EP3195373A1 - Semi-transparent photovoltaic device comprising a through-hole - Google Patents
Semi-transparent photovoltaic device comprising a through-holeInfo
- Publication number
- EP3195373A1 EP3195373A1 EP15770483.4A EP15770483A EP3195373A1 EP 3195373 A1 EP3195373 A1 EP 3195373A1 EP 15770483 A EP15770483 A EP 15770483A EP 3195373 A1 EP3195373 A1 EP 3195373A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- forming
- stack
- holes
- layers
- 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- Withdrawn
Links
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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
- H01L31/04—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
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
- H01L31/0463—PV modules composed of a plurality of thin film solar cells deposited on the same substrate characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active layers
-
- 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
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
- H01L31/0468—PV modules composed of a plurality of thin film solar cells deposited on the same substrate comprising specific means for obtaining partial light transmission through the module, e.g. partially transparent thin film solar modules for windows
-
- 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 the field of producing photovoltaic cells in thin films that are semitransparent to the solar spectrum.
- the subject of the invention is more particularly a photovoltaic device comprising a substrate, in particular transparent in all or part of the solar spectrum, and a stack of thin layers formed on the substrate and comprising at least a first layer of electrically conductive material forming a rear electrode. , a second photo-absorbing layer in the solar spectrum and a third layer of electrically conductive material forming a front electrode.
- It also relates to a method of manufacturing such a photovoltaic device.
- a solar cell illuminated by the sun is capable of supplying an open-circuit voltage which is typically of the order of 0.5 to 1 V.
- an electric current of several tens of mA can be obtained.
- the electrical power thus provided may be sufficient to power small electrical devices consuming little power.
- a module with a surface area of 1 m 2 lit by the sun provides a power of about 100 W.
- These modules can be installed to serve as a power plant in highly sunny areas. Placed directly on the roof, they can also be used to power a domestic or industrial installation.
- the photovoltaic module can be taken directly as a building material for a roof or facade: it is called “Building Integrated Photovoltaics" or “BIPV” and this market presents a strong development potential.
- the aesthetic aspect is an important criterion and one can look for different effects, such as color or semi-transparency to the solar spectrum.
- CGS generally abbreviation for a compound of Cu, In, Ga, Se and S
- CGS generally abbreviation for a compound of Cu, In, Ga, Se and S
- it has a uniform black appearance that integrates well into the building and can be deposited in thin layers (with a thickness in a range of values between 0.5 and 5 ⁇ ) on many flexible or rigid substrates such as glass, steel or steel.
- polymers Other materials may also be deposited in thin layers such as "CZTS” (general abbreviation for a compound of Cu, Zn, Sn, Se, S), hydrogenated amorphous silicon, hydrogenated microcrystalline silicon or cadmium tellurium " CdTe ".
- a thin-film solar cell is generally composed of a substrate, a layer forming an electrode on the back, a layer of light-absorbing material in the solar spectrum, a possible buffer layer and a layer forming an electrode on the front face.
- the front face electrode and / or the back face electrode is transparent in the solar spectrum.
- a photovoltaic device comprises such layers organized and configured so that a plurality of such cells electrically connected in series with each other.
- the most widespread structure is composed of a glass substrate having a thickness for example of 3 mm and a stack of thin layers comprising a first layer of molybdenum Mo, forming a rear electrode, whose thickness is for example 1 ⁇ , a second layer of CIGS whose thickness is for example 1.5 ⁇ , a CdS buffer layer whose thickness is for example 50 nm and a third layer zinc doped aluminum oxide whose thickness is for example of the order of 500 nm and forming a front electrode.
- a glass substrate having a thickness for example of 3 mm and a stack of thin layers comprising a first layer of molybdenum Mo, forming a rear electrode, whose thickness is for example 1 ⁇ , a second layer of CIGS whose thickness is for example 1.5 ⁇ , a CdS buffer layer whose thickness is for example 50 nm and a third layer zinc doped aluminum oxide whose thickness is for example of the order of 500 nm and forming a front electrode.
- deposit methods and materials that
- the document US2010 / 0126559 describes a photovoltaic module of superstrate type, in which the substrate and the rear electrode are transparent. An opening is obtained during an etching step corresponding to an electrical isolation step used in the serialization of several cells by monolithic interconnection for the realization of a module.
- This opening is made through the light absorbing layer and the front electrode.
- This width can for example vary between 5 and 10% of the width of a photovoltaic cell.
- the photovoltaic module obtained can transmit between about 5 and 50% of the incident light.
- this solution has disadvantages.
- the openings made in the photovoltaic module are in the form of lines. They are then relatively visible to the eye and do not allow a uniform transmission of light.
