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WO2012093187A1 - Matériau photo voltaïque multijonction de type p-i-n, dispositif céramique photovoltaique comprenant ce dernier et procédés d'obtention de ceux-ci - Google Patents

Matériau photo voltaïque multijonction de type p-i-n, dispositif céramique photovoltaique comprenant ce dernier et procédés d'obtention de ceux-ci Download PDF

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Publication number
WO2012093187A1
WO2012093187A1 PCT/ES2011/070744 ES2011070744W WO2012093187A1 WO 2012093187 A1 WO2012093187 A1 WO 2012093187A1 ES 2011070744 W ES2011070744 W ES 2011070744W WO 2012093187 A1 WO2012093187 A1 WO 2012093187A1
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limits
type
layer
ceramic
percentage
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English (en)
Spanish (es)
Inventor
María de los Ángeles HERNÁNDEZ FENOLLOSA
Javier OROZCO MESSANA
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Universidad Politecnica de Valencia
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Universidad Politecnica de Valencia
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    • 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
    • H10F10/17—Photovoltaic cells having only PIN junction potential barriers
    • H10F10/172—Photovoltaic cells having only PIN junction potential barriers comprising multiple PIN junctions, e.g. tandem 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
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/17—Photovoltaic cells having only PIN junction potential barriers
    • H10F10/174—Photovoltaic cells having only PIN junction potential barriers comprising monocrystalline or polycrystalline materials
    • 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
    • H10F71/10—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells

Definitions

  • the present invention is framed in the field of photovoltaic energy production, that is, the direct transformation of solar radiation into electrical energy, specifically the semiconductor materials used to produce said energy when integrated into devices such as cells solar. More specifically, the invention is part of the field of application of these photovoltaic devices in the manufacture of ceramic products of the construction industry, such as tiles, tiles or ventilated facade panels.
  • JP2002246621 and JP2002293644 or of the way in which both, active element and constructive element, combine with each other - mechanical incorporation, recessed in ceramics ...-
  • the present invention is directed specifically to the PIN-type solar cells, which are composed of two thin layers, P and N, doped with various elements and between which a third intrinsic semiconductor layer is integrated.
  • PIN-type solar cells which are composed of two thin layers, P and N, doped with various elements and between which a third intrinsic semiconductor layer is integrated.
  • Ceramic silicon is common, currently being of special interest for its properties the use of amorphous silicon (US5646050, US6635307 and US5246505) and, to a lesser extent, microcrystalline silicon.
  • These solar cells can be of the simple type
  • patent EP0729190 which can be considered the state of the art closest to the present invention, consists in a process of deposition of a multi-junction photovoltaic material type PIN in tandem by means of PECVD of amorphous silicon and aggregates of microcrystalline silicon using in addition various components Dopants and barrier layers of the solar cell.
  • the present invention proposes multiple solutions at different scales by developing a process for obtaining a multilayer photovoltaic material that is integrated into a conventional ceramic support, such as those used in the construction industry (by for example, ceramic tiles or ventilated façade ceramic panels), to obtain a more economical, efficient and easy-to-use ceramic photovoltaic module or device:
  • composition of the multilayer photovoltaic material type P-I-N has been improved, both in terms of semiconductor material and doping materials;
  • a mechanism for conditioning and coating the surface of the ceramic support has been developed prior to the deposition of the semiconductor material, mainly through an enamelling formulation of a novel composition, in order to reduce its roughness and prevent the migration of contaminants.
  • the present invention seeks to integrate photovoltaic utilization facilities into traditional architecture by means of integrated and multifunctional devices of long duration and easy maintenance, which minimize the economic and operational impact.
  • the main object of the present invention resides in a thin layer PIN type photovoltaic material based on crystalline amorphous silicon (or what is the same, amorphous silicon with microcrystalline cores), suitable for integration on a ceramic substrate or piece in order to obtain an improved efficiency photovoltaic device (panel).
  • said photovoltaic material is composed of three or more PIN-type junctions stacked in tandem on one another, comprising hydrogenated microcrystalline silicon contained in an amorphous silicon matrix (which can be represented as a-Si: H / yc-Si: H ) as a semiconductor material.
