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EP0000715B1 - Procédé de fabrication de cellules solaires sulfure de cadmium-sulfure de cuivre et cellules solaires réalisées selon ce procédé - Google Patents

Procédé de fabrication de cellules solaires sulfure de cadmium-sulfure de cuivre et cellules solaires réalisées selon ce procédé Download PDF

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Publication number
EP0000715B1
EP0000715B1 EP78100452A EP78100452A EP0000715B1 EP 0000715 B1 EP0000715 B1 EP 0000715B1 EP 78100452 A EP78100452 A EP 78100452A EP 78100452 A EP78100452 A EP 78100452A EP 0000715 B1 EP0000715 B1 EP 0000715B1
Authority
EP
European Patent Office
Prior art keywords
grid
cover glass
heat
sulfide layer
support
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.)
Expired
Application number
EP78100452A
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German (de)
English (en)
Other versions
EP0000715A1 (fr
Inventor
Gerhard Dipl.-Ing. Bilger
Gert Dr.-Ing. Hewig
Fritz Dipl.-Phys. Pfisterer
Hans-Werner Dipl.-Ing. Schock
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Individual
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Individual
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Publication date
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Publication of EP0000715A1 publication Critical patent/EP0000715A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/169—Photovoltaic cells having only PN heterojunction potential barriers comprising Cu2X/CdX heterojunctions, wherein X is a Group VI element, e.g. Cu2O/CdO PN heterojunction photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/807—Double-glass encapsulation, e.g. photovoltaic cells arranged between front and rear glass sheets
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • 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 method for producing solar cells with a pn thin-film heterojunction from an electrically conductive base applied to a carrier, a cadmium sulfide layer vapor-deposited thereon and a copper sulfide layer chemically produced thereon, onto which an electrically conductive grid is placed, which is covered, heat-sealed and pressed with a cover glass which is provided with a heat-sealing adhesive on the side facing the grating, the carrier with the base, with the cadmium sulfide layer and with the copper sulfide layer being produced as a prefabricated component.
  • Cadmium sulfide solar cells have a lower efficiency than the known silicon single-crystal solar cells, but they have the considerable advantage that they can be manufactured much more cheaply. It is known to produce a semiconductor photo element from a thin silicon single crystal with p- and n-type zones, which is then or the like by enveloping with a casting resin. is encapsulated. Cadmium sulfide solar cells, which belong to the so-called thin-film solar cells, have a polycrystalline semiconductor layer which is evaporated onto an electrically conductive base, usually a metallic support, so that their production is considerably cheaper.
  • the invention is based on the object of further improving the method for producing cadmium sulfide solar cells of the type mentioned at the outset in order to obtain a favorable efficiency and at the same time to produce a self-contained, encapsulated cell.
  • This object is achieved in that the prefabricated lower part is heat-sealed and pressed with a prefabricated upper part which consists of the cover glass, the heat-sealing adhesive and the grid, which is sealed onto the cover glass in the form of a film with the aid of the heat-sealing adhesive, after which the heat sealing is carried out and pressing the upper part and the lower part out of the foil, the grid is etched out.
  • the heat seal adhesive used in this training has several functions. First, it has the function of holding the copper foil on the upper part and then establishing the connection to the lower part, at the same time obtaining an encapsulated cell. This has the advantage that the grid is etched out of the film while it is held by the upper part, so that the risk of deformation or damage is further reduced, so that the possible efficiency is obtained with greater certainty.
  • the lower part contains a glass plate, on which, preferably using an adhesion promoter, a base made of silver or zinc is applied, onto which the cadmium sulfide layer is evaporated.
  • a glass plate in the lower part has the advantage that not only the mechanical strength is increased, but also that uniform thermal expansions of the entire cell are ensured, so that destruction or damage by thermal stresses is not to be expected, even if this is particularly true for terrestrial application certain solar cell is set up in areas where, for example, very large differences between the day and night temperatures occur.
  • the heat seal adhesive is applied in liquid form and then dried in vacuo and, if appropriate, thereafter in the atmosphere.
  • first drying under vacuum, all gases and vapors that may interfere with the electrical properties of the solar cell are removed, an adhesive layer is created, which then enables heat sealing and whose thickness is somewhat thicker than the thickness of the grid.
  • subsequent drying to be carried out under atmospheric conditions leads to an appropriate oxidation of the heat seal adhesive layer in some cases.
  • a thin gold layer is applied galvanically before the upper part and lower part are joined onto the grid in order to achieve a barrier-free contact.
  • a solar cell is produced according to the method according to the invention, in which the cover glass with the grid and the base plate with the base are laterally offset from one another in such a way that on one side one of the base and on the other side one of the Contact formed by the grid is exposed.
  • Such a solar cell is very easy to connect to other solar cells, since the necessary contacts are created and freely accessible.
  • a large cover glass is provided as the upper part with a plurality of electrically conductive grids arranged in a row, each of which is assigned a lower part, which are arranged so offset to the grids that the documents are on one side with the grating assigned to the adjacent lower part are in contact and that on one side of the cover glass an edge of the outer grid is exposed as a contact, while on the other side an edge of the base of the outer lower part is exposed as a contact.
  • a large cover glass is provided with several rows of grids and accordingly with several rows of lower parts. This results in a very efficient production, the somewhat simple upper part taking up a larger area, while the lower parts are designed as individually manufactured elements which are of a size which is favorable for the application of the cadmium sulfide layer.
  • the solar cell shown in Fig. 1 has a prefabricated lower part 1 and a prefabricated upper part 2, which are assembled into a self-contained cell in a subsequent operation.
  • the lower part 1 has a base plate 3, which preferably consists of a substrate glass. This glass is ultrasonically cleaned in a solvent before an adhesion-promoting layer 4 is applied on one side, for which vapor-deposited chromium (Cr) is preferably used. A layer 5 of silver (Ag) is also applied to this adhesion promoter by vapor deposition. This vapor deposition of both the adhesion promoter and the silver takes place at approximately 400 ° C., which on the one hand leads to water vapor being released and on the other hand to good crystallization of the silver layer 5, which is advantageous for the subsequent operations.