- Document GB-A1 -2472608 proposes to produce a semi-transparent photovoltaic cell from a stack comprising a transparent substrate, a transparent back electrode, an opaque light-absorbing layer and an opaque front electrode. Small holes are formed through the front electrode and the photoactive layer so as to allow transmission of light through these two layers via these holes obtained by wet etching. Thus, an etching liquid is deposited on the surface of the photovoltaic cells by means of an ink jet head so as to allow localized etching.
- Figures 1 to 3 relate to a known solution in which holes are made by a method called "lift-off".
- the process begins with the deposition of an ink or resin on a substrate 1 of soda-lime glass 3 mm thick.
- the ink is deposited by ink jet in the form of pads 2 200 ⁇ spaced 400 ⁇ ( Figure 1).
- a layer 3 of molybdenum is then deposited over a thickness of 450 nm by sputtering.
- a photosabsorbent layer 4 of CIGS is formed by a sequential method: first Cu, In, Ga precursors are deposited by cathodic sputtering, then a thin layer of Si is deposited, then a rapid annealing under a protective atmosphere.
- the layer 4 of CIGS formed thus has a thickness of approximately 1.5 ⁇ .
- a buffer layer of 50 nm CdS is then deposited by chemical bath, then a 50 nm layer of ZnO and a 400 nm layer of ZnO doped with aluminum are deposited by sputtering.
- the use of the ZnO layer is optional.
- the stack of the ZnO layer and Al doped ZnO is marked 6.
- the ZnO layer doped with aluminum is known under the name "TCO" for "Transparent Conductive Oxide". The structure obtained is shown in FIG. 2.
- the structure is immersed during 2 minutes in a solvent chosen according to the nature of the ink deposited by ink jet, in an ultrasonic bath, and then dried under a stream of nitrogen.
- This treatment has the effect of removing all the material from the layers
- FIG. 1 An example of a photovoltaic device obtained by this method is shown in FIG.
- the layer 5 and the layer 6 are represented by a single and only identified layer 8.
- the object of the present invention is to provide a photovoltaic solution that overcomes the disadvantages listed above.
- an object of the invention is to provide a photovoltaic device and its manufacturing method that allow:
- a photovoltaic device comprising a substrate, in particular transparent in all or part of the solar spectrum, and a stack of layers formed on the substrate and comprising at least a first layer of electrically conductive material forming a back electrode, a second photo-absorbing layer in the solar spectrum and a third layer of electrically conductive material forming a front electrode, the stack comprising a plurality of individual holes each passing through the first, second and third layers to open onto the substrate and each having an inner wall delimited at the first layer, in the plane of the first layer and over the entire thickness of the first layer, by the material of the second layer.
- the value of the material thickness of the second layer in the plane of the first layer is between 5 and 450 ⁇ , preferably between 5 and 200 ⁇ .
- the holes are distributed in such a way that the ratio between, on the one hand, the perforated surface of the stack, corresponding to the sum of the surfaces of the holes of the plurality, and, on the other hand, the total area of the stacking in the main plane of the stack, is between 1% and 99%.
- each hole is spaced from the nearest adjacent hole, in the main plane of the stack, by a distance of between 200 and 1000 ⁇ .
- the holes may be distributed in the main plane of the stack according to a periodic tiling at the vertices of a basic pattern having the shape of a polygon such as a square or a hexagon.
- the invention also relates to a method of manufacturing a photovoltaic device comprising a step of providing a substrate, in particular transparent in all or part of the solar spectrum, and a step of forming a stack of thin layers on the substrate and having a first layer of electrically conductive material forming a back electrode, a second photo-absorbing layer in the solar spectrum, a third layer of electrically conductive material forming a front electrode, and a plurality of individual holes each passing through the first, second and third layer each having an inner wall delimited at the first layer, in the plane of the first layer and over the entire thickness of the first layer, by the material of the second layer.
- the step of forming the stack may include:
- a step of forming the first layer on the substrate a step of forming a plurality of individual through apertures in the first layer where each aperture passes through the first layer
- the step of forming the plurality of openings can be performed before the step of forming the plurality of holes.
- the dimensions of each opening in the main plane of the stack are strictly greater than the dimensions of each hole in the main plane of the stack.
- each hole in the main plane of the stack is preferably between 10 and 500 ⁇ .
- each opening in the main plane of the stack is preferably between 20 and 1000 ⁇ .
- the step of forming the plurality of openings may comprise a first step of chemical, mechanical or laser etching of the first layer.
- the step of forming the plurality of apertures comprises a first lift-off step performed through the first layer only at areas of the first layer coinciding with the locations of the openings to be formed.
- the method may comprise a step of forming a plurality of first pads of a first resin on the substrate at the locations of the openings to be formed, and after the step for forming the first layer, the method may comprise a step of applying a first solvent to the first layer, the first resin-first solvent pair being chosen so that said application step removes the first pads and the zones. of the first layer located above the first pads.