  • the at least three layers P and three layers N further comprise boron and phosphorus as doping agents, respectively.
  • the layer I of all the joints in the series consists essentially of the aforementioned silicon
  • the composition of each of the at least three layers P and the at least 3 layers N differs between them; in its essential composition, the P layer of the second P-I-N junction further comprises arsenic, while the P layer of the third P-I-N junction further comprises gallium.
  • the N layer of the second P-I-N junction further comprises gallium, and the N layer of the third P-I-N junction further comprises arsenic.
  • Table 1 the composition of the material disclosed is illustrated in Table 1 below.
  • the photovoltaic material comprises more than 3 semiconductor junctions type P-I-N as mentioned, which is the minimum defined for said material, the doping sequence in the odd and even junctions is analogous to that represented in Table 1.
  • photovoltaic material in question can be obtained by a sequential process (i.e., forming a PIN junction over another PIN junction and so on ) of Chemical Deposition in Phase Steam Supported by Plasma, from the injection into a series of gases inside an ultra-high vacuum reactor.
  • the photovoltaic material described in this application can be specifically supported on a conventional ceramic substrate, the assembly giving rise to a photovoltaic ceramic device that is also part of the present invention, since it is novel.
  • the use of photovoltaic material to coat ceramic substrates is another object of the present application.
  • the method of obtaining the photovoltaic material disclosed here is another object of protection of this application.
  • Said method comprises forming (growing) sequentially and in tandem (that is, mounted on top of each other) by means of Chemical Deposition in Steam Phase Supported by Plasma each of the P, I and N type layers of each of the PIN type joints that they make up the photovoltaic material, from the first P-type layer of the first PIN-type junction to the last N-type layer of the last PIN-type junction, dosing into an ultra-empty reactor chamber at least the following gases: SiCH 4 , H 2 , B 2 H 6 , PH 3 , CH 4 , Ga (CH 3 ) 3 and AsH 3 , and applying a high frequency electromagnetic field.
  • gases SiCH 4 , H 2 , B 2 H 6 , PH 3 , CH 4 , Ga (CH 3 ) 3 and AsH 3 , and applying a high frequency electromagnetic field.
  • another object thereof is a method of conditioning a ceramic substrate that is used in the manufacture of photovoltaic devices, and which comprises coating the surface of said substrate with a Sodium-free enamel and which in its formulation comprises at least borax, anatase, zinc oxide, metallic zinc powder, boron oxide and feldspar, before firing the ceramic substrate.
  • the ceramic substrate itself obtainable from this procedure, as well as the enamelling formulation itself and its use to coat ceramic substrates are also encompassed in this invention. It has been proven that the developed enamel works optimally as a barrier layer that prevents the migration of harmful species (chemical elements) from the ceramic substrate to the photovoltaic material that is deposited on it. In addition, it allows to obtain an ideal morphology on the surface of the substrate, to achieve a micropore free roughness.
  • each of the at least three P-I-N type semiconductor junctions comprised in the photovoltaic material in question has the following formulation:
  • the second and third unions type P-I-N also comprising nanostructured gallium arsenide in a percentage between 0.3% and 1.2%, including both limits.
  • the at least three P-IN semiconductor junctions of the photovoltaic material are sequentially obtained in tandem (one after the other, stacked) by Plasma-backed Chemical Phase Deposition from the mixture of at least the following gases: SiCH 4 , H 2 , B 2 H 6 , PH 3 , CH 4 , Ga (CH 3 ) 3 and AsH 3 , which are dosed into a chamber of an ultra-high vacuum reactor in the that a high frequency electromagnetic field is applied.
  • the radicals form a layer on the heated electrode (or surface to be treated) and thus form layers P, I and N of the first junction, the P, I and N layers of the second junction on the N layer of the first, the P, I and N layers of the third junction on the N layer of the second, and so on in case there were more of three unions.
