US20080093221A1 - Roll-To-Roll Electroplating for Photovoltaic Film Manufacturing - Google Patents
Roll-To-Roll Electroplating for Photovoltaic Film Manufacturing Download PDFInfo
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- US20080093221A1 US20080093221A1 US11/875,784 US87578407A US2008093221A1 US 20080093221 A1 US20080093221 A1 US 20080093221A1 US 87578407 A US87578407 A US 87578407A US 2008093221 A1 US2008093221 A1 US 2008093221A1
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Images
Classifications
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- 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
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- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0635—In radial cells
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- 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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
- H01L31/03928—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- 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 present invention relates to methods and apparatus for preparing thin films of Group IBIIIAVIA compound semiconductor films for radiation detector and photovoltaic applications.
- Solar cells are photovoltaic devices that convert sunlight directly into electrical power.
- the most common solar cell material is silicon, which is in the form of single or polycrystalline wafers.
- the cost of electricity generated using silicon-based solar cells is higher than the cost of electricity generated by the more traditional methods. Therefore, since early 1970's there has been an effort to reduce cost of solar cells for terrestrial use.
- One way of reducing the cost of solar cells is to develop low-cost thin film growth techniques that can deposit solar-cell-quality absorber materials on large area substrates and to fabricate these devices using high-throughput, low-cost methods.
- Group IBIIIAVIA compound semiconductors comprising some of the Group IB (Cu, Ag, Au), Group IIIA (B, Al, Ga, In, Tl) and Group VIA (O, S, Se, Te, Po) materials or elements of the periodic table are excellent absorber materials for thin film solar cell structures.
- compounds of Cu, In, Ga, Se and S which are generally referred to as CIGS(S), or Cu(In,Ga)(S,Se) 2 or CuIn 1-x Ga x (S y Se 1-y ) k , where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 and k is approximately 2, have already been employed in solar cell structures that yielded conversion efficiencies approaching 20%.
- FIG. 1 The structure of a conventional Group IBIIIAVIA compound photovoltaic cell such as a Cu(In,Ga,Al)(S,Se,Te) 2 thin film solar cell is shown in FIG. 1 .
- the device 10 is fabricated on a substrate 11 , such as a sheet of glass, a sheet of metal (such as aluminum or stainless steel), an insulating foil or web, or a conductive foil or web.
- the absorber film 12 which comprises a material in the family of Cu(In,Ga,Al)(S,Se,Te) 2 , is grown over a conductive layer 13 , which is previously deposited on the substrate 11 and which acts as the electrical contact to the device.
- FIG. 1 Various conductive layers comprising Mo, Ta, W, Ti, and stainless steel etc. have been used in the solar cell structure of FIG. 1 . If the substrate itself is a properly selected conductive material, it is possible not to use a conductive layer 13 , since the substrate 11 may then be used as the ohmic contact to the device.
- a transparent layer 14 such as a CdS, ZnO or CdS/ZnO stack is formed on the absorber film. Radiation 15 enters the device through the transparent layer 14 .
- Metallic grids (not shown) may also be deposited over the transparent layer 14 to reduce the effective series resistance of the device. It should be noted that the structure of FIG. 1 may also be inverted if substrate is transparent. In that case light enters the device from the substrate side of the solar cell.
- the cell efficiency is a strong function of the molar ratio of IB/IIIA. If there are more than one Group IIIA materials in the composition, the relative amounts or molar ratios of these IIIA elements also affect the properties.
- the efficiency of the device is a function of the molar ratio of Cu/(In+Ga).
- some of the important parameters of the cell such as its open circuit voltage, short circuit current and fill factor vary with the molar ratio of the IIIA elements, i.e. the Ga/(Ga+In) molar ratio.
- Cu/(In+Ga) molar ratio is kept at around or below 10.0.
- Ga/(Ga+In) molar ratio increases, on the other hand, the optical bandgap of the absorber layer increases and therefore the open circuit voltage of the solar cell increases while the short circuit current typically may decrease. It is important for a thin film deposition process to have the capability of controlling both the molar ratio of IB/IIIA, and the molar ratios of the Group IIIA components in the composition.
