is increased by the nickel content in the subsequent heat treatment.
Fig. 5 zeigt einen Querschnitt durch eine solchermaßen hergestellte Kupferfolie 13 und eine später aufgebrachte CIS- Schicht 20. Durch die Strukturierung der Trommel 8 weist die Kupferfolie 13 halbkugelförmigen Aufwölbungen 19 auf, die bei einem fertigen Solarmodul die Lichtabsorption erhöhen. Auf die möglichst glatt gehaltenen konvexe Seite 16 dieser Aufwölbungen wird später die photovoltaisch wirksame CIS- Schicht 20 aufgebracht. Die andere, konkave Seite 21 kann degegen eine gewisse Rauhigkeit aufweisen. Die konvexe Seite 16 weist aufgrund der polierten Oberfläche der Trommel 8 nur eine geringe Rauhigkeit auf .5 shows a cross section through a copper foil 13 produced in this way and a CIS layer 20 applied later. By structuring the drum 8, the copper foil 13 has hemispherical bulges 19 which increase the light absorption in a finished solar module. The photovoltaically effective CIS layer 20 is later applied to the convex side 16 of these bulges, which is kept as smooth as possible. The other, concave side 21, however, can have a certain roughness. The convex side 16 has only a slight roughness due to the polished surface of the drum 8.
Zur Verschaltung von mehreren Solarzellen zu einem Solarmodul ist kann eine besondere Randgestaltung, z. B. zur Unterteilung des Trägermaterials in einzelne Solarzellen, vorgesehen sein, die sich im Herstellungsprozeß gleich mit einbringen läßt . Zur Auflage einer nächsten Solarzelle dient in dem hier gezeigten Ausführungsbeispiel ein abgebogener Randstreifen 18, während an der anderen Randseite, die mit einem Randstreifen 18 einer nächsten Solarzelle kontaktiert wird, zur Kontaktverbesserung aufgewölbte Kontaktpunkte 17 vorgesehen sind. Zugleich dient der Randstreifen zur Eingrenzung der eigentlichen, mit der CIS-Schicht 20 beschichteten Zellenfläche. Er kann, die Kontaktpunkte 17 ausgenommen, mit einem Isoliermaterial beschichtet sein. To connect several solar cells to one solar module, a special edge design, e.g. B. for subdivision of the carrier material into individual solar cells, can be provided, which can be introduced in the manufacturing process. In the exemplary embodiment shown here, a bent edge strip 18 is used to support a next solar cell, while on the other edge side, which is contacted with an edge strip 18 of a next solar cell, curved contact points 17 are provided to improve the contact. At the same time, the edge strip serves to limit the actual cell area coated with the CIS layer 20. Except for the contact points 17, it can be coated with an insulating material.