  • the gases are dosed into the reactor chamber with the following flow rates:
  • SiCH 4 flow rate between 25 ncc / min and 47 ncc / min, including both limits;
  • H 2 flow rate between 110 ncc / min and 186 ncc / min, including both limits;
  • PH 3 flow rate between 14 ncc / min and 19 ncc / min, including both limits;
  • CH 4 flow rate between 43 ncc / min and 47 ncc / min, including both limits
  • Ga (CH 3 ) 3 flow rate between 2 ncc / min and 5 ncc / min, including both limits
  • AsH 3 flow rate between 4 ncc / min and 8 ncc / min, including both limits.
  • the P-I-N type junctions are deposited with a deposition rate between 0.1 nm / sec and 2 nm / sec, both limits included.
  • each PIN type junction of the photovoltaic material has a thickness between 150 nm and 210 nm, including both limits, the thickness of each of its three layers P, I and N being comprised between 50 nm and 70 nm, including both limits, that is, what could be called "thin layer”.
  • the photovoltaic material in any of its variants is further defined as comprising a metallic contact layer, on which the at least three semiconductor PIN-type junctions are deposited sequentially (i.e. the layer metallic would be in direct contact with the P layer of the first PIN junction).
  • Said metal contact layer is preferably Ni-Mo and has a thickness between 2 and 3 microns, including both limits.
  • the photovoltaic material further comprises at least one transparent layer of a conductive oxide coating of the last semiconductor junction type PIN, which is supported on the first two (ie, said transparent layer will be in direct contact with the Layer n of the last PIN type junction deposited).
  • the transparent layer of a conductive oxide has a thickness between 200 and 300 nm, including both limits.
  • said layer is indium tin oxide (commonly referred to as ITO).
  • the photovoltaic material further comprises at least one polymeric sheet of a transparent, moisture and air-tight optical polymer (protective encapsulation), which covers all the photovoltaic material (i.e., on the previous transparent layer ).
  • the polymeric layer has a preferable thickness between 80 and 100 microns, including both limits.
  • said encapsulated layer is EVA (vinyl ethyl acetate).
  • the photovoltaic material is characterized in that it additionally comprises at least one layer of transparent epoxy on the polymeric sheet. In this way, the tightness and lasting resistance of the layer is guaranteed without compromising the properties of the cell by ionic diffusion.
  • this photovoltaic material is preferably designed to cover ceramic substrates, so that its use allows to obtain photovoltaic ceramic devices, which for example may be applicable to the construction industry. Therefore, the present invention encompasses the use of said material to coat ceramic substrates, as well as a device photovoltaic ceramic characterized in that it comprises at least one photovoltaic material as described above, in any of its variants, supported on a substrate of a ceramic nature.
  • said substrate is a porcelain tile (more preferably with a vitreous finish) or a non-porous ceramic, of those commonly used in the construction industry, and which can be selected from roof tiles, tiles, rustic tiles and ventilated facade panels, among other enclosures.
  • Another object of the present invention is the method of obtaining a photovoltaic material as described herein, characterized in that it comprises at least the following steps:
  • the gases are dosed into the reactor with the following flow rates:
  • SiCH 4 flow rate between 25 ncc / min and 47 ncc / min, including both limits;
  • B 2 H 6 Flow rate between 12 ncc / min and 19 ncc / min, including both limits;
  • PH 3 flow rate between 14 ncc / min and 19 ncc / min, including both limits;
  • CH 4 flow rate between 43 ncc / min and 47 ncc / min, including both limits;
  • Ga (CH 3 ) 3 flow rate between 2 ncc / min and 5 ncc / min, including both limits; and ⁇ AsH 3 : flow rate between 4 ncc / min and
  • the flow rate selected will depend on the specific conditions that are desired for the P-I-N type junctions that are obtained from the procedure.
  • the method may comprise a stage of cleaning the reactor circuits between successive depositions of layers, using Helium gas as a purge.
  • Said Helium gas can be dosed with a flow rate between 20 ncc / min. And 50 ncc / min, and would not be part of the composition of the photovoltaic material.
