WO2012153017A1 - Dispositif et procédé de dépôt par enduction à la racle d'encre à base de cuivre et d'indium - Google Patents
Dispositif et procédé de dépôt par enduction à la racle d'encre à base de cuivre et d'indium Download PDFInfo
- Publication number
- WO2012153017A1 WO2012153017A1 PCT/FR2012/000176 FR2012000176W WO2012153017A1 WO 2012153017 A1 WO2012153017 A1 WO 2012153017A1 FR 2012000176 W FR2012000176 W FR 2012000176W WO 2012153017 A1 WO2012153017 A1 WO 2012153017A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ink
- substrate
- coating
- copper
- indium
- Prior art date
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- 239000010949 copper Substances 0.000 title claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 23
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 20
- 238000010345 tape casting Methods 0.000 title abstract 2
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 239000011248 coating agent Substances 0.000 claims abstract description 59
- 238000000576 coating method Methods 0.000 claims abstract description 59
- 238000000151 deposition Methods 0.000 claims description 17
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 4
- 239000011810 insulating material Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 238000009736 wetting Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical group CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/001—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work incorporating means for heating or cooling the liquid or other fluent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
- B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
- B05C11/04—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface with blades
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
- B05C11/10—Storage, supply or control of liquid or other fluent material; Recovery of excess liquid or other fluent material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4885—Wire-like parts or pins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C3/00—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
- B05C3/18—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material only one side of the work coming into contact with the liquid or other fluent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0254—Coating heads with slot-shaped outlet
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to a device and a process for coating by coating with a doctor blade a layer of copper-indium-based ink, particularly in the production of solar cells.
- the coating deposition process is an inexpensive process since it is not carried out under vacuum.
- it is commonly used on an industrial scale in various fields such as plastics, paper mills and so on.
- the doctor blade coating is based on a principle which consists in placing a doctor blade at a fixed distance from the substrate to be coated. Then, the solution is distributed on the substrate, in front of the doctor blade which is moved linearly on the entire substrate, which leads to the formation of a continuous film of controlled thickness.
- CIGS-based solar cells CIGS for copper alloy, indium, gallium and selenium
- CIGS-based solar cells CIGS for copper alloy, indium, gallium and selenium
- M. Kaelin et al. Thin Solid Films, 480-481, 2005, p.486-490.
- an ink containing precursors based on copper, indium and gallium was deposited on a substrate to make thin layers for solar cells.
- this type of ink, based on copper and indium also has additives that serve as a binder between the particles.
- a device for coating by coating a layer of copper-indium-based ink on a substrate, comprising an ink distribution reservoir cooperating with a doctor blade. coating, the device also comprising means for maintaining the ink, the substrate and the coating doctor at distinct and increasing respective temperatures.
- FIG. 1 shows, schematically, in section, the deposition by coating with a doctor blade of a thin layer according to a first embodiment of the invention
- FIG. 2 shows, schematically, in section, a second embodiment of a deposition by coating the doctor blade according to the invention
- FIG. 3 and 4 show, schematically, in section, successive steps of a thin film deposition process by coating according to the invention.
- a reliable and inexpensive means for performing copper-indium ink deposition over a large area, for the production of thin films with uniform thicknesses and morphologies, is to use a coating deposition device with the squeegee.
- the device comprises means for controlling the temperature of the ink and elements that are in contact with the ink, namely the substrate and the doctor blade. More particularly, the ink, the substrate, and the doctor blade are maintained at distinct and increasing temperatures during coating.
- FIG. 1 diagrammatically illustrates a particular embodiment of a doctor blade deposition device 10 of a layer of ink 11 based on copper and indium on a substrate 12.
- the device comprises a support 13 on which substrate 12 is arranged.
- the support 13 comprises a receiving plane, preferably a horizontal plane, and means 13a for controlling the temperature of the substrate 12.
- the temperature control means 13a may comprise, for example, a thermostat conventional heating means.
- the heating of the substrate 12 can be obtained by Joule effect or by electromagnetic induction.
- the support 13 is provided with a thermostat controlling one or more coils inside which circulates an alternating current of predetermined frequency.
- the deposition device 10 also comprises a coating doctor 14 cooperating with a dispensing reservoir 15.
- the reservoir 15 is intended to store and distribute an ink 19 based on copper and indium.
- the ink 19 may also comprise gallium.
- the reservoir 15 comprises, in FIG. 1, lateral walls extending in vertical and / or inclined directions, relative to the support 13, from the peripheral edges of a bottom 17 to an upper surface (not represented). .