- the step of forming the plurality of holes may comprise a second step of chemical, mechanical or laser etching of the second and third layers.
- the step of forming the plurality of holes may comprise a second lift-off step performed through the second layer and the third layer, only at the level of zones of the stack coinciding with the locations of the holes to be formed.
- the method may comprise a step of forming a plurality of second pads of a second resin on the substrate at the locations of the holes to be formed, each second pad being formed in the center of a corresponding opening previously formed, and subsequent to the step of forming the second and third layers, the method may comprise a step of applying a second solvent on the stack, the second pair of resin-second solvent being chosen so that said application step removes the second pads and the areas of the second and third layers above the second pads.
- the step of forming the second layer on the first layer may comprise a step of depositing at least one layer of compounds able to form, by crystallization annealing, the photo-absorbing material of the second layer, then a step of crystallization annealing of said compounds in order to finalize the second layer and the step of forming the plurality of holes may comprise a second lift-off step, implemented between the step of depositing said at least one layer of compounds and the crystallization annealing step, and carried out through said compound layers only at areas of the stack coinciding with the locations of the holes to be formed.
- the method may comprise a step of forming a plurality of second pads of a second resin on the substrate at the locations of the holes to be formed, each second pad being formed in the center of a corresponding opening previously formed, and after the deposition step of said at least one layer of compounds and before the crystallization annealing step, the method may comprise a step of applying a second solvent on the stack, the pair second resin-second solvent being chosen so that said application step removes the second pads and the areas of said at least one layer of compounds located above the second pads.
- each first pad its dimensions in the main plane of the stack, preferably between 20 and 1000 ⁇ , are preferably strictly greater than the dimensions, in said main plane, of the second stud formed in the center of the opening corresponding to said first pad, preferably between 10 and 500 ⁇ .
- FIGS. 1 to 3 already described, illustrate various successive phases of a manufacturing method according to the prior art
- FIGS. 4A to 4D already described, illustrate the phenomenon of formation of short circuits between the front and rear electrodes;
- FIGS. 5 to 9 illustrate the different phases of a first exemplary method of manufacturing a photovoltaic device; according to the invention.
- FIGS. 10 to 13 illustrate different phases of a second exemplary method of manufacturing a photovoltaic device according to the invention
- FIGS. 14 and 15 illustrate different phases of a third exemplary method of manufacturing a photovoltaic device according to the invention. Description of preferred modes of the invention
- a photovoltaic device comprising on the one hand a substrate 10, on the other hand a stack of thin layers formed on the substrate 10 and comprising at least: a first layer 30 formed in an electrically conductive material and constituting a rear electrode, also called an electrode on the rear face,
- a second photo-absorbing or photo-active layer 40 in the solar spectrum intended to absorb all or part of the incident solar radiation on the front or upper face of the stack
- the invention also relates to a method of manufacturing such a photovoltaic device, various embodiments being detailed below.
- the substrate 10 is in particular of the type having transparency characteristics along its thickness in all or part of the solar spectrum.
- sandwich layer it is understood that the thickness of each of the layers preferably varies from a few atomic layers to about ten micrometers.
- the substrate 10 which is preferably transparent to light in all or part of the spectrum, is for example formed of glass, for example a soda-lime glass with a thickness of between 0.5 and 5 mm, and typically of 3 mm which is a standard thickness in the photovoltaic field. More generally, the substrate 10 may be formed of any other material such as an organic material, a plastic or polymer-based material, of treated glass, for example frosted glass, tinted.
- the notion of transparency of the substrate 10 refers to what a human eye can perceive wavelengths present in the solar spectrum: it is therefore wavelengths between 250 nm and 850 nm.
- the transparency of the substrate 10 is particularly advantageous in the particularly targeted application where the photovoltaic device is intended to be taken directly as a construction material for a roof or facade, that is to say in the context of a photovoltaic device of type "Building Integrated Photovoltaics" or "BIPV".
- the substrate 10 is not transparent according to its thickness, being then for example formed in a metallic material, a construction material, by example in concrete, composite material, etc., possibly covered with a layer of paint and / or protection.
- a first example of a photovoltaic device allows an observer located on the side of the substrate (especially located inside a building) to receive the light that reaches him on the front side of the photovoltaic device (especially from outside the building).
- the photovoltaic device can serve as a demonstration showcase for example: in this case the observer located on the front side of the photovoltaic device observes an object located at the rear of the substrate.
- the substrate may itself have functions other than the light transmission function. It could be functionalized by covering it with a printed image or carried on a second substrate; it could still, by a suitable device, have a backlight.
- the first layer 30 preferably has both ohmic properties to ensure optimum recovery of the charges emitted by the second layer 40 but also optical properties to ensure reflection towards the second layer 40 of the light spectrum portion not absorbed in direct transmission.