  • Chemical Steam Phase Deposition supported by Plasma is carried out according to the following parameters:
  • each of the P, I and N type layers of each P-I-N semiconductor junction is deposited with a deposition rate between 0.1 nm / sec and 0.2 nm / sec, including both limits.
  • each PIN type connection obtained by the method described here preferably has a thickness between 150 nm and 210 nm, including both limits, the thickness of each of its three layers P, I and N being between 50 nm and 70 nm, including both limits.
  • the method disclosed herein in any of the variants mentioned further comprises the following step:
  • the method may also comprise the following stage:
  • Said coating layer preferably has a thickness between 200 and 300 nm, including both limits.
  • the method may comprise the stage of:
  • the sheet or layer Polymeric must be suitable for sealing and mechanical protection, and must possess the necessary optical transparency for the visible spectrum. Preferably, it has a thickness between 80 and 100 microns, including both limits, and being more preferably 100 microns.
  • the method of obtaining the photovoltaic material comprises the three steps described above.
  • the metal contact layer it is preferably deposited by an electrode-free chemical deposition process that comprises at least immersing the surface of the support in a hot bath having the following formulation:
  • At least one source of metal ions At least one source of metal ions
  • the bath temperature being between 80 ° C and 85 ° C, including both limits, and the duration of the bath being between 3 and 5 minutes, including both limits.
  • the reducing agent is hydrated sodium hypophosphite of the formula NaH 2 P0 2 ⁇ H 2 0; the complexing agent is ammonium hydroxide; and the stabilizers are gluconic acid and sodium tartrate.
  • This process offers metallic layers with high corrosion resistance, since the deposited nanoparticles have very particular physical and chemical characteristics, due to their small size.
  • the metal layer is preferably Ni-Mo, since it has the appropriate electrical and corrosion resistance properties to act as a rear contact of the photovoltaic material.
  • the sources of metal ions would be nickel sulfate and molybdenum sulfate. If the electrode-free chemical deposition process described here is applied to deposit the metal layer on the substrate, it is advisable and preferable to selectively catalyze the surface of the support prior to said deposition of the metal layer, such that thanks to the location of the Catalyst The deposition of the metallic layer is selective, thus achieving an optimal contact distribution for the performance and segmentation of photovoltaic materials.
  • Said selective catalysis is optionally carried out with a catalyst comprising palladium in suspension and applied to the surface of the substrate for 30 minutes, subsequently activating said surface at a temperature between 190 ° C and 200 ° C including both limits, during a time between 120 and 150 minutes including both limits.
  • said coating is carried out by sputtering in a cathodic spray at a pressure between 10 ⁇ 6 and 10 ⁇ 8 mbar, including both limits.
  • the encapsulation is carried out by thermal softening of the vacuum polymer, at a pressure less than 10 ⁇ 6 , and more preferably at a pressure between 10 ⁇ 6 and 10 ⁇ 8 mbar, including both limits.
  • the present invention contemplates any combination of the characteristics given for all of them.
  • the encapsulation stage of the photovoltaic material is protected by spraying and polymerizing a transparent epoxy layer, at a temperature between 220 ° C and 250 ° C, including both limits (preferably, in the oven).
  • Another object of the present invention is the photovoltaic material obtainable from the method described above, in any of its variants.
  • the invention described herein is directed to a method of conditioning a ceramic substrate as a support for manufacturing photovoltaic devices, characterized in that it comprises at least the following steps:
  • Y depositing a sodium-free enamel on the surface of the ceramic substrate and whose formulation comprises at least borax, anatase, zinc oxide, metallic zinc powder, boron oxide and feldspar;
  • the enamel comprises the following components in percentage by weight of dry powder:
  • Cooking of the material after the deposition of the enamel is preferably carried out between 1000 ° C and 1100 ° C including both limits, and preferably for a minimum period between 1 and 2 hours including both limits. More preferably, cooking is carried out at a temperature of 1100 ° C for 1 hour.
  • said surface is selectively catalyzed.
