WO1998038683A1 - Structure a couches resistant aux intemperies et a la corrosion - Google Patents

Structure a couches resistant aux intemperies et a la corrosion Download PDF

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Publication number
WO1998038683A1
WO1998038683A1 PCT/EP1998/000832 EP9800832W WO9838683A1 WO 1998038683 A1 WO1998038683 A1 WO 1998038683A1 EP 9800832 W EP9800832 W EP 9800832W WO 9838683 A1 WO9838683 A1 WO 9838683A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
barrier
barrier layer
corrosion
thin
Prior art date
Application number
PCT/EP1998/000832
Other languages
German (de)
English (en)
Inventor
Volker Probst
Jörk RIMMASCH
Walter Stetter
Hermann Calwer
Original Assignee
Siemens Aktiengesellschaft
Siemens Solar Gmbh
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
Application filed by Siemens Aktiengesellschaft, Siemens Solar Gmbh filed Critical Siemens Aktiengesellschaft
Priority to EP98906951A priority Critical patent/EP0966765A1/fr
Priority to JP53724698A priority patent/JP2001513264A/ja
Publication of WO1998038683A1 publication Critical patent/WO1998038683A1/fr

Links

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
    • H01L31/04—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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • 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
    • H01L31/04—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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • 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

Definitions

  • the invention relates to a layer structure with at least one moisture and / or corrosion sensitive layer arranged on a substrate, in particular an optically and / or electrically active thin layer.
  • a layer structure with at least one moisture and / or corrosion sensitive layer arranged on a substrate, in particular an optically and / or electrically active thin layer.
  • Such layers are found, for example, in optical or electrical components. Examples of these are radiation-sensitive components such as detectors, solar cells or solar modules, or optoelectronic components such as display devices and in particular LCD screens.
  • solar modules In order to meet the quality requirements in demand on the market, solar modules have to successfully undergo a number of different test procedures.
  • One of these methods which is supposed to check the climate resistance of the solar modules, is the steam-heat climate test.
  • the modules According to the well-known standard IEC 1215, the modules are exposed to a temperature of 85 ° C at 85 percent relative humidity for 1000 hours.
  • Laminated solar modules with boron-doped zinc oxide electrode layers show an unusually strong degradation in this test method, ie an inadmissibly high decrease in efficiency after the climate test.
  • the main reason for this is their instability with regard to the conductivity of the boron-doped CVD zinc oxide layers against water vapor at elevated temperatures.
  • the surface resistance of such layers increases after the test by a factor of more than 10 ⁇ to a value of more than 1 k ⁇ / square.
  • a value of less than 10 ⁇ / square is required to achieve a high fill factor for solar modules. This can be achieved by simple encapsulation with a laminate structure using a ner adhesive film and possibly a second glass pane can not be reached.
  • CIGS Iron (Gallium) diselenide
  • the absorber shows degradation phenomena on the surfaces that are exposed to the climate test conditions unprotected or only covered with a conventional laminate structure.
  • the back electrode which is made of molybdenum, additional climate-independent degradations occur at the interface with the CIGS absorber layer.
  • One way of preventing moisture from diffusing into a laminate and in particular into a solar module is to extend the diffusion path for the moisture.
  • laminates with a sufficiently wide edge of more than 15 cm the degradation of a boron-doped zinc oxide layer is delayed sufficiently.
  • such a wide margin is unacceptable for a solar module because of the then high proportion of inactive module surface.
  • the object of the present invention is to provide a layer structure which is insensitive to moisture and / or corrosion and which can be produced simply and without too much additional production expenditure and which has increased stability both in relation to the test conditions specified and in conventional use.
  • a moisture and / or corrosion-sensitive layer can be easily protected against a climatic and, in particular, moist by an additional barrier layer applied directly above the layer. degradation-related or can be protected.
  • an additional barrier layer can be used, for example, to obtain thin-film solar modules which can withstand the steam-heat climate test mentioned at the outset without any appreciable loss in performance and without any visible corrosion damage.