  • a base plate 3 which preferably consists of a substrate glass. This glass is ultrasonically cleaned in a solvent before an adhesion-promoting layer 4 is applied on one side, for which vapor-deposited chromium (Cr) is preferably used.
  • Cr chromium
  • a layer 5 of silver (Ag) is also applied to this adhesion promoter by vapor deposition. This vapor deposition
  • a layer of cadmium sulfide (CdS) of approximately 3011 is evaporated onto the layer 5 made of silver. This vapor deposition takes place in the device shown in FIG. 4, which will be explained later.
  • the previously prefabricated lower part 1 is kept at a temperature of 200 °.
  • the cadmium sulfide layer 6 is roughened using an aqueous hydrochloric acid (HCl) to reduce reflection and to etch out grain boundaries.
  • a copper sulfide (Cu 2S) layer 7 is then produced on the cadmium sulfide layer 6, which is done by a chemical reaction by briefly immersing the lower part in a monovalent copper ion solution for about 5 to 10 seconds. This copper sulfide layer should have an order of magnitude of 0.2 ⁇ thickness.
  • a copper (Cu) layer 8 which has a thickness of 30 to 100 ⁇ , is also evaporated onto the copper sulfide layer 7. Subsequently, the lower part is heated at about 180 ° under atmosphere, which makes it possible to fill in vacancies due to copper diffusing into the copper sulfide layer and to form a copper oxide layer (Cu z O). With this operation, the manufacture of the lower part 1 is finished. As can be seen from FIG. 1, the layers 6, 7 and 8 are applied in such a way that an edge strip 9 of the base 5 made of silver remains free in FIG. 1 on the right, which can later be used as a contact.
  • the upper part 2 is also manufactured separately. It contains a cover glass 10, which is also cleaned with ultrasound in a solvent before further processing. On this cover glass 10, a liquid heat seal adhesive 11 with a layer thickness of 120 to 150 .mu.m is applied on one side by means of a doctor or the like. applied. In practice, an adhesive from Kömmerling, Zweimaschiner Landstrasse, 6780 Pirmasens, which has the company identification AK 543, is suitable. The cover slip 10 and the initially applied liquid heat seal adhesive 11 are in one Vacuum oven then subjected to drying at about 100 ° C for 4 to 5 hours, so that vapors and chamfers can escape from the initially liquid heat seal adhesive.
  • the heat seal adhesive 11 reduces its thickness to approximately 25% of the original application thickness of 120 to 15 ⁇ ⁇ .
  • a copper foil with a thickness of approximately 35 p is then sealed onto the cover glass 10 at approximately 170 ° to 180 °.
  • the grid 12 shown in FIG. 1 is then etched out of this copper foil, using the technique known in the production of printed circuit boards.
  • a lacquer grid is applied using the screen printing process, which corresponds to the grid 12 that remains afterwards.
  • a layer 13 of gold is applied galvanically to the grid in order to enable a barrier-free contact.
  • the layer thickness is approximately 100 to 1000 A, preferably 250 A.
  • the now finished upper part 2 is connected to the lower part 1 in a vacuum press at approx. 170 ° to 180 °, the connection being obtained by the layer 11 of the heat seal adhesive, which has a layer thickness which is somewhat larger than the thickness of the grid 12 .
  • the grid 12 lies with its gold layer 13 on the layer 8 made of copper and establishes a secure contact, while subsequently the grid 12 penetrates into the layer 11 during heating, which also has an adhesive connection between the cover glass 10 and the layer 8 manufactures.
  • the upper part 2 is applied so offset on the lower part 1 that on the left in the drawing, i.e. A strip 14 of the grid 12, which also serves as a contact, is exposed opposite the contact strip 9.
  • a solar battery can be assembled from several of the solar cells shown in FIG. 1, the contacts of the adjacent solar cells formed by the edge strips 9 and 14 then being connected to one another.
  • a common cover glass 15 can be provided for several solar cells, as shown in FIGS. 2 and 3.
  • lower parts 1 are used which have been produced in accordance with the preceding description. These bases are appropriately manufactured in a certain size in which they can be manufactured economically.
  • the contacts between the individual solar cells are produced in the manner described for FIG. 1, which are only indicated schematically in FIG. 2. In this case, contact is made between the grid 12 and the layer 5 of silver serving as an electrically conductive base for those solar cells lying in a row. As can be seen in Fig.
  • FIG. 4 schematically shows a device with which a homogeneous layer of cadmium sulfide can be evaporated onto a lower part 1 of a solar cell.
  • a graphite furnace 16 is provided, which is surrounded by a graphite heating coil 17 to which a power supply 18 is connected.
  • the outside of the graphite heating coil 17 is surrounded by a radiation reflector 19.
  • a thermocouple 20 measuring the temperature for temperature control projects into the graphite furnace 16.
  • the graphite furnace is seated on an insulating ceramic ring 21.
  • the graphite furnace 16 has the shape of a cylinder, in which an upwardly open chamber 23 is divided by an annular collar 22, into which cadmium sulfide in powder form is filled.
  • the chamber 23 is closed at the top by a porous quartz frit 24 which is closely fitted into the cylindrical part adjoining the collar 22 to the outside.
  • the quartz frit 24 and the inner surface of the graphite furnace 16 are expediently ground.
  • the quartz frit 24 is secured in its position in a manner not shown by one or more pins.
  • the quartz frit 24 is arranged at a sufficient distance from the end of the graphite furnace 16, that is to say approximately one third of the height, so that a temperature high enough to be maintained in the region of the quartz frit is that vaporization and so that the quartz frit can be prevented from becoming impermeable.
  • thermocouple 20 adjoins the graphite furnace, which sits on the ceramic ring. This approach envelops the thermocouple 20 over a sufficient length so that it is ensured that the temperature measured by the thermocouple 20 corresponds as closely as possible to the temperature of the chamber 23.
  • a displaceable diaphragm 26 Arranged above the outlet of the graphite furnace 16 is a displaceable diaphragm 26, with which the evaporating gas from the lower part 1 of the solar cell can initially be maintained.
  • This lower part 1 rests on a support 27, which leaves a section of the size to be vaporized on the lower part 1 with cadmium sulfide.
  • a heating part 28 designed as a graphite meander is provided, which is covered by a radiation reflector 29. This heating part 28 ensures that the lower part of the solar cell maintains a temperature of approximately 200 ° C. when the cadmium sulfide is evaporated.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Claims (9)