  • Said selective catalysis is carried out with a catalyst comprising palladium in suspension and applied on the surface of the ceramic substrate for 30 minutes, subsequently activating said surface at a temperature between 190 and 200 ° C including both limits, for a time between 120 and 150 minutes including both limits.
  • a metallic contact layer is deposited on the substrate surface, on which a photovoltaic material is deposited.
  • the ceramic substrate may be a porcelain stoneware or a non-porous ceramic of those used in construction. More preferably the porcelain stoneware or Non-porous ceramics are selected from tiles, tiles, ventilated facade ceramic panels and other similar enclosures.
  • the present invention covers the ceramic substrate obtainable from this conditioning method to obtain photovoltaic devices.
  • the described method of conditioning a ceramic substrate can be perfectly combined with the method of obtaining a photovoltaic material discussed above, so that the conditioning of the substrate would be carried out first, and then the deposition of the photovoltaic material on said enameled substrate.
  • the method of conditioning the substrate is especially preferred to obtain a photovoltaic device such as the one described herein.
  • the invention also comprises, by its novel and inventive nature, a dry powder (flux) formulation for the enamelling of ceramic substrates, characterized in that it lacks sodium and comprises at least the following ceramic powder products (i.e., the formulation is consisting of a mixture of ceramic powders containing the following components): borax, anatase, zinc oxide, metallic zinc powder, boron oxide and feldspar.
  • Said formulation in one of its preferred embodiments, comprises the following components in percentage by weight of dry powder:
  • the formulation which is presented in the form of dry powder, has an equal average particle size
  • the formulation further incorporates water for the milling process, and at least one dispersant, at least one binder and at least one plasticizer. Thanks to these components, the formulation is presented in the form of a slip, which facilitates its application on the surface of the substrate (a slip is understood as a suspension formed by inorganic oxides in a liquid medium, said medium being composed of water, dispersants, binders and plasticizers.
  • a slip is understood as a suspension formed by inorganic oxides in a liquid medium, said medium being composed of water, dispersants, binders and plasticizers.
  • the enamelling formula developed here can be used as an enamel in a method of conditioning a ceramic substrate in accordance with the present specification to obtain photovoltaic devices, since it has advantageous properties when functioning as a barrier layer for the migration of harmful species from ceramics to the photovoltaic material itself that is deposited on it.
  • the assembly is subjected to cooking, preferably between 1000 ° C and 1100 ° C including both limits, and preferably for a minimum period between
  • cooking is carried out at a temperature of 1,100 ° C for 1 hour.
  • the packaging of the particles in the enamelling formulation depends on the particle size distribution of the oxides.
  • a very small particle size makes the surface area high which requires a high concentration of additives.
  • the dispersed particles join together to form a dense body where the small particles occupy the interstices between the large ones, hence a bimodal size distribution will improve the packing.
  • a greater proportion of solids with an adequate size distribution in the slip will increase the packing of the particles in the formulation sheet that is prepared.
  • Dispersant keep the suspension stable, because it makes the repulsive forces superior to those of attraction.
  • the addition of the dispersant produces a decrease is the viscosity of the slip and allows to work with a higher solids content.
  • Binder provide resistance to the sheet in green and thus facilitate its handling and storage because it remains in the green sheet forming organic bridges between the ceramic particles that cause strong adhesion after evaporation of the solvent.
  • the addition of binder to the slip produces other effects, such as better wetting, settling delay and a tolerable increase in the viscosity of the slip.
  • Plasticizers confer sufficient plasticity and flexibility to the green tape for easy handling and storage. They are substances of low molecular weight compared to the binder and are soluble in the solvent.
  • the at least one dispersant is optionally derived from ammonium salts of NH 4 PA polyacrylic acids in a proportion less than 1% by weight of the dry powder;
  • the at least one binder is preferably an acrylic polymer (preferably, latex) in proportions between 1.5% and 3% by weight of the dry powder, including both limits;
  • the plasticizer is preferably benzylbutylphthalate in a proportion comprised between 3% and 5% by weight of the dry powder, including both limits.