- the first layer 30 is in particular of metal type, for example Molybdenum Mo.
- the thickness noted “h" of the first layer 30 is preferably between 100 nm and 2 ⁇ , typically 1 ⁇ . It is deposited by any method, for example by a vacuum technique by sputtering or evaporation.
- the first layer 30 may however comprise other materials such as chromium Cr and / or tungsten W and / or Manganese Mn and / or Tantalum Ta and / or Niobium Nb and / or Titanium Ti.
- the second layer 40 is disposed, directly or indirectly, between the first layer 30 and the third layer 60 in the direction D. It is preferably made of inorganic semiconductor materials of type II l l-VI. In particular but not exclusively, the material in which the second layer 40 is formed comprises a compound of Cu, In, Ga, Se and S, known under the name "CIGS".
- the CIGS layer formed has, for example, a thickness of approximately 1.5 ⁇ .
- Other materials may be envisaged for the second layer 40, such as CdTe, hydrogenated amorphous silicon, hydrogenated microcrystalline silicon or any compound based on copper, zinc, tin, sulfur and selenium.
- the third layer 60 may be formed by a double layer composed of a ZnO layer having for example a thickness of 50 nm and a layer of ZnO doped with group II elements such as aluminum, for example having a thickness of 400 nm. These two layers are deposited for example by sputtering.
- the ZnO layer doped with aluminum is known under the name "TCO” for "Transparent Conductive Oxide".
- TCO Transparent Conductive Oxide
- the use of the ZnO layer is however optional. This layer may be omitted in the case where the buffer layer 50 is in CdS, or replaced by a layer of Zn ( i- X) Mg x O when the buffer layer 50 is Zn (O, H) S.
- transparent and conductive electrodes based on metal nanowires (Ag or Cu in particular), graphene, or other transparent conductive oxides such as indium tin oxide ( ITO) or fluorine-doped tin oxide (SnO 2 : F) can be used.
- ITO indium tin oxide
- SnO 2 : F fluorine-doped tin oxide
- a buffer layer 50 or "buffer” may be disposed between the third layer 60 and the second layer 40 depending on the thickness of the stack. It can be formed in a material comprising CdS cadmium sulphide.
- the CdS layer may be replaced by any other suitable material such as, for example, Zn (O, H) S or In 2 S 3 .
- a heterojunction is formed between the second layer 40 and the layer 50 of CdS.
- the CIGS of the second layer 40 has a p-type doping originating from intrinsic defects, whereas the ZnO is n-type thanks to the incorporation of aluminum for example.
- the stack comprises a plurality of individual holes 72 (FIG. 9) each passing through the first, second and third layers 30, 40, 60 (or even the buffer layer 50 when it is present) to open towards the substrate 10.
- Each hole opens freely towards the outside of the stack on the opposite side of the substrate 10 to allow part of the light spectrum incident on the third layer 60 to penetrate the holes 72.
- This makes it possible to confer on the stack the faculty of allowing the light incident on the photovoltaic device, on the opposite side of the substrate 10, to traverse its thickness at the level of specific zones delimited by these holes 72.
- Each hole 72 comprises an inner wall delimited at the level of the first layer 30, in the plane of the first layer 30 and over the entire thickness h of the first layer 30, by the maté second layer 40.
- the inner wall of each hole 72 is delimited, in the plane of the second layer 40 and over the entire thickness of the second layer 40, by the material of the second layer 40.
- the third layer 60 the inner wall of each hole 72 is delimited, in the plane of the third layer 60 and over the entire thickness of the third layer 60, by the material of the third layer 60.
- the inner wall of each hole 72 is delimited, in the plane of the buffer layer 50 and over the entire thickness of the buffer layer 50, by the material of the buffer layer 50.
- a thickness 45 of material of the second layer 40 is interposed between the inner wall of each hole 72 and the first layer 30.
- each hole 72 and the first layer 30 there is interposition of a thickness 45 of material of the second layer 40, this interposition being made in the plane of the first layer 30 (which is perpendicular to the direction D in which the layers 30, 40, 50, 60 are stacked to form the stack) and over the entire thickness h of the first layer 30.
- the defined volume by the inner wall of each hole 72 is preferably free of solid material from the first, second and third layers.
- a transparent polymer such as EVA (for Ethylene-vinyl acetate) can fill the holes 72.
- the value or dimension denoted "A1" of this thickness 45 of material of the second layer, counted in a plane parallel to the main plane P, is preferably between 5 and 450 ⁇ , preferably between 5 and 200 ⁇ .
- the holes 72 are distributed in such a way that the ratio between, on the one hand, the perforated surface of the stack, corresponding to the sum of the areas of the holes 72 of the plurality counted in the main plane. P, and secondly the total surface of the stack in the main plane P of the stack, is between 1% and 99%.