  • the layer structure is part of an electrical or optical component in which the barrier layers have a vapor barrier and / or a corrosion protection effect, parts of the component which are optically active and / or working with electrical potential differences being covered with electrically insulating barrier layers layers with no potential difference, on the other hand, with conductive barrier layers.
  • the moisture and / or corrosion sensitive layer in the sense of the invention is a substrate-bound layer, which can be applied as a thin or thick layer and is amorphous, polycrystalline or metallic.
  • the additional barrier layer is a thin layer which is selected from aluminum oxide Al2O3, silicon nitride Si3N4 # titanium nitride TiN, molybdenum nitride MoN and silicon oxynitride SiO x Ny.
  • a thin layer is simple and inexpensive to produce and can be easily integrated into the manufacturing process of the moisture or corrosion-sensitive layer or of the layer structure or component containing this layer, in particular if the layer structure itself is a thin layer structure.
  • the barrier layer adapts to the function of the covered layer and is, for example, optically transparent, electrically conductive or insulating, it shows no negative influence on the Layer structure. It neither impairs the operation of an optical or electrical component containing the layer structure, nor does it impair its properties.
  • the thin-film barrier layers mentioned can be classified as dense, i.e. Deposit pore-free, optically transparent and edge-covering layers in known processes. Depending on the density or the freedom from pores with which such a layer can be produced, a barrier layer of 100 nm thickness may be sufficient to ensure complete protection against moisture and / or corrosion. A thicker barrier layer is of course possible, but not necessary. In the case of deposition processes which lead to barrier layers which are not completely pore-free or not completely homogeneous or which do not cover edges well, a higher layer thickness is preferably selected. If there are high topography levels on the layer structure, a layer thickness of up to approximately 2 ⁇ m is chosen for good edge coverage of the barrier layer.
  • Plasma-assisted CVD processes are particularly preferred for the production of both dense and well-covering barrier layers of small layer thickness with the lowest possible deposition temperatures.
  • the barrier layer has good adhesion to most materials used as an electrical or optical functional layer. If necessary, an adhesion promoter layer may also be required.
  • the layer structure according to the invention has the barrier layer as an additional layer to the conventional layer structure comprising one or any number of layers, it can also be covered with a conventional cover, for example with a laminate structure.
  • a laminate structure In the case of solar modules, it is in particular a laminate which is at least still an artificial Layer of material and optionally a protective film and / or a cover plate made of glass.
  • the plastic layer is preferably a hot-melt adhesive layer on which the cover film and optionally the glass pane are also laminated.
  • Other components can additionally or alternatively be covered or encased with other covers, for example with cast resin layers or other casting compounds, over the barrier layer.
  • the barrier layer as the uppermost and covering layer is sufficient to protect the solar cell.
  • the barrier layer according to the invention is particularly suitable for a laminate structure, since it has good adhesion to or under conventional hotmelt adhesive layers used for this purpose.
  • the good adhesion of the hot-melt adhesive film and thus of the entire laminate structure leads to an additional improved seal which prevents the diffusion of
  • the barrier layer is arranged over the edge of the layer to be protected so that its entire surface, including the side walls, is covered. To the side of the sensitive layer, the barrier layer closes with a climate-stable layer. Such layers are sealed against moisture and / or hot and humid environments and do not show any corrosion or other disadvantageous changes even after prolonged exposure.
  • the barrier layer preferably encloses the moisture-sensitive thin layer from above and from the side and, for example, excludes it at the bottom edge Glass existing substrate, a metal layer or a passivation layer.
  • the passivation layer can also be a barrier layer.
  • silicon oxide is also suitable for special applications.
  • Titanium and molybdenum nitride can be made electrically conductive and are also particularly hard and scratch-resistant. It is therefore suitable as a passivation layer for, in particular, metallic and therefore, in principle, corrosion-sensitive electrode layer, as is used in particular as a lower electrode for thin-film components.
  • the barrier layers show good adhesion to all of the layers mentioned and thus form moisture-tight and chemically stable interfaces to these layers.
  • the layer structure is an electrical component with at least two electrodes, in which one electrode is formed from an electrode layer arranged directly above the substrate.