- the bottom 17 has an orifice 18 allowing the distribution of the ink on the substrate 12 to be coated.
- the orifice 18 may also be arranged in one of the lateral walls of the reservoir 15.
- the orifice 18 may, for example, comprise a dispensing valve, intended to regulate the volume of the ink 19.
- the reservoir 15 and the doctor blade 14 are, in this embodiment, each provided with means for controlling the temperature, respectively the ink 19 stored in the reservoir 15 and the portion of the doctor blade 14 in contact with the ink 19 distributed above the substrate 12.
- these means may comprise thermostats and conventional heating means.
- the means for controlling the temperature of the support 13, the ink 19 and the doctor blade 14 are, moreover, controlled to maintain during the coating operation the respective temperatures, of the ink 19, of the substrate 12, and the doctor blade 14, distinct and growing.
- the reservoir 15 and / or the doctor blade 14 are formed by thermally conductive materials.
- the reservoir 15 and the doctor blade 14 may, for example, be made of steel, aluminum or any other material allowing an efficient transfer of heat.
- the means for controlling the temperature, respectively associated with the reservoir 15 and with the doctor blade 14, may comprise heating elements 15a, 15b and 14a.
- the heating elements 15a and 15b associated with the reservoir 15 are arranged in the sidewalls and / or the bottom of the reservoir 15. They make it possible to heat the contents of the reservoir thanks to a transfer of heat, facilitated by the thermal conductivity of the material of the reservoir 15.
- the doctor blade 14 comprises a heating element 14a, which makes it possible to adjust the temperature of the surface of the doctor blade 14 in contact with the ink 19, distributed on the substrate 12.
- Each heating elements 15a, 15b and 14a are furthermore advantageously controlled by a thermostat.
- the doctor blade 14 in order to deposit an ink layer 11 on the substrate 12, the doctor blade 14 is disposed in a coating position.
- the coating position corresponds to the position in which the doctor blade 14 is placed at a fixed distance from the substrate 12, for example between 5 ⁇ and 500 ⁇ .
- This fixed distance separating the doctor blade 14 from the substrate 12 makes it possible, in particular, to fix the thickness of the ink layer 11 deposited on the substrate 12.
- the reservoir 15 and the doctor blade 14 can be provided with displacement relative to the support 13 (not shown in the figures).
- Such displacement means allow the blade 14 and the tank 15 to move in a vertical direction 16 and / or horizontal 16 'relative to the substrate 12.
- these displacement means can allow the blade to pass a rest position at the coating position during the coating operation.
- the coating deposition device 10 comprises a distribution reservoir 21 and a coating doctor 22 which are integral and which form a single element 20. They are separated from each other. one of the other by a layer 23 of thermally insulating material.
- the element 20 is, moreover, provided with displacement means similar to the means described for the embodiments illustrated in FIG. 1.
- the element 20 comprises at least two lateral walls 24 and 25 participating in the formation of the distribution tank 21 and the doctor blade 22.
- at least one side wall extends in a direction inclined relative to the support 13.
- a zone 28 is disposed under the reservoir 21.
- This zone 28 comprises a flat outer surface constituting the coating doctor 22.
- the element 20 also comprises a layer 23 arranged in such a way as to thermally isolate the distribution reservoir 21 from the zone 28.
- the reservoir 21 and the coating doctor 22 are furthermore provided with temperature control means comprising heating elements 21a, 21b and 22a, similar to the means described for the modes of the invention. previous embodiments.
- the temperature of the ink 19 stored in the reservoir 21 and the temperature of the coating doctor 22 can be adjusted separately.
- the element 20 contributes to the simplification of the structure of the coating deposition device 10, allowing easy use and maintenance.
- the element 20 of the device 10 advantageously serves to fulfill both the role of dispensing reservoir and that of coating doctor blade.
- the device 10 comprises unique displacement means for the element 20.
- FIGS. 3 and 4 illustrate a particular method of deposition by doctor coating of a layer of ink 11 based on copper and indium on a substrate 12 using the device 10 according to FIG. the deposited layer is advantageously a thin layer based on copper and indium or based on copper, indium and gallium, intended to be used in a photovoltaic cell production process.
- the substrate 12 may be based on any material on which an ink layer 11 may be deposited.
- the substrate 12 is, for example, formed by a soda-lime glass covered by a layer based on an electrically conductive material.
- this layer is formed by a thin layer of molybdenum (Mo) with a thickness of about 400 nm.
- the ink 19 is, in particular, based on precursors of copper and indium. Preferably, it is an ink suitable for producing CIS or CIGS layers on the substrate 12. According to a particular mode of implementation, the ink 19 also comprises a gallium precursor.