  • the formulation may additionally comprise polyethylene glycol in a proportion of 2.5% by weight of the dry powder and cyclohexanone in a proportion of 0.5% by weight of the dry powder.
  • the formulation is manipulated within the established ranges to adapt the enamel dilatometry to the properties of the ceramic substrate.
  • the enamel layer or enamelling formula is applied to the surface of the ceramic substrate by tape casting. It is advisable to guarantee a thickness of the enamel layer of 1 mm. after the cooking stage.
  • a deflocculated suspension is actually prepared.
  • the object of the dispersion of the mill is to break the weak agglomerates that have formed as a result of the high surface area of the ceramic particles, while the suspension is homogenized and the particle size distribution is adapted.
  • the characteristics of this slip are critical for the later stages of the tape casting process because they influence the viscosity of the suspension and the packaging of the sheet. At this point, high solids suspensions with low viscosity are required to facilitate mixing and dispersion.
  • the second stage mixing and homogenization of the binder and plasticizer is carried out in the slip.
  • the technical characteristics of some binders indicate that it is necessary to avoid mixing by grinding or by very energetic means, called high shear, due to the breakage of the polymer chains.
  • This stage is preferably performed by mechanical agitation on blades.
  • the addition of casting additives causes an increase in the viscosity of the slip.
  • the order of addition of the additives (dispersant, binder, plasticizer, etc.) to the slip is critical, because on the surface there is competitive adsorption of the additives, according to studies conducted for non-aqueous systems.
  • the dispersant is added last, the viscosity increases with respect to when it is added first because if the other organic components are added they must first be desorbed before the dispersant is adsorbed on the surface. Desorption is a very slow process and therefore prevents adsorption of the dispersant on the surface of the powder which decreases its effectiveness.
  • a third deaeration stage follows in order to eliminate the possible occluded bubbles inside the slip because air bubbles cause defects in the sheet.
  • Superficial "punctures" are the most common defects that result in cracking after drying.
  • the preferable technique is vacuum deaeration. This deaeration optionally occurs in a vacuum hood (preferably up to 10 ⁇ 5 bar) where the bubbling is very vigorous during the initial stage, and decreases as the occluded air disappears. Very viscous slippers are much harder to deaerate than low viscosity slippers, so a longer time is required.
  • the slip is deaerated, it is prepared for casting using preferably an industrial tape casting system (or "tape casting").
  • the enamel layer on the ceramic substrate After the deposition of the enamel layer on the ceramic substrate, it is dried in the environment, to then be cooked following the above indications.
  • Example 1- Obtaining an enamelling formulation of a ceramic substrate that will be used as supports to prepare a photovoltaic device.
  • An enamelling formulation is prepared with the following components:
  • the formulation is presented as a slip, suitable for tape casting on the ceramic substrate, and which is prepared as follows:
  • Example 2- Enameling of a ceramic substrate by the formulation prepared in Example 1, to prepare a support.
  • a ceramic tile As a ceramic substrate, a ceramic tile was selected, one of those commonly used in the construction industry, trying to have a closed porosity and polished finish at the structural level.
  • the ceramic formulation obtained in Example 1 was applied to the exposed surface of the tile using the industrial tape casting system.
  • the ceramic substrate After enameling the surface, the ceramic substrate was subjected to cooking at a temperature of 1100 ° C for 1 hour. After cooking, it was found that the enamel layer had a thickness of at least 1 mm over the entire surface of the substrate.
  • Example 3- Deposition of a metallic contact layer on the enameled surface of the ceramic support prepared in Example 2.
  • the enameled ceramic product was cooked, the previously enameled ceramic surface was metallized to obtain a contact layer with the photovoltaic material to be deposited on the ceramic support.
  • the catalyst used is formulated based on Palladium using 0.5 gr of Palladium Acetate, dissolved in two drops of ammonium.
  • a 50% solution of polymer type B70, B90 or the like in ethanol is created.
  • the catalysis of the surface is carried out by applying the catalyst suspension on the ceramic for 30 minutes.
  • the dry surface is activated in an oven at 200 ° C for 2 hours.