  • This electrode layer can be structured to produce the above-mentioned electrode and thus represent an electrode structure as is particularly suitable for integrated series-connected thin-film solar modules.
  • the electrical connections for the at least two electrodes can also be formed from this lower electrode layer and led out laterally from the region of the component.
  • Such an arrangement has the advantage that, compared to a conventional arrangement with, for example, soldered electrical connections, it can be made particularly flat without additional structural steps. This facilitates an edge covering covering with the barrier layer according to the invention.
  • Those led out of the layer structure of the component under the barrier layer and out of the first electrode layer trained electrical connections can consist of a corrosion-resistant metal. However, they are preferably covered with the electrically conductive passivation layer mentioned, in particular a titanium or molybdenum nitride layer.
  • the passivation layer can completely cover the lower electrode layer and can be structured accordingly. It is also possible to cover the lower electrode layer only in the area of the electrical connections with the passivation layer, and in particular only in the area of the implementation of the connections under the barrier layer.
  • Another advantageous embodiment of the invention relates to the CIGS thin-film solar modules already mentioned.
  • a defined alkali content is required in the CIGS absorber layer for maximum efficiency of the solar cell.
  • a barrier layer according to the invention which is designed as a passivation layer, can advantageously be placed over the base or back electrode deploy.
  • a barrier layer made of titanium or molybdenum nitride can simultaneously serve as a passivation layer for the electrical connections leading to the outside or as a barrier layer for the entire lower electrode. It has particularly good adhesion to an additional barrier layer above the solar cell and thus forms a particularly good and tight interface to the barrier layer.
  • FIG. 1 shows a schematic cross section through a test arrangement with a climate-sensitive thin layer.
  • FIGS 2 to 5 show schematic cross sections through climate-stable layer arrangements.
  • FIG. 6 shows a schematic cross section
  • FIGS. 7 and 8 show a special application of the invention on the basis of schematic cross sections through a series-connected thin-film solar cell.
  • FIG. 1 shows a thin-layer arrangement serving as a test structure with a known encapsulation.
  • a carrier consisting of a 2 mm thick window glass (soda-lime glass)
  • a 1.5 ⁇ m thick boron-doped zinc oxide layer 2 is applied by means of the CVD process in such a way that the carrier 1 remains free in the entire peripheral edge area.
  • Metal contact strips 3 are now soldered on two opposite sides in such a way that the electrical surface conductivity of the zinc oxide layer 2 can be reliably determined.
  • a conventional laminate structure 5 is now produced above this, for example by laminating an approximately 0.5 mm thick EVA film at approximately 160 ° C.
  • the laminate structure has an overlap area of 1 cm with the substrate on the side of the thin-layer arrangement.
  • FIG. 2 now shows a first construction according to the invention, in which a boron-doped zinc oxide layer 2 arranged on a substrate 1 with electrode strips 3 applied thereon is again used as the test structure.
  • a barrier layer 4 is now applied over this arrangement.
  • a plasma CVD method is used for application, which can be carried out at low process temperatures of, for example, 200 to 300 ° C.
  • a barrier layer 4 of approximately 0.5 to 2 ⁇ m and in particular 0.8 ⁇ m thick silicon nitride is deposited at 200 ° C. in a plasma CVD process.
  • the barrier layer is deposited in such a way that the thin layer 2 is completely covered with the barrier layer 4.
  • the likewise electrically insulating Al 2 O 3 and SiO x N y layers can also be used as barrier layers.
  • a laminate structure 5 is applied above this, as already described in FIG.
  • the thin layer arrangement according to the invention survives the climatic test without detectable degradation, that is to say without the initial surface conductivity of the thin layer being reduced. Since, as stated, this parameter is an excellent probe for the detection of exposure to moisture, this measurement result shows the high effectiveness of the encapsulation according to the invention.
  • FIG. 3 shows a schematic cross section of a layer structure in which a moisture-sensitive layer and in particular a thin layer 2 are arranged on a substrate 1 between a lower electrode 3a and an upper electrode 3b.
  • electrical connections 6 are provided which are formed directly on the substrate by structuring the lower electrode layer 3a. While the lower electrode 3a is contacted via an electrical connection 6, the upper electrode 3b is connected to the electrical connection 6 ', which is connected by a Structure line is electrically isolated from the lower electrode 3a.