- the ink 19 comprises particles of a gallium-indium alloy and copper particles dispersed in an organic solvent such as ethanol or a thiolated organic solvent.
- the ink 19 does not need additives of binder or dispersant type, such as ethylcellulose or other polymers.
- the ratio (Ga / ln + Ga) between the gallium concentration and the sum of the indium and gallium concentrations, in the ink 19, is between 0.2 and 0.5 .
- This concentration ratio (Ga / ln + Ga) of the ink 19 advantageously makes it possible to control the width of the forbidden band of the CIGS layer so as to obtain a better absorption efficiency of the solar radiation. As a result, the conversion efficiency of thin-film solar cells into CIGS is improved.
- the ratio (Cu / Cu + ln + Ga) between the copper concentration and the sum of the concentrations of copper, indium and gallium is between 0 and 0. , 7 and 1, 0.
- a report can be called a composition report.
- a thin layer of CIGS having a copper concentration complying with this condition makes it possible to improve the conversion efficiency of the solar cells.
- a low composition ratio (Cu / Cu + ln + Ga) generally results in the formation of a single phase of low copper chalcopyrite, with a small grain size, which degrades the conversion efficiency of the cells.
- the composition ratio (Cu / Cu + ln + Ga) is greater than 1, a two-phase compound is generally formed. It contains chalcopyrite and impurities of Cu x Se. Because of their high electrical conductivity, these impurities cause a decrease in the efficiency of light conversion.
- the ink 19 is contained in a storage and dispensing reservoir 21 of a coating deposition device, so that the ink 19 is maintained at a temperature TE.
- the latter is maintained at a temperature Ts greater than the temperature TE of the ink 19.
- the element 20 is then displaced in a vertical direction 16 relative to the support 13, so as to dispose the element 20 in the coating position, that is to say at a predetermined distance from the surface to be coated.
- the ink 19 is distributed above the substrate 12.
- the coating doctor 22 is maintained at a temperature TR greater than the temperature Ts of the substrate 12.
- the coating element 20 and the substrate 12 move relative to each other in a direction 16 'horizontal with respect to the substrate 12.
- This linear displacement allows the formation of a continuous thin layer of the ink 11 on the substrate 12, with a controlled thickness.
- the displacement means allow the substrate 12 and the element 20 to move relative to each other at an optimum speed, which allows a distribution of a suitable volume of ink 19 on the substrate 12 before coating.
- the volume 50 comprises a zone 50-R disposed near the coating doctor 22, and therefore has a temperature T 50 -R close to the TR temperature.
- the volume 50 also comprises a second zone 50S arranged near the substrate 12, which maintains this second zone at a temperature T 50 -S close to the temperature Ts of the substrate 12. Between the first and second zones 50-S and 50-R is interposed a third zone 50-E.
- the third zone is sufficiently spaced from the coating doctor 22 and the substrate 12 so that it has a temperature T 5 OE close to the temperature TE of the ink 19. Therefore, the volume 50 disposed above the substrate 12 has a temperature gradient such as T 50 -E ⁇ T 50 -S ⁇ T 50 -R .
- This temperature gradient induces a viscosity gradient such that ⁇ -R ⁇ -s ⁇ - ⁇ where ⁇ -R, ⁇ -s, ⁇ - ⁇ respectively represent the viscosities of the zones 50-R, 50-S and 50-E.
- the viscosity gradient thus generated, advantageously allows optimum wetting of the ink 19 above the substrate 12.
- the thin layer 1 1, based on the ink 19, deposited on the substrate 12 is a homogeneous layer with uniform morphology.
- the optimization of the temperatures of the zones of the volume of ink 50 distributed on the substrate 12 advantageously makes it possible to obtain optimum wetting of the ink 19 on the substrate 12 without the addition of additives in the ink 19.
- the difference between the respective temperatures of the ink 9 and the substrate 12 is between 20 ° C and 100 ° C and / or the difference between the respective temperatures of the substrate 12 and the coating doctor 22 is between 20 ° C and 100 ° C and ° C and 100 ° C.
- the temperature of the ink TE is between 20 ° C and 100 ° C.
- the ink 19 also has a viscosity of between 0.005 and 0.08 Pa.s at a shear rate of 500 s-1.
- These ranges of temperature and viscosity of the ink 19 advantageously make it possible to improve the wetting quality of the ink 19 deposited on the substrate 12.
- a thin layer of copper, indium and gallium, 3 ⁇ thick was deposited on an area of 20 cm 2 .
- the layer thus deposited, by squeegee coating is a homogeneous layer, continuous and has a uniform morphology.