BezugszeichenlisteLIST OF REFERENCE NUMBERS
1. Kupferfolie1. Copper foil
2. Nickelschicht 3. Nickelschicht2. Nickel layer 3. Nickel layer
4. Nickel-Molybdänschicht4. Nickel-molybdenum layer
5. CIS-Schicht5th CIS layer
6. Schicht aus Nickel-Palladium oder Nickel-Wolfram6. Layer of nickel-palladium or nickel-tungsten
7. Nickel (20) -Palladium (80) -Legierungsschicht 8. Trommel7. Nickel (20) -Palladium (80) alloy layer 8. Drum
9. Becken9. Basin
10. Elektrolyt10. Electrolyte
11. Zulauf (für Elektrolyt)11. Inlet (for electrolyte)
12. Ablauf (für Elektrolyt) 13. Kupferfolie12. Drain (for electrolyte) 13. Copper foil
14. Haspel14. Reel
15. Behälter15. Container
16. Konvexe Seite (der Kupferfolie)16. Convex side (the copper foil)
17. Kontaktpunkte 18. Randstreifen17. Contact points 18. Edge strips
19. Aufwölbungen19. Bulges
20. CIS-Schicht20th CIS layer
21. Konkave Seite (der Kupferfolie) 21. Concave side (of the copper foil)

Claims

Patentansprüche claims
1. Flexibles metallisches Substrat für CIS-Solarzellen, gekennzeichnet dadurch, daß es aus einem Schichtaufbaus aus einer Grundschicht aus Chrom, Nickel oder Nickel-Eisen und einer Kontaktschicht aus Molybdän, Wolfram oder Palladium oder einer Nickel- Molybdän-, Nickel-Wolfram- oder Nickel-Palladium- Legierung oder nur aus einer Kontaktschicht aus einer Nickel-Molybdän- , Nickel-Wolfram- oder Nickel-Palladium- Legierung auf einer bandförmigen Kupferfolie besteht, wobei der Schichtaufbau galvanisch hergestellt ist.1. Flexible metallic substrate for CIS solar cells, characterized in that it consists of a layer structure of a base layer made of chromium, nickel or nickel-iron and a contact layer made of molybdenum, tungsten or palladium or a nickel-molybdenum, nickel-tungsten or Nickel-palladium alloy or consists only of a contact layer made of a nickel-molybdenum, nickel-tungsten or nickel-palladium alloy on a band-shaped copper foil, the layer structure being produced galvanically.
2. Verfahren zur Herstellung eines flexiblen metallischen Substrats für eine CIS-Solarzelle, gekennzeichnet dadurch, daß auf eine bandförmige Kupferfolie galvanisch zunächst eine Chrom, Nickel- oder Nickel-Eisen-Grundschicht und nachfolgend eine Kontaktschicht aus Molybdän, Wolfram oder Palladium oder einer Nickel-Molybdän- , Nickel- Wolfram- oder Nickel -Palladium-Legierung aufgebracht wird.2. A process for the production of a flexible metallic substrate for a CIS solar cell, characterized in that initially a chrome, nickel or nickel-iron base layer and subsequently a contact layer made of molybdenum, tungsten or palladium or a nickel are electroplated onto a band-shaped copper foil. Molybdenum, nickel-tungsten or nickel-palladium alloy is applied.
3. Verfahren zur Herstellung eines flexiblen metallischen Substrats für eine CIS-Solarzelle, gekennzeichnet dadurch, daß auf eine bandförmige Kupferfolie galvanisch eine Kontaktschicht aus Nickel-Molybdän- , Nickel-Wolfram- oder einer Nickel -Palladium-Legierung aufgebracht wird. 3. A method for producing a flexible metallic substrate for a CIS solar cell, characterized in that a contact layer made of nickel-molybdenum, nickel-tungsten or a nickel-palladium alloy is applied galvanically to a band-shaped copper foil.
4. Verfahren nach Anspruch 2 oder 3 , gekennzeichnet dadurch, daß die Kupferfolie nach dem Beschichten mit der Grundschicht und/oder Kontaktschicht einer Wärmebehandlung unterzogen wird.4. The method according to claim 2 or 3, characterized in that the copper foil is subjected to a heat treatment after coating with the base layer and / or contact layer.
5. Verfahren nach Anspruch 2 , gekennzeichnet dadurch, daß die Nickelschicht aus einem Nickelelektrolyt mit Nickel - bromiden abgeschieden wird.5. The method according to claim 2, characterized in that the nickel layer is deposited from a nickel electrolyte with nickel - bromides.
6. Bandförmige Kupferfolie als Trägermaterial für eine CIS- Solarzelle gekennzeichnet dadurch, daß sie durch elektrolytisches Abscheiden hergestellt ist.6. Ribbon-shaped copper foil as a carrier material for a CIS solar cell, characterized in that it is produced by electrolytic deposition.