  • the metal layer is Mi-No and was deposited by an electrode-free or "electroless" process, following the following formulation of the hot bath in which the enameled surface of the substrate is submerged:
  • Ni ions, Mo nickel sulfate in 1.77 M solution and molybdenum sulfate in simultaneous 1 M solution;
  • the reduction of nickel is carried out with the presence of one or more reducing agents in the solution.
  • hydrated sodium hypophosphite NaH 2 P02 ⁇ ⁇ 2 0
  • NaH 2 P02 ⁇ ⁇ 2 0 hydrated sodium hypophosphite
  • Nickel ions in aqueous solution interact with a certain number of molecules, this being the coordination number, which in the case of divalent nickel can be two, 4 and 6.
  • the temperature of the bath is 85 ° C.
  • the pottery is introduced in the hot bath, until a metallic layer of 1 thick thickness is formed in 3 minutes.
  • Example 4- Deposition of a photovoltaic material according to the present invention by Chemical Deposition in Steam Phase supported by Plasma, on a ceramic support prepared according to Example 3.
  • the ceramic substrate is in a position to be used as a support for a photovoltaic material type P-I-N.
  • the support is introduced into an ultra high vacuum reactor chamber and deposited on an electrode, heating to 300 ° C, after which the photovoltaic material begins to form on the metal contact layer of the ceramic substrate by deposition. Steam Phase Chemistry supported by Plasma.
  • the deposition or growth of the material is carried out sequentially, layer by layer; first, the P layer of the first P-I-N type joint, followed by the I layer and the N layer, then the P layer of the second P-I-N type joint, followed by the layer and the N layer; and so on until depositing the layer N of the third joint P-I-N that forms the semiconductor material.
  • the deposition is carried out by dosing the following gases inside the chamber, modulating the flow rate within the ranges indicated:
  • SiCH 4 flow rate between 25 nec / min and 47 nec / min, including both limits;
  • H 2 flow rate between 110 nec / min and 186 nec / min, including both limits;
  • CH 4 flow rate between 43 nec / min and 47 nec / min, including both limits;
  • Ga (CH 3 ) 3 flow rate between 2 ncc / min and 5 ncc / min, including both limits; and AsH 3 : Flow rate between 4 ncc / min and 8 ncc / min, including both limits.
  • the plasma is generated by means of a radio frequency equipment that works at 13.56 MHz, with a deposition rate that ranges between 0.1 and 0.2 nm / sec.
  • the RF Power is between 50 and 100 w, including both limits; Pressure, between 0.1 mbar and 10 mbar, including both limits; and the distance between electrodes is between 10 mm and 35 mm, including both limits.
  • the thickness of each of the deposited layers P, I and N varies between 50 nm and 70 nm each, thus varying the thickness of each junction between 150 and 210 nm. this thickness being adequate to consider that a thin layer photovoltaic material has been obtained.
  • Example 5- Coating of the photovoltaic device obtained in Example 4.
  • the photovoltaic device obtained in the previous Example is subjected to coating by a transparent conductive layer of ITO by means of the sputtering technique. Previously, the individual areas and their interconnection will have been screened to achieve the electrical conditions of generation in the specific application (voltage and intensity).
  • the sputtering process takes place in a vacuum chamber. To avoid the residual gas causing considerable contamination in the deposited coatings it is necessary to achieve a high vacuum (high vacuum is considered for the sputtering process pressures below 10 ⁇ 6 mbar).
  • the working pressure is achieved by introducing the process gas (argon) at a pressure of the order of 1.5 ⁇ 10 ⁇ 3 mbar.
  • the target that has been used is ITO.
  • the compounds Stoichiometric form the ITO are ln 2 0 3 and Sn0 2 in concentrations of 90% and 10% by weight respectively.
  • the purity of the ITO material used is 99.99%.
  • the applied voltage is 500 V in direct current on the substrate heated to 200 ° C. This process is maintained until it reaches 1 millimeter thick (about 23 minutes).
  • Example 6- Encapsulation and protection of the coated photovoltaic device obtained in Example 5.
  • the device or photovoltaic cell must be closed by an encapsulant.