- Cu(In,Ga)(S,Se) 2 a more accurate formula for the compound is Cu(In,Ga)(S,Se) k , where k is typically close to 2 but may not be exactly 2. For simplicity we will continue to use the value of k as 2.
- Cu(In,Ga) means all compositions from CuIn to CuGa.
- Cu(In,Ga)(S,Se) 2 means the whole family of compounds with Ga/(Ga+In) molar ratio varying from 0 to 1, and Se/(Se+S) molar ratio varying from 0 to 1.
- the first technique used to grow Cu(In,Ga)Se 2 layers was the co-evaporation approach which involves evaporation of Cu, In, Ga and Se from separate evaporation boats onto a heated substrate, as the deposition rate of each component is carefully monitored and controlled.
- Another technique for growing Cu(In,Ga)(S,Se) 2 type compound thin films for solar cell applications is a two-stage process where at least two of the components of the Cu(In,Ga)(S,Se) 2 material are first deposited onto a substrate, and then reacted with S and/or Se in a high temperature annealing process.
- CuInSe 2 growth thin sub-layers of Cu and In are first deposited on a substrate to form a precursor layer and then this stacked precursor layer is reacted with Se at elevated temperature. If the reaction atmosphere contains sulfur, then a CuIn(S,Se) 2 layer can be grown. Addition of Ga in the precursor layer, i.e.
- Cu/In/Ga stacked film precursor allows the growth of a Cu(In,Ga)(S,Se) 2 absorber.
- Other prior-art techniques include deposition of Cu—Se/In—Se, Cu—Se/Ga—Se, or Cu—Se/In—Se/Ga—Se stacks and their reaction to form the compound.
- Mixed precursor stacks comprising compound and elemental sub-layers, such as a Cu/In—Se stack or a Cu/In—Se/Ga—Se stack, have also been used, where In—Se and Ga—Se represent selenides of In and Ga, respectively.
- 6,048,442 disclosed a method comprising sputter-depositing a stacked precursor film comprising a Cu—Ga alloy sub-layer and an In sub-layer to form a Cu—Ga/In stack on a metallic back electrode and then reacting this precursor stack film with one of Se and S to form the compound absorber layer.
- U.S. Pat. No. 6,092,669 described sputtering-based equipment and method for producing such absorber layers.
- the present invention provides a roll to roll system to form solar cell absorbers by continuously processing a surface of a flexible foil as the flexible foil is advanced through processing units of the roll to roll system.
- An aspect of the present invention provides a system for forming an absorber structure for solar cells on a front surface of a continuous flexible workpiece as the continuous flexible workpiece is advanced through units of the system.
- the system includes a conditioning unit to condition the front surface of the continuous flexible workpiece to form activated surface portions.
- the system further includes a first electroplating unit to form a first layer of a precursor stack by electroplating a metal belonging to one of Group IB and Group IIIA of the periodic table on an activated surface portion of the continuous flexible workpiece as the continuous flexible workpiece is advanced through the first electroplating station.
- a first cleaning unit of the system is to clean the first layer deposited in the first electroplating unit.
- the system further includes a second electroplating unit to form a second layer of the precursor stack by electroplating a metal belonging to one of Group IB and Group IIIA of the periodic table onto the first layer as the continuous flexible foil is advanced through the first and the second electroplating units and while the first layer is continued to be electroplated onto a following activated surface portion of the surface of the continuous flexible foil in the first electroplating unit.
- the first layer is different from the second layer.
- a second cleaning unit of the system is to clean the second layer deposited in the second electroplating unit.
- the system further includes a third electroplating unit to form a third layer by electroplating a metal belonging to one of Group IB and Group IIIA of the periodic table onto the second layer to complete the precursor stack as the flexible foil is advanced through the first, second and third electroplating stations and while the second layer is continued to be electroplated in the second electroplating station on the first layer that is electroplated on the following activated portion of the surface of the flexible foil, and while the first layer is continued to be electroplated onto another following activated portion of the surface of the flexible foil in the first electroplating station.
- the third layer is different from the first and second layers.