- This ratio corresponds to an opening rate which is a pure geometrical factor that does not depend on the optical properties of the materials. This rate of aperture should not be confused with a transparency or transmission rate which corresponds to the ratio between the total light intensity passing through the device and the incident light intensity on the front panel.
- the layer 30 is a transparent conductive oxide and / or layer 40 is sufficiently thin (typically less than 500 nm thick).
- each hole 72 is spaced from the nearest adjacent hole 72, in the main plane P of the stack, by a distance marked "A2" of between 200 and 1000 ⁇ .
- Each hole 72 has dimensions E2 in the main plane P of the stack between 10 and 500 ⁇ .
- Each thickness 45 is formed in an opening 71 made beforehand in the first layer 30.
- Each opening 71 has dimensions E1 in the main plane P of the stack between 20 and 1000 ⁇ .
- the holes 72 are preferably distributed in the main plane P of the stack according to a periodic tiling at the vertices of a basic pattern having the shape of a polygon such as a square or a hexagon.
- the holes 72 are unevenly distributed in the main plane P, for example according to a non-periodic tiling, but the visual comfort is likely to be less good. It can also be envisaged that, although positioned at the nodes of a regular network, the sizes of the holes 72 are adjusted in a continuous variation to create an opening gradient which may be of interest in the case of the BIPV: this would allow, for example to produce a totally opaque portion in the upper part of the device, then a continuous gradient of transparency down the device.
- the holes 72 may all have a constant section in the direction D, for example but not exclusively of circular shape.
- the overall shape of the section of the holes 72 is generally identical to the general shape of the section of the openings 71. But the realistic case is that the section is neither constant nor perfectly circular.
- the dimension E2 corresponds to the diameter of the circular section.
- the opening 71 may also have a circular section and the difference between the radii of the sections of the openings 71 and holes 72 defines the value A1 of the thickness 45.
- these characteristics are not limiting, in particular as a function of the result of the first and second lift-off steps described below.
- the method of manufacturing a photovoltaic device generally comprises a step of providing a substrate 10, in particular transparent in all or part of the solar spectrum, and a step of forming a stack of thin layers on the substrate 10 and comprising:
- the step of forming this stack comprises successively or not:
- each opening 71 passes through the first layer 30, in particular over the entire thickness of the first layer 30 so as to open towards the substrate 10,
- the step of forming the second and third layers 40, 60 may provide for the implementation of a step of forming the buffer layer 50 on the second layer 40 previously formed and before the formation of the third layer 60 on the buffer layer 50 thus formed.
- the step of forming the plurality of holes 72 can be performed after the finalization of the second and third layers.
- the step of forming the plurality of holes 72 may possibly be performed at least partially before the step of forming the second and third layers.
- the holes may be formed through the second layer, at the end of its formation, or during its formation when the second lift-off step described below is carried out before the crystallization annealing of the second layer, and before the formation of the third layer 60.
- the second photoabsorbent layer 40 which is for example made of CIGS may be formed by a sequential process: in a first step precursors of Cu copper, indium In, gallium Ga are deposited for example by cathodic sputtering on the first layer 30 and in the openings 71, then a thin layer of selenium Se is deposited, then a rapid annealing under a nitrogen atmosphere at atmospheric pressure is carried out in order to crystallize the CIGS.
- any other method for obtaining the layer 40 may be envisaged.
- the step of forming the plurality of openings 71 is advantageously performed before the step of forming the plurality of holes 72.
- each opening 71 in the plane main P of the stack are strictly greater than the dimensions E2 of each hole 72 in the main plane P of the stack. It is the difference between these dimensions E1, E2 and the manner in which each hole 72 is aligned with the corresponding aperture which define the value A1 of the thickness 45 at any point of the inner wall of the hole 72. In particular, as indicated previously, it is the difference of the radii of the sections of the openings 71 and the holes 72 which defines A1. It is recalled that the section of the holes 72 and that of the openings 71 are not necessarily perfectly circular or constant. Openings 71 formed in the first layer 30 may be obtained using any known and appropriate technique.
- the step of forming the plurality of openings 71 comprises a first step of chemical, mechanical or laser etching of the first layer 30.
- the plurality formation step aperture 71 includes a first lift-off step made through the first layer 30 only at areas of the first layer 30 coinciding with the locations of the apertures 71 to be formed.
- This first lift-off step can essentially comprise:
- lift-off corresponds to a technique well known to those skilled in the art and which can indifferently be replaced by "detachment of material induced by elimination of the underlying material” or “uprising of matter” throughout the present document.
- This lifting or detachment is locally implemented at the level of only appropriate resin studs previously deposited and located below the material undergoing the action of lifting or detachment.