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Coating Apparatus (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Chemically Coating (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280021875.9A CN103503170A (zh) | 2011-05-06 | 2012-05-03 | 刮涂铜铟基墨水的设备和方法 |
KR1020137029371A KR20140022060A (ko) | 2011-05-06 | 2012-05-03 | 구리 및 인듐에 기초한 잉크를 나이프 코팅하기 위한 디바이스 및 방법 |
US14/113,664 US9305790B2 (en) | 2011-05-06 | 2012-05-03 | Device and method for knife coating an ink based on copper and indium |
JP2014508853A JP5797835B2 (ja) | 2011-05-06 | 2012-05-03 | 銅及びインジウムを基剤とするインクをナイフコーティングする装置及び方法 |
EP12728628.4A EP2705542A1 (fr) | 2011-05-06 | 2012-05-03 | Dispositif et procédé de dépôt par enduction à la racle d'encre à base de cuivre et d'indium |
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FR1101406 | 2011-05-06 | ||
FR1101406A FR2974745B1 (fr) | 2011-05-06 | 2011-05-06 | Dispositif et procede de depot par enduction a la racle d'encre a base de cuivre et d'indium |
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WO2012153017A1 true WO2012153017A1 (fr) | 2012-11-15 |
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PCT/FR2012/000176 WO2012153017A1 (fr) | 2011-05-06 | 2012-05-03 | Dispositif et procédé de dépôt par enduction à la racle d'encre à base de cuivre et d'indium |
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US (1) | US9305790B2 (fr) |
EP (1) | EP2705542A1 (fr) |
JP (1) | JP5797835B2 (fr) |
KR (1) | KR20140022060A (fr) |
CN (1) | CN103503170A (fr) |
FR (1) | FR2974745B1 (fr) |
WO (1) | WO2012153017A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104812502A (zh) * | 2012-11-23 | 2015-07-29 | 3S瑞士太阳能系统股份公司 | 制造带有密封剂的太阳能组件及其系统的方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2999441B1 (fr) * | 2012-12-14 | 2016-01-01 | Commissariat Energie Atomique | Boitier hermetique, en particulier pour l'encapsulation d'un dispositif medical implantable. |
CN106925491B (zh) * | 2017-04-27 | 2022-12-20 | 三峡大学 | 疏水除污膜镀膜刮刀及镀膜方法 |
CN110355048A (zh) * | 2018-03-26 | 2019-10-22 | 宝武炭材料科技有限公司 | 一种锂离子电池用浆料涂布装置 |
CN114904744B (zh) * | 2022-04-14 | 2023-07-04 | 南京邮电大学 | 一种制备铜铟硒薄膜的刮涂方法及其应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0336274A2 (fr) * | 1988-04-02 | 1989-10-11 | Röhm Gmbh | Procédé pour revêtir des surfaces ou des bandes en matière plastique |
DE9208951U1 (de) * | 1992-07-03 | 1992-11-19 | Friz Maschinenbau GmbH, 7102 Weinsberg | Vorrichtung zum Auftragen von Klebstoff |
JP2006068708A (ja) * | 2004-09-06 | 2006-03-16 | Matsushita Electric Ind Co Ltd | 塗工ヘッドとそれを用いた塗工装置、貼り合わせ装置 |
FR2929548A1 (fr) * | 2008-04-02 | 2009-10-09 | Michelin Soc Tech | Buse comprenant une palette d'applique articulee. |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3935059C1 (fr) * | 1989-10-20 | 1991-02-21 | Juergen 8609 Bischberg De Ruemmer | |
EP0577136B1 (fr) * | 1992-07-03 | 1997-01-08 | FRIZ MASCHINENBAU GmbH | Dispositif d'application de colle |
AU6544394A (en) * | 1993-05-12 | 1994-12-12 | Ciba-Geigy Ag | Process and device for coating printed circuit boards |
DE19717524C2 (de) * | 1997-04-25 | 2002-04-04 | Roland Man Druckmasch | Farbwerk für eine Druckmaschine |
JP2002126606A (ja) * | 2000-10-27 | 2002-05-08 | Kurz Japan Kk | 接着剤塗布装置 |
JP2004082059A (ja) * | 2002-08-28 | 2004-03-18 | Nec Corp | 厚膜塗布装置、厚膜塗布方法、及び、プラズマディスプレイパネルの製造方法 |
DE102004032568B4 (de) * | 2004-07-05 | 2007-09-20 | Jakob Weiß & Söhne Maschinenfabrik GmbH | Rakelvorrichtung und Rakelverfahren |