- the system further includes a moving assembly to hold and linearly move the continuous flexible workpiece through the units of the system, wherein the moving assembly comprises a feed spool to unwrap and feed unprocessed portions of the continuous flexible workpiece into the system and a take-up spool to receive the processed portions and wrap them around.
- FIG. 1 is a cross-sectional view of a solar cell employing a Group IBIIIAVIA absorber layer.
- FIG. 2 shows a roll to roll electrodeposition system of the present invention.
- FIG. 3 shows another roll to roll electrodeposition system of the present invention comprising multiple electroplating units and cleaning units.
- FIG. 3A shows a structure of the flexible foil base.
- FIG. 4 shows a roll to roll processing system comprising additional processing units including a Group VIA material electroplating unit.
- FIG. 5 shows a flow chart of an embodiment of a process using roll to roll system
- Present invention provides a low-cost, high throughput two-stage process for fabrication of CIGS(S) type absorber layers for manufacturing of solar cells.
- FIG. 2 schematically shows an embodiment of the process and the tool of the present invention.
- a roll-to-roll processing technique is used to electrodeposit a Group IB material (preferably Cu) and a Group IIIA material (preferably at least one of In and Ga) in a continuous manner on a continuous flexible workpiece 22 such as a flexible foil base including a flexible substrate and a contact layer.
- the tool 19 has a supply spool 20 and a return spool 21 and the flexible foil base 22 is directed from the supply spool 20 to the return spool 21 through a series of electroplating units 23 .
- the process units 23 may include at least one Group IB material electroplating unit, and at least one Group IIIA material electroplating unit.
- each electroplating unit 23 there may preferably be cleaning units 24 A, 24 B.
- the cleaning units rinse the electroplated surface after each electroplating process, and thus avoid cross contamination of the electroplating electrolytes or baths in the electroplating units 23 .
- the section passes through a cleaning unit where the chemical residues of the Cu plating bath on the section are rinsed off and the section moves into a Group IIIA electroplating unit such as a Ga electroplating unit.
- the section may also be dried after the rinsing step; however, in general it is preferable to keep the surface of the already plated material layer wet as it goes into another electroplating bath.
- a packing sheet 26 may be fed from a packing spool 27 , to between the layers of the flexible foil base 22 comprising the electroplated Group IB and Group IIIA materials on the return spool 21 .
- the packing sheet 26 may be a paper or thin polymeric sheet.
- Flow chart 100 shown in FIG. 5 provides an exemplary process flow for an embodiment of the roll to roll system of the present invention.
- a contact layer may be formed on the continuous flexible substrate to form a continuous flexible workpiece on which a precursor stack of the present invention would be built using the system of this invention.
- surface of the contact layer is conditioned to form an activated surface for the following electrodeposition process.
- the surface of the conditioned contact layer may be cleaned, e.g., rinsed with a cleaning solution before an electrodeposition process to remove possible chemical residues and particles from the surface of the contact layer.
- the surface activation step is very important because electrodeposition efficiency on a surface depends on the nature of that surface on which a material is deposited.
- An activated surface is a material surface that is electrochemically active and can be electroplated with efficiency. If the surface is electrochemically passive, electrodeposition efficiency is generally low and adhesion is poor. However, on an active, or activated, surface electrodeposition efficiency is higher and more consistent. Consistent electrodeposition efficiency yields consistent thickness for the electrodeposited material.
- CIGS type absorber layers are formed employing precursor stacks such as Cu/Ga/In or Cu/Ga/Cu/In stacks.
- the thicknesses of the layers within the stack need to be tightly controlled to be able to control the Cu/(In+Ga) and Ga/(In+Ga) molar ratios which are typically below 1 and which are important for the quality of the resulting absorbers and the performance of solar cells fabricated on such absorbers.
- a typical target ratio for Cu/(In+Ga) may be in the range of 0.8-0.95.
- the contact layer on which a first layer such as a Cu layer would be deposited may be exposed to the atmosphere for different periods of time depending on the location on the roll.
- the contact layer at the beginning of the roll may be coated with Cu within a few minutes whereas a portion of the contact layer at the end of the roll may be coated after 41 hours if the continuous flexible workpiece moves at a rate of 2 ft/minute.