1. Procédé pour la réalisation de cellules solaires avec une hétéro-transition en couche mince pn constituée d'une sous-couche électriqement conductrice rapportée sur un support, d'une couche de sulfure de cadmium vaporisée par dessus, et d'une couche de sulfure de cuivre obtenue chimiquement sur la couche précédente, et sur laquelle est posée une grille électriquement conductrice, qui est recouverte d'un verre muni sur sa face tournée vers la grille d'une colle pour scellement à chaud, et qui est scellée à chaud et pressée, le support avec la sous-couche et avec la couche de sulfure de cadmium et la couche de sulfure de cuivre étant réalisé en tant que partie inférieure préfabriquée, procédé caractérisé en ce que la partie inférieure préfabriquée est scellée à chaud et pressée avec une partie supérieure préfabriquée, qui est constituée du verre de recouvrement, de la colle pour scellement à chaud et de la grille, laquelle est appliquée sous la forme d'une feuille, à l'aide de a colle pour scellement à chaud, sur le verre de recouvrement, après quoi, avant le scellement à chaud et le pressage de la partie supérieure et de la partie inférieure, la grille est formée de la feuille par attaque chimique.
2. Procédé selon la revendication 1, caractérisé en ce que la partie inférieure (1) contient une plaquette de verre (3), sur laquelle est vaporisée à environ 400°C, de préférence avec utilisation d'un intermédiaire d'adhérence (4), une sous-couche (5) d'argent ou de zinc, sur laquelle est vaporisée la couche (6) de sulfure de cadmium.
3. Procédé selon la revendication 1, caractérisé en ce que la colle pour scellement à chaud (11) est appliquée sous forme liquide et est ensuite séchée sous vide puis éventuellement dans l'atmosphère.
4. Procédé selon la revendication 1 ou 2, caractérisé en ce que, avant l'assemblage de la partie supérieure (2) et de la partie inférieure
(1), une couche mince d'or (13) est appliquée galvaniquement sur la grille (12) pour obtenir un contact exempt de couche de blocage.
5. Cellule solaire réalisée conformément au procédé selon l'une des revendications 1 à 4, caractérisée en ce que comme partie supérieure, (10) avec la grille (12), et la plaque de base (3) avec la sous-couche (5), sont décalés latéralement l'un par rapport à l'autre de façon telle, que sur l'un des côtés est dégagé un contact (9) constitué par la sous-couche (5) tandis que sur l'autre côté est dégagé un contact (14) constitué par la grille (12).
6. Cellule solaire selon la revendication 5, caractérisé en ce que comme partie supérieure, il est prévu un verre de recouvrement (15) de grande surface avec plusieurs grilles électriquement conductrices disposées selon une rangée, et à chacune desquelles est associée une partie inférieure (1), cette partie inférieure étant décalée par rapport aux grilles de façon telle que les sous-couches (5) sont d'un côté en contact avec la grille associée à la partie inférieure voisine, et que sur l'un des côtés du verre de recouvrement, un bord de la grille externe est dégagé comme contact, tandis que sur l'autre côté un bord de la sous-couche (5) de la partie inférieure externe (1) est dégagé comme contact.
7. Cellule solaire selon la revendication 6, caractérisée en ce qu'il est prévu un verre de recouvrement (15) de grande surface avec plusieurs rangées de grilles et, de façon correspondante, avec plusieurs rangées de parties inférieures (1).
8. Cellule solaire selon au moins l'une des revendications 5 à 7, caractérisée en ce que les bords du verre de recouvrement (10, 15) ne se trouvant pas dans la zone des contacts dégagés (9, 14), et la plaque de base (3), sont reliés ensemble de façon étanche.
EP78100452A 1977-07-21 1978-07-20 Procédé de fabrication de cellules solaires sulfure de cadmium-sulfure de cuivre et cellules solaires réalisées selon ce procédé Expired EP0000715B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2732933A DE2732933C2 (de) 1977-07-21 1977-07-21 Verfahren zum Herstellen von Dünnschicht-Solarzellen mit pn-Heteroübergang
DE2732933 1977-07-21