JP2010251694A (ja) * | 2009-03-26 | 2010-11-04 | Fujifilm Corp | 光電変換半導体層とその製造方法、光電変換素子、及び太陽電池 |
WO2011013657A1 (fr) * | 2009-07-30 | 2011-02-03 | 京セラ株式会社 | Procédé de fabrication d'un semi-conducteur composé, procédé de fabrication d'un dispositif de conversion photoélectrique et solution pour réalisation d'un semi-conducteur |
WO2011017237A2 (fr) * | 2009-08-04 | 2011-02-10 | Precursor Energetics, Inc. | Précurseurs polymères pour photovoltaïques caigs et aigs contenant de l'argent |
KR20120043051A (ko) * | 2009-08-04 | 2012-05-03 | 프리커서 에너제틱스, 인코퍼레이티드. | Cis 및 cigs 광기전체를 위한 중합체성 전구체 |
US20110308616A1 (en) * | 2009-09-29 | 2011-12-22 | Kyocera Corporation | Photoelectric Conversion Device |
CN101826574A (zh) * | 2010-02-10 | 2010-09-08 | 昆山正富机械工业有限公司 | 非真空制作铜铟镓硒光吸收层的方法 |
CN101820032A (zh) * | 2010-02-11 | 2010-09-01 | 昆山正富机械工业有限公司 | 一种非真空环境下配置铜铟镓硒浆料制作光吸收层的方法 |
-
2011
- 2011-05-06 FR FR1101406A patent/FR2974745B1/fr not_active Expired - Fee Related
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2012
- 2012-05-03 EP EP12728628.4A patent/EP2705542A1/fr not_active Withdrawn
- 2012-05-03 JP JP2014508853A patent/JP5797835B2/ja not_active Expired - Fee Related
- 2012-05-03 US US14/113,664 patent/US9305790B2/en not_active Expired - Fee Related
- 2012-05-03 CN CN201280021875.9A patent/CN103503170A/zh active Pending
- 2012-05-03 WO PCT/FR2012/000176 patent/WO2012153017A1/fr active Application Filing
- 2012-05-03 KR KR1020137029371A patent/KR20140022060A/ko not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0336274A2 (fr) * | 1988-04-02 | 1989-10-11 | Röhm Gmbh | Procédé pour revêtir des surfaces ou des bandes en matière plastique |
DE9208951U1 (de) * | 1992-07-03 | 1992-11-19 | Friz Maschinenbau GmbH, 7102 Weinsberg | Vorrichtung zum Auftragen von Klebstoff |
JP2006068708A (ja) * | 2004-09-06 | 2006-03-16 | Matsushita Electric Ind Co Ltd | 塗工ヘッドとそれを用いた塗工装置、貼り合わせ装置 |
FR2929548A1 (fr) * | 2008-04-02 | 2009-10-09 | Michelin Soc Tech | Buse comprenant une palette d'applique articulee. |
Non-Patent Citations (4)
Title |
---|
DING I K ET AL: "Deposition of hole-transport materials in solid-state dye-sensitized solar cells by doctor-blading", ORGANIC ELECTRONICS, ELSEVIER, AMSTERDAM, NL, vol. 11, no. 7, 1 July 2010 (2010-07-01), pages 1217 - 1222, XP027074913, ISSN: 1566-1199, [retrieved on 20100603], DOI: 10.1016/J.ORGEL.2010.04.019 * |
KAELIN M ET AL: "Low-cost CIGS solar cells by paste coating and selenization", THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 480-481, 1 June 2005 (2005-06-01), pages 486 - 490, XP025387500, ISSN: 0040-6090, [retrieved on 20050601] * |
M. KAELIN ET AL.: "Low-cost CIGS solar cells by paste coating and selenization", THIN SOLID FILMS, 2005, pages 480 - 481,486-490 |
See also references of EP2705542A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104812502A (zh) * | 2012-11-23 | 2015-07-29 | 3S瑞士太阳能系统股份公司 | 制造带有密封剂的太阳能组件及其系统的方法 |
Also Published As
Publication number | Publication date |
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FR2974745A1 (fr) | 2012-11-09 |
KR20140022060A (ko) | 2014-02-21 |
FR2974745B1 (fr) | 2013-04-26 |
JP2014522296A (ja) | 2014-09-04 |
US9305790B2 (en) | 2016-04-05 |
US20140051245A1 (en) | 2014-02-20 |
EP2705542A1 (fr) | 2014-03-12 |
CN103503170A (zh) | 2014-01-08 |
JP5797835B2 (ja) | 2015-10-21 |
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