- the material of the first layer 30 remains intact outside the zones occupied by the first pads 20. It is the combination of this phenomenon of shrinkage of the first layer 30 above the first pads 20 and this phenomenon. non-removal of material from the first layer outside the first studs which has the effect of forming the openings 71.
- the dimensions of the first pads 20 are equal to those of the openings 71 which result from the first lift-off stage.
- the studs 20 have rather in reality a rounded section (even hemispherical) and it is only for simplification that they have been represented by rectangles in FIG. 5.
- the dimensions of the first studs 20 are between 20 and 1000 ⁇ and they are spaced a distance between 200 and 1000 ⁇ .
- the first resin may be of the family of methacrylates which are effectively dissolved by weakly polar solvents of the family of ketones.
- the resin may be constituted by an "IJC 256" ink sold by "Fujifilm” and the first solvent may be acetone.
- the first resin may also consist of the ink "FW-D001 -OP1" sold by the company "Toyo" and the first solvent may be methyl-ethyl ketone.
- the first pads 20 are formed, then the first layer 30 is formed, before the first solvent is applied to the stack to create the openings 71.
- the first pads 20 may be formed for example by an inkjet deposition, screen printing or any ink printing process for making patterns, that is to say, localized deposits.
- the shape of the pads 20 will generally be hemispherical.
- FIG. 5 represents the situation following the step of forming the first pads 20 and the step of forming the first layer 30. Areas of the first layer 30 are then removed locally at the first pads 20 by this lift-off technique.
- the sample can be immersed in the bath of the first solvent, for example acetone, in the presence of ultrasound for a period of between 5 seconds and 10 minutes, typically 2 minutes.
- FIG. 6 then illustrates the situation following the first lift-off step, the sample then being provided with a plurality of openings 71 whose location and dimensions are directly related to those of the first formed pads. on the sample.
- the section of the openings 71 has the shape of the section of the first pads 20 resin from which they are derived.
- the section of the openings 71 is circular in shape if the first resin pad 20 is circular.
- the thickness of the material of the first layer 30 is constant in practice and it is only by simplification of representation that the thickness of this material above the pads 20 has been represented different from the thickness above the substrate. 10 in Figure 5.
- An advantage of using the lift-off technique for the formation of the apertures 71 is that this solution is simple and inexpensive and that the edges of the apertures 71 are well defined, without splinters of material, scratch or mark.
- the step of forming the plurality of holes 72 comprises a second step of chemical, mechanical or laser etching of the second and third layers 30, 40, 60 (and also through the buffer layer 50 when she is here).
- the step of forming the plurality of holes 72 may comprise a second lift-off step made through the second and third layers 40, 60 (and also through the layer buffer 50 when present) only at areas of the stack coinciding with the locations of the holes 72 to be formed.
- the second lift-off step is performed separately and after the first lift-off step described above. This second lift-off step can include:
- the material of the second layer 40, the buffer layer 50 and the third layer 60 remains intact against the areas occupied by the second pads 21. It is the combination of this phenomenon of shrinkage of the layers 40, 50, 60 above the second studs 21 and of this phenomenon of non-removal of material from the layers 40, 50, 60 outside the second studs 21 which has the effect of forming the holes 72.
- the dimensions of the second studs 21 are equal to those of the holes 72 which result from the second lift-off stage. In general, the second studs 21 have in reality a rounded section and it is only for simplification that they have been represented by rectangles in FIGS. 7 and 8. The dimensions of the second studs 21 are between 10 and 500 ⁇ and they are spaced a distance between 200 and 1000 ⁇ .
- the second resin-second couple The solvent may consist of any resin-solvent pair whose Hildebrand parameters are close and which can have an annealing temperature of about 500-600 ° C. without major degradation.
- the second resin may be of the family of methacrylates which are effectively dissolved by weakly polar solvents of the family of ketones.
- the second resin may consist of an "IJC 256" ink marketed by "Fujifilm” and the second solvent may be acetone.
- the second resin may also consist of the ink "FW-D001 -OP1" sold by the company "Toyo" and the second solvent may be methyl-ethyl ketone.
- Each second stud 21 is formed in the center of a corresponding opening 71 previously formed. More specifically, for each first stud 20, its dimensions in the main plane P of the stack, preferably between 20 and 1000 ⁇ , are strictly greater than the dimensions, in the main plane P, of the second stud 21 formed in the center of the opening 71 corresponding to the first pad 20, preferably between 10 and 500 ⁇ . This avoids the creation of fractures in the second layer 40 which otherwise could leave areas where the first layer 30 could be directly short-circuited by the buffer layer 50 and the third layer 60.
- FIG. 7 represents the situation following the step of forming the second pads 21.