7. Kupferfolie nach Anspruch 6, gekennzeichnet dadurch, daß ihre die Oberfläche durch Auswölbungen (19) vergrößert ist7. Copper foil according to claim 6, characterized in that its surface is enlarged by bulges (19)
8. Verfahren zur Herstellung bandförmiger Kupferfolie als Trägermaterial für eine CIS-Solarzelle, gekennzeichnet dadurch, daß die Kupferfolie als Endlosband durch Abscheiden aus einem elektrolytischen Bad hergestellt wird und daß dem Bad Legierungsbestandteile zugesetzt werden, die in der Kupferfolie die Zugfestigkeit und/oder Temperaturbeständigkeit erhöhen und/oder den Ausdehnungkoeffizienten vermindern . 8. A process for the production of ribbon-shaped copper foil as a carrier material for a CIS solar cell, characterized in that the copper foil is produced as an endless belt by deposition from an electrolytic bath and that alloy components are added to the bath which increase the tensile strength and / or temperature resistance in the copper foil and / or reduce the coefficient of expansion.
. Verfahren nach Anspruch 8 , gekennzeichnet dadurch, daß als Legierungsbestandteil Nickel verwendet wird., A method according to claim 8, characterized in that nickel is used as the alloy component.
10. Verfahren nach Anspruch 8, gekennzeichnet dadurch, daß als Legierungsbestandteil Zink verwendet wird.10. The method according to claim 8, characterized in that zinc is used as the alloy component.
11. Verfahren nach Anspruch 8, gekennzeichnet dadurch, daß als Legierungsbestandteil Eisen verwendet wird.11. The method according to claim 8, characterized in that iron is used as the alloy component.
12. Verfahren nach Anspruch 8, gekennzeichnet dadurch, daß dem Bad Substanzen zugesetzt werden, die später in die CIS-Schicht eindiffundieren sollen.12. The method according to claim 8, characterized in that substances are added to the bath which are later to diffuse into the CIS layer.
13. Verfahren nach Anspruch 12, gekennzeichnet dadurch, daß als zugesetzte Substanz eine Natrium-Verbindung verwendet wird.13. The method according to claim 12, characterized in that a sodium compound is used as the added substance.
14. Verfahren nach Anspruch 8 bis 13, gekennzeichnet dadurch, daß die Kupferfolie beim Abscheiden an einer oberflächen- strukturierten Trommel mit oberflächenvergrößernden Aus- wölbungen versehen wird. 14. The method according to claim 8 to 13, characterized in that the copper foil is provided with surface-enlarging bulges during deposition on a surface-structured drum.
15. Verfahren nach Anspruch 8 bis 14, gekennzeichnet dadurch, daß die Kupferfolie beim Abscheiden an einer oberflächenstrukturierten Trommel mit Strukturen versehen wird, die die Solarzelle begrenzen oder unterteilen.15. The method according to claim 8 to 14, characterized in that the copper foil is provided during the deposition on a surface-structured drum with structures that limit or subdivide the solar cell.
16. Verfahren nach Anspruch 8 bis 15, gekennzeichnet dadurch, daß die Kupferfolie beim Abscheiden an einer oberflächen- strukturierten Trommel mit Kontaktnocken versehen wird. 16. The method according to claim 8 to 15, characterized in that the copper foil is provided with contact cams during deposition on a surface-structured drum.
EP01911618A 2000-02-07 2001-02-07 Flexible metal substrate for cis solar cells, and method for producing the same Withdrawn EP1261990A1 (en)

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DE10005680A DE10005680B4 (en) 2000-02-07 2000-02-07 Support material for a flexible, band-shaped CIS solar cell
DE10005680 2000-02-07
DE10006823 2000-02-08
DE10006823A DE10006823C2 (en) 2000-02-08 2000-02-08 Process for producing a flexible metallic substrate for a CIS solar cell and CIS solar cell
PCT/EP2001/001313 WO2001057932A1 (en) 2000-02-07 2001-02-07 Flexible metal substrate for cis solar cells, and method for producing the same

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