  • a barrier layer 4 is now applied over this arrangement, which completely covers the upper electrode 3b and the thin layer 2. The masked application or subsequent structuring of the barrier layer exposes the electrical connections 6 and 6 'and does not cover the barrier layer 4.
  • the climate-tight encapsulation of the component shown here can be reinforced by applying a laminate structure 5 according to FIGS. 1 or 2.
  • the thin-film component can be a solar cell, for example.
  • Figure 4 shows a further embodiment of the invention. This differs from the embodiment according to FIG. 3 in that the lower electrode layer 3a is completely covered with a metallically conductive passivation layer 7 before structuring.
  • the further structure corresponds to the exemplary embodiment described with reference to FIG. 3.
  • the lower electrode layer which can consist, for example, of a corrosion-sensitive metal, is also protected against moisture and other external corrosion-promoting effects by the electrically conductive passivation layer 7.
  • This arrangement is implemented, for example, in a CIGS solar cell which, for example, a glass substrate 1, a molybdenum back electrode 3a, a titanium or molybdenum nitride passivation layer 7, the thin layer 2 with the CIGS absorber layer having a semiconductor junction, and an upper electrode 3b, for example one Boron doped zinc oxide electrode.
  • the barrier layer 4 is a by CVD or plasma CVD applied thin film made of aluminum oxide, silicon nitride or silicon oxynitride.
  • the exemplary embodiment according to FIG. 5 differs from the exemplary embodiment described with reference to FIG. 4 in that the lower electrode layer 3a is covered with an electrically conductive passivation layer 7 and 7 'only in the area of the electrical connections 6 and 6'.
  • the passivation layer can either be applied masked or applied over the entire surface immediately before the structuring of the lower electrode layer 3a and then structured.
  • the passivation layer is deposited or sputtered on using a thin-film process such as reactive sputtering or a plasma-assisted CVD process.
  • a thin-film process such as reactive sputtering or a plasma-assisted CVD process.
  • 100 to 150 nm layer thickness is sufficient for a titanium nitride layer.
  • FIG. 6 shows, on the basis of a schematic cross section, a possibility of structuring a thin layer 2 arranged between two electrodes 3a and 3b by means of two separating joints 8 extending to a climate-stable layer, in order to subsequently apply a barrier layer 4 (not shown) in the separating joints 8 to achieve a climate-tight seal or a climate-tight adhesion of the barrier layer on the underlying climate-stable layer.
  • a passivation layer 7 above the lower electrode 3a serves as a climate-stable layer.
  • FIGS. 7 and 8 show a further embodiment of the invention on the basis of schematic cross sections through a solar module with integrated series-connected solar cells in thin-film construction.
  • the solar cell is applied, for example, to a substrate 1 and comprises a lower electrode 3a, a thin layer 2 with the semiconductor structure and an upper electrode 3b.
  • the solar cells are structured, for example, in the form of strips, with a series connection with the respectively adjacent strip-shaped solar cell being achieved by leading a strip-shaped upper electrode 3b down onto the respectively adjacent strips of the lower electrode 3a.
  • the first structuring step serves for structuring the lower electrode 3a, the second for structuring the semiconductor layers (thin layer) 2 and the third for separating the upper electrode 3b.
  • the latter structuring step either the semiconductor layer
  • FIG. 7 shows structuring trenches P3 reaching as far as the lower electrode 3a.
  • edge-covering barrier layer 4 is filled and leveled by overgrowth.
  • the barrier layer 4 is applied to a surface which projects beyond the layer structure on all sides and also overlaps the electrical connections 6 and 6 '.
  • the barrier layer 4 can then be partially removed again via the electrical connections 6 and 6 ′ in order to enable an external electrical connection, for example by soldering on metal strips 9.
  • the barrier layer also takes place after the metal strips 9 have been soldered on so that the solder joint is also covered by the barrier layer 4. In this way, the passivation layer (7) for the lower electrode 3a can be omitted.
  • the climate and corrosion-stable encapsulation of any layer structures and in particular large-area thin-layer arrangements which have layers sensitive to climate and corrosion are achieved. It is particularly suitable for the climate-tight encapsulation of solar cells, but of course it is not restricted to such. The invention is particularly suitable for those thin-film arrangements which are exposed to hot and / or humid environments. Of course, this also applies to layer structures that are usually not exposed to such corrosion-supporting environmental conditions.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