- Figure 8 shows the situation following the step of forming the second and third layers 40, 60 (and the step of forming the buffer layer 50).
- Figure 9 illustrates the situation at the end of the second lift-off stage.
- the second pads 21 are formed, then the second layer 40 is formed, and then the third layer 60 is formed before the second solvent is applied to create the holes 72.
- the second pads 21 may be formed for example by a deposit of ink-jet type, screen printing or any ink printing process for making patterns, it is ie localized deposits.
- the shape of the second studs 21 will generally be hemispherical.
- the layers 40 and 60 are formed.
- Figure 8 shows this situation. Areas of the layers 40, 50, 60 are then removed locally at the second pads 21 by this lift-off technique.
- the sample may be immersed in the bath of the second solvent, for example acetone, in the presence of ultrasound for a period of between 5 seconds and 10 minutes, typically 2 minutes.
- FIG. 9 then illustrates the situation following the second lift-off step, the sample then being provided with a plurality of holes 72 whose location and dimensions are directly related to those of the second pads 21 formed on the sample.
- the section of the holes 72 has the overall shape of the section of the second resin pads 20 from which they are derived.
- holes 72 One advantage of using the lift-off technique for forming holes 72 is that this solution is simple and inexpensive and that the edges and inner walls of holes 72 have limited defects compared to other embodiments. holes mentioned above (including mechanical drilling).
- the step of forming the plurality of holes 73, 74 may possibly be carried out at least partially before the step of finalizing the second layer 40 and the third layer 60.
- the holes 73, 74 may be formed through the second layer 40, before its formation, when the second lift-off step is performed before the crystallization annealing necessary for the finalization of the second layer 40, and before the depositing the third layer 60 and the buffer layer 50.
- the step of forming the second layer 40 on the first layer 30 comprises a step of depositing at least one layer 41, 42 of compounds (exemplified above) capable of forming, by crystallization annealing , the photo-absorbing material of the second layer 40, then a step of crystallization annealing of said compounds in order to finalize the second layer 40, then it can be very advantageous to ensure that the step of forming the plurality of holes comprises a second lift-off step, implemented between the step of depositing said at least one layer 41, 42 of compounds and the crystallization annealing step, and carried out through these layers 41, 42 of compounds only at the level of areas of the stack coinciding with the locations of the holes to be formed.
- the second lift-off step is carried out only through the 41, 42, and this advantageously before the crystallization annealing step necessary for the subsequent finalization of the second layer 40.
- the method comprises a step of forming a plurality of second pads 21 of a second resin on the substrate 10 at the locations of the holes 73, 74 to be formed, each second pad 21 being formed in the center of a corresponding opening 71 previously formed.
- the method comprises a step of applying a second solvent on the stack, the second pair resin-second solvent being chosen so that said application step removes the second pads 21 and the zones of said at least one layer 41, 42 of compounds located above the second pads 21.
- the lift-off step is implemented before the annealing step leading to the formation and finalization of the second layer 40.
- the first steps of the second exemplary method are strictly identical to those described with reference to FIGS. 5 to 7.
- the advantage is that the second studs 21 can here be made using a resin that does not require any keeping high temperature since, as will be explained later, these second pads 21 are removed before the crystallization step of the second layer 40 at high temperature, especially between 500 and 600 ° C, resulting from the annealing step .
- a layer 41 for example of a copper-gallium alloy, is deposited by cathodic sputtering.
- target of an alloy of Copper and Gallium is deposited, also by cathodic sputtering of an Indium target.
- the amounts of the various metals are adjusted, for example so as to set an atomic concentration ratio between the copper concentration and the sum of the concentrations of gallium and ndium between 0.5 and 1, and preferably 0.88 .
- the thickness of the layer 40 in CIGS that will be obtained after the implementation of an annealing of selenization is between 500 nm and 5 ⁇ , and preferably 1, 4 ⁇ .
- the elements Copper, Indium, and Gallium can also be provided by other methods than sputtering, such as an electroplating process. It will be appropriate in this case to ensure that the electrolytic medium is not a solvent for the resin of the pads 21.
- the stack obtained is shown in FIG.
- the second lift-off stage of the second pads 21 via the second solvent is carried out under conditions identical to those described above with reference to FIG. 9.
- the layers 41 and 42 located above pads 21 are removed by this lift-off.
- the characteristics A3 and E3 of these holes 73 in FIG. 11 are identical to A1 and E2 respectively of FIG. 9.
- the advantage of this example of the method is that all the pads 21 of resin were removed before the crystallization annealing step of the second layer 40 at high temperature.
- the step of crystallization annealing of the layer 40 is then carried out with reference to FIG. 12, under an atmosphere of selenium at a temperature of between 500 ° C.
- the selenium may be provided, for example, in the form of metallic selenium vapors, either in the form of H 2 Se gas (or else other volatile compounds based on Selenium).