- Such variation in exposure of the contact layer to atmosphere may induce differences in the condition of the contact layer surface due to oxidation, exposure to chemical fumes etc.
- Plating efficiency of the Cu layer on the contact layer may then be different on portions of the contact layer at the beginning of the roll and at the end of the roll. Such differences in efficiency, in turn, cause differences in the thickness of the Cu layer throughout the flexible workpiece and thus cause a change in the Cu/(In+Ga) molar ratio.
- Conditioning process of the present invention results in an electroplating efficiency of more than 90% when a subsequent electroplating process is performed and the first metal layer such as a copper layer is electroplated onto the activated surface.
- an activated surface formed on the contact layer by a cathodic conditioning process provides more than 90% electroplating efficiency for the subsequent electroplating process, such as copper electroplating.
- the electroplating efficiency is low, less than 90%, maybe even as low as 20-50%.
- Boxes 104 through 108 show a process sequence to form a precursor stack of the present invention.
- a Group IB material such as copper
- a cleaning step to clean the surface of the electrodeposited Group IB material, box 105 .
- a first Group IIIA material such as gallium
- a cleaning step to clean the surface of the electrodeposited first Group IIIA material layer, box 107 .
- a second Group IIIA material such as indium
- a second Group IIIA material may be electrodeposited on the surface of the cleaned first Group IIIA material layer, which completes the precursor stack.
- the precursor stack may be cleaned and dried following step, box 109 .
- the precursor stack may be reacted in presence of Group VIA materials, such as selenium and sulfur with gas phase delivery, to form an absorber, box 10 .
- the precursor layer in box 108 may be just cleaned without drying, as shown in box 111 , to electrodeposit a Group VIA material onto the precursor stack as shown in box 112 .
- the precursor stack with the Group VIA layer is cleaned, box 113 , and reacted to form an absorber, box 114 .
- additional Group VIA materials may be introduced to the forming absorber.
- Electrodeposition is a surface sensitive process. Defects in electrodeposited layers mostly originate from the surface they are plated on. Therefore, it is preferable to minimize handling of substrates in an electroplating approach. Surfaces to be plated need to be protected from physical contact, particles etc. that may later cause defectivity in the films deposited on such surfaces. Plating efficiency and the thickness uniformity of electroplated layers are also affected by the condition of the surface they are plated on. For example, electrodeposition of Cu, Ga or In on a chemically active, fresh surface is a much more repeatable process compared to electrodeposition on a surface that may be exposed to air, chemical vapors or, in general, to outside environment for varying amounts of time.
- a material such as Cu is plated on a section of the base.
- the surface of this plated material is fresh and active after plating and after the water rinse step. Therefore, when section moves into the next plating bath, for example a Ga or In plating bath, within a few seconds or minutes, deposition initiates on this active surface. If the velocity of the foil base is constant, then the Ga or In plating always operates on the same Cu surface in terms of activity. This provides highly repeatable results in terms of thickness and uniformity of the In and Ga layers. Same is true for the Cu layer also.
- the surface of the flexible foil base may first be activated by passing it through a pre-deposition electrolyte and applying a pre-deposition process step or conditioning to the surface.
- the predeposition process step may be an etching step or an electrotreating step such as a cathodic conditioning step comprising applying a cathodic voltage to the base with respect to an electrode in the pre-deposition electrolyte or an anodic conditioning step comprising applying an anodic voltage to the base with respect to an electrode in the pre-deposition electrolyte.
- Conditioning step may also include a pickling step; or a deposition step comprising depositing a fresh layer on the base before the deposition of Cu.
- an active surface may be provided to the Cu electrodeposition step so that this step yields repeatable results in terms of Cu layer thickness and uniformity.
- thickness and uniformity control for deposited Cu, In and/or Ga layers are of utmost importance since Cu/(In+Ga) and Ga/(In+Ga) molar ratios need to be controlled throughout the base.
- FIG. 3 shows an exemplary roll-to-roll electroplating system 30 with capability to produce, on a flexible foil base 22 , metallic stacks comprising Cu, In and Ga with excellent thickness control and uniformity.