Structure à couches dotée d'au moins une couche sensible à la corrosion et/ou d'une couche sensible à l'humidité, par exemple pour une cellule solaire, sur laquelle est appliquée une couche barrière destinée à encapsuler ladite structure et à la rendre résistante aux intempéries et à la corrosion. Selon la présente invention, la couche barrière est une couche mince constituée de nitrure de titane ou de molybdène, d'oxyde d'aluminium, de nitrure de silicium ou d'oxynitrure de silicium. Cette couche barrière peut être combinée avec une structure stratifiée supplémentaire du type utilisé pour les cellules solaires.
PCT/EP1998/000832 1997-02-24 1998-02-13 Structure a couches resistant aux intemperies et a la corrosion WO1998038683A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98906951A EP0966765A1 (fr) 1997-02-24 1998-02-13 Structure a couches resistant aux intemperies et a la corrosion
JP53724698A JP2001513264A (ja) 1997-02-24 1998-02-13 耐候性及び耐食性の層構造体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19707280.1 1997-02-24
DE19707280A DE19707280A1 (de) 1997-02-24 1997-02-24 Klima- und korrosionsstabiler Schichtaufbau

Publications (1)

Publication Number Publication Date
WO1998038683A1 true WO1998038683A1 (fr) 1998-09-03

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PCT/EP1998/000832 WO1998038683A1 (fr) 1997-02-24 1998-02-13 Structure a couches resistant aux intemperies et a la corrosion

Country Status (4)

Country Link
EP (1) EP0966765A1 (fr)
JP (1) JP2001513264A (fr)
DE (1) DE19707280A1 (fr)
WO (1) WO1998038683A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6407329B1 (en) * 1999-04-07 2002-06-18 Bridgestone Corporation Backside covering member for solar battery, sealing film and solar battery
US8993877B2 (en) 2009-06-23 2015-03-31 Toray Engineering Co., Ltd. Solar battery

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ES2396118T3 (es) 2002-02-01 2013-02-19 Saint-Gobain Glass France S.A. Capa barrera hecha de una resina curable que contiene un poliol polimérico
DE102004040277B4 (de) * 2004-06-30 2015-07-30 Osram Opto Semiconductors Gmbh Reflektierendes Schichtsystem mit einer Mehrzahl von Schichten zur Aufbringung auf ein III/V-Verbindungshalbleitermaterial
KR101405018B1 (ko) 2007-10-08 2014-06-10 주성엔지니어링(주) 박막형 태양전지 및 그 제조방법
JP5219538B2 (ja) * 2008-02-12 2013-06-26 大成建設株式会社 太陽光発電薄膜を基材に直接形成した太陽電池
JP2010087339A (ja) * 2008-10-01 2010-04-15 Fujifilm Corp 有機太陽電池素子
JP2010093172A (ja) * 2008-10-10 2010-04-22 Fujifilm Corp 封止デバイス
FR2939240B1 (fr) * 2008-12-03 2011-02-18 Saint Gobain Element en couches et dispositif photovoltaique comprenant un tel element
JP2012522393A (ja) * 2009-03-31 2012-09-20 エルジー イノテック カンパニー リミテッド 太陽光発電装置及びその製造方法
JP5114683B2 (ja) * 2009-09-07 2013-01-09 新日鐵住金株式会社 太陽電池用ガラス基板の裏面電極及びその製造方法
TWI514608B (zh) 2010-01-14 2015-12-21 Dow Global Technologies Llc 具曝露式導電柵格之防溼光伏打裝置
CN102812558B (zh) * 2010-02-09 2015-09-09 陶氏环球技术有限责任公司 具有改善的屏障膜粘附的抗湿光伏器件
JP5602700B2 (ja) * 2010-11-02 2014-10-08 富士フイルム株式会社 光電変換素子およびその製造方法
KR101305810B1 (ko) * 2011-10-25 2013-09-09 엘지이노텍 주식회사 태양전지 모듈

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6407329B1 (en) * 1999-04-07 2002-06-18 Bridgestone Corporation Backside covering member for solar battery, sealing film and solar battery
US8993877B2 (en) 2009-06-23 2015-03-31 Toray Engineering Co., Ltd. Solar battery

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Publication number Publication date
JP2001513264A (ja) 2001-08-28
EP0966765A1 (fr) 1999-12-29
DE19707280A1 (de) 1998-08-27

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