- the partially formed stack, which includes the second finalized layer 40, is visible in FIG.
- It is a semi-transparent photovoltaic device, wherein a passage of light through the holes 74 and the back of the substrate 10 is made.
- the buffer layer 50 is present at the bottom of the holes 73.
- the buffer layer 50 may result in a yellowish appearance because of the gap (around 2 , 4 eV) of the CdS. It can be remedied by replacing the CdS by a buffer layer formed in a material having a larger gap. It may be for example materials based on Zn (0, S), as described above and whose gap is 3.4 eV.
- the deposition steps of the layers 41 and 42 may be followed by a step of depositing a layer 44 of selenium having a thickness of between 100 nm and 10 ⁇ , and preferably 2 ⁇ , provided by evaporation of a metal Selenium source.
- a layer 44 of selenium having a thickness of between 100 nm and 10 ⁇ , and preferably 2 ⁇ , provided by evaporation of a metal Selenium source.
- the second lift-off step of the layers 41, 42 and 44 is performed by the same methods as those already used previously and previously described for the layers 41 and 44 in the second embodiment.
- the result of the second stage of off is shown in Figure 1 5.
- the second lift-off step is performed before the implementation of the crystallization annealing resulting in the finalization of the second layer 40.
- the resin used here does not require, once again, a high temperature resistance since it is removed before the crystallization step of the second layer 40.
- the annealing step is carried out in order to crystallize the second layer 40, the temperature being between 500 and 600 ° C.
- the result is identical to that of FIG. 1 2.
- the steps of formation of the layers 50 and 60 are identical to those of the passage of FIG. 12 in FIG.
- the solution described in this document provides for making openings 71 in the first layer 30, then to come there deposit the resin (second pads 21) which will be used to lift-off at least of the layer 40, or even together the layers 40, 50, 60 greater than the layers 41, 42 and possibly 44 compounds before the crystallization annealing of the second layer 40.
- the first layer 30 is not stressed and the Fractures at the edges of the resin pads are not problematic.
- the first layer 30 is not stressed by the resin.
- the upper layers 40, 50, 60 may be subjected to stress, but the possible fractures which appear do not open on the rear electrode formed by the first layer 30 on the one hand, and on the other hand facilitate the access of the solvent for the dissolution of the resin pads 21.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1458880A FR3026230B1 (en) | 2014-09-19 | 2014-09-19 | SEMI-TRANSPARENT PHOTOVOLTAIC DEVICE WITH THROUGH HOLE |
PCT/EP2015/071131 WO2016041986A1 (en) | 2014-09-19 | 2015-09-15 | Semi-transparent photovoltaic device comprising a through-hole |
Publications (1)
Publication Number | Publication Date |
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EP3195373A1 true EP3195373A1 (en) | 2017-07-26 |
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EP15770483.4A Withdrawn EP3195373A1 (en) | 2014-09-19 | 2015-09-15 | Semi-transparent photovoltaic device comprising a through-hole |
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EP (1) | EP3195373A1 (en) |
FR (1) | FR3026230B1 (en) |
WO (1) | WO2016041986A1 (en) |
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KR102506156B1 (en) * | 2020-11-13 | 2023-03-06 | 한국광기술원 | Solar Cell Module with Holes and Method for Manufacturing the Same |
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JP4340246B2 (en) * | 2005-03-07 | 2009-10-07 | シャープ株式会社 | Thin film solar cell and manufacturing method thereof |
US7982127B2 (en) * | 2006-12-29 | 2011-07-19 | Industrial Technology Research Institute | Thin film solar cell module of see-through type |
US20100126559A1 (en) * | 2008-11-26 | 2010-05-27 | Applied Materials, Inc. | Semi-Transparent Thin-Film Photovoltaic Modules and Methods of Manufacture |
US7795067B1 (en) * | 2009-03-30 | 2010-09-14 | Solopower, Inc. | Semitransparent flexible thin film solar cells and modules |
GB2472608B (en) * | 2009-08-12 | 2013-09-04 | M Solv Ltd | Method and Apparatus for making a solar panel that is partially transparent |
FR2997227B1 (en) * | 2012-10-23 | 2015-12-11 | Crosslux | THIN-FILM PHOTOVOLTAIC DEVICE, IN PARTICULAR FOR SOLAR GLAZING |
-
2014
- 2014-09-19 FR FR1458880A patent/FR3026230B1/en not_active Expired - Fee Related
-
2015
- 2015-09-15 EP EP15770483.4A patent/EP3195373A1/en not_active Withdrawn
- 2015-09-15 WO PCT/EP2015/071131 patent/WO2016041986A1/en active Application Filing
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WO2016041986A1 (en) | 2016-03-24 |
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