Publications (2)

Publication Number Publication Date
EP0000715A1 EP0000715A1 (fr) 1979-02-21
EP0000715B1 true EP0000715B1 (fr) 1981-09-02

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EP78100452A Expired EP0000715B1 (fr) 1977-07-21 1978-07-20 Procédé de fabrication de cellules solaires sulfure de cadmium-sulfure de cuivre et cellules solaires réalisées selon ce procédé

Country Status (4)

Country Link
US (1) US4283590A (fr)
EP (1) EP0000715B1 (fr)
AU (1) AU519312B2 (fr)
DE (1) DE2732933C2 (fr)

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US7898054B2 (en) 2000-02-04 2011-03-01 Daniel Luch Substrate structures for integrated series connected photovoltaic arrays and process of manufacture of such arrays
US9865758B2 (en) 2006-04-13 2018-01-09 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US9236512B2 (en) 2006-04-13 2016-01-12 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US8884155B2 (en) 2006-04-13 2014-11-11 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US8729385B2 (en) 2006-04-13 2014-05-20 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US8822810B2 (en) 2006-04-13 2014-09-02 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US9006563B2 (en) 2006-04-13 2015-04-14 Solannex, Inc. Collector grid and interconnect structures for photovoltaic arrays and modules
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AU3810878A (en) 1980-01-24
DE2732933C2 (de) 1984-11-15
EP0000715A1 (fr) 1979-02-21
AU519312B2 (en) 1981-11-26
DE2732933A1 (de) 1979-02-08
US4283590A (en) 1981-08-11

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