  • the encapsulation of the cell is carried out under vacuum (less than 10 ⁇ 6 bar) by means of EVA sheets of 100 microns thick heated to creep, and later sprayed (maximum final thickness 200 microns) and polymerization of a transparent epoxy layer ( Masterbond type) in oven at 250 ° C.

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  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un matériau photovoltaïque de type P-I-N caractérisé en ce qu'il comprend au moins trois jonctions semi-conductrices de type P-I-N empilées en tandem, les couches de type P, I et N comprenant du silicium monocristallin hydrogéné contenu dans une matrice renfermant du silicium amorphe dans sa composition et chacune des couches P et N de chaque jonction de type P-I-N présentant une composition particulière. Le matériau selon l'invention convient pour produire des dispositifs photovoltaïques à support céramique, de préférence des matériaux classiques utilisés dans l'industrie de la construction. La présente invention porte également sur un procédé d'obtention du matériau photovoltaïque ainsi que sur un procédé de conditionnement de la surface du support céramique concerné et l'émail utilisé pour ledit conditionnement, qui présente une composition novatrice et inventive.
PCT/ES2011/070744 2011-01-07 2011-10-26 Matériau photo voltaïque multijonction de type p-i-n, dispositif céramique photovoltaique comprenant ce dernier et procédés d'obtention de ceux-ci Ceased WO2012093187A1 (fr)

Applications Claiming Priority (2)

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ES201130011A ES2385871B1 (es) 2011-01-07 2011-01-07 Material fotovoltaico multiunión tipo p-i-n, dispositivo cerámico fotovoltaico que lo comprende y métodos de obtención de los mismos.
ESP201130011 2011-01-07

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WO2012093187A1 true WO2012093187A1 (fr) 2012-07-12

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0729190A2 (fr) * 1995-02-24 1996-08-28 Mitsui Toatsu Chemicals, Incorporated Dispositif photovoltaique
EP1069625A2 (fr) * 1999-07-14 2001-01-17 Canon Kabushiki Kaisha Composant photovoltaique microcristallin connecté en série, sa méthode de fabrication, matériau de construction et dispositif de production d'énergie utilisant ce composant
US20020011264A1 (en) * 1998-02-26 2002-01-31 Keishi Saito Stacked photovoltaic element
EP1420460A2 (fr) * 2002-11-13 2004-05-19 Canon Kabushiki Kaisha Composant photovoltaique
US20080096291A1 (en) * 2006-10-12 2008-04-24 Canon Kabushiki Kaisha Method for forming semiconductor device and method for forming photovoltaic device
WO2010005439A1 (fr) * 2008-07-09 2010-01-14 Applied Materials, Inc. Cellules solaires et leurs procédés et appareils de formation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0729190A2 (fr) * 1995-02-24 1996-08-28 Mitsui Toatsu Chemicals, Incorporated Dispositif photovoltaique
US20020011264A1 (en) * 1998-02-26 2002-01-31 Keishi Saito Stacked photovoltaic element
EP1069625A2 (fr) * 1999-07-14 2001-01-17 Canon Kabushiki Kaisha Composant photovoltaique microcristallin connecté en série, sa méthode de fabrication, matériau de construction et dispositif de production d'énergie utilisant ce composant
EP1420460A2 (fr) * 2002-11-13 2004-05-19 Canon Kabushiki Kaisha Composant photovoltaique
US20080096291A1 (en) * 2006-10-12 2008-04-24 Canon Kabushiki Kaisha Method for forming semiconductor device and method for forming photovoltaic device
WO2010005439A1 (fr) * 2008-07-09 2010-01-14 Applied Materials, Inc. Cellules solaires et leurs procédés et appareils de formation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
REYES-TOLOSA, M.D. ET AL.: "Desarrollo of sustratos conductores sin corrosion para aplicaciones fotovoltaicas sobre gres porcelánico mediante the proceso ''libre electrodos''", BOL.SOC.ESP.CERAM.V., vol. 49, 2010, pages 351 - 356 *

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