- the electroplating system 30 comprises a series of process units, a supply spool 20 , a return spool 21 and a mechanism (not shown) to direct the flexible foil base 22 from the supply spool 20 to the return spool 21 through the series of process units.
- the series of process units comprises at least one Cu electroplating unit 31 , at least one Ga electroplating unit 32 , and at least one In electroplating unit 33 . It should be noted that the order of these electroplating units may be changed to obtain various stacks on the base.
- the order of the electroplating units shown in FIG. 3 would yield a stack of Cu/Ga/In on the base.
- Changing this order and optionally adding other electroplating units one may obtain stacks such as Cu/In/Ga, In/Cu/Ga, Ga/Cu/In, Cu/Ga/Cu/In, Cu/Ga/Cu/In/Cu, Cu/In/Cu/Ga, Cu/In/Cu/Ga/Cu etc. It should be noted that many more iterations of such stacks are possible.
- stacks initiating with a Cu layer are preferred because Cu plating yields highly controlled, good morphology coatings at high plating efficiency, and Cu is a good base on which Ga and/or In films can be electroplated.
- the present invention will be described using the configuration in FIG. 3 with the electroplating system 30 comprising one of each of a Cu electroplating unit, a Ga electroplating unit and an In electroplating unit.
- a conditioning unit 34 that conditions the surface of the flexible foil base 22 on which a Cu layer will be deposited in the Cu electroplating unit 31 .
- a typical structure of the flexible foil base 22 is shown in FIG. 3A .
- the flexible foil base 22 comprises a flexible foil substrate 45 and a conductive layer 46 or a contact layer deposited on a first surface 45 A of the flexible foil substrate 45 .
- the flexible foil substrate 45 may be made of any polymeric or metallic foil, but preferably it is a metallic foil such as a 20-250 um thick stainless steel foil, Ti foil, Al foil or aluminum alloy foil.
- the conductive layer 46 may be in the form of a single layer or alternately it may comprise a stack of various sublayers (not shown).
- the conductive layer comprises at least one diffusion barrier layer that prevents diffusion of impurities from the flexible foil substrate 45 into the layers to be electrodeposited and into the CIGS(S) layer during its formation.
- Materials of the conductive layer 46 include but are not limited to Ti, Mo, Cr, Ta, W, Ru, Ir, Os, and nitrides and oxy-nitrides of these materials.
- the free surface 46 A of the conductive layer 46 comprises at least one of Ru, Ir and Os for better nucleation of the electroplated layers.
- electrodeposition is carried out on the free surface 46 A of the conductive layer 46 .
- the back surface 45 B of the flexible foil substrate 45 may optionally be covered with a secondary layer 47 (shown with dotted line) to protect the flexible foil substrate 45 during annealing/reaction steps that will follow to form the CIGS(S) compound, or to avoid buckling of the flexible foil substrate 45 .
- a secondary layer 47 shown with dotted line
- the material of the secondary layer 47 be stable in chemistries of the Cu, In and Ga plating baths, i.e. not dissolve into and contaminate such baths, and also be resistant to reaction with Group VIA elements.
- Materials that can be used in the secondary layer 47 include but are not limited to Ru, Os, Ir, Ta, W etc.
- a secondary layer 47 comprising at least one of Ru, Ir and Os has an added benefit. Such materials are very resistant to reaction with Se, S and Te. Therefore, after any reaction step that forms CIGS(S) compound layer on the free surface 46 A of the conductive layer 46 , the secondary layer protects the flexible foil substrate 45 from reaction with Se, S or Te and leaves a surface that can be soldered easily.
- Mo was used as the secondary layer 47 . During selenization and/or sulfidation processes or during the growth of the CIGS(S) absorber, this Mo layer reacted with Se and/or S forming a Mo(S,Se) surface layer. After solar cells are completed, they need to be interconnected to form modules.
- Interconnection involves soldering or otherwise attaching back surface of each cell to the front surface of the adjacent cell.
- a Mo(S,Se) layer on the back of the cell cannot be soldered effectively, therefore physical removal of the selenized and/or sulfidized Mo surface is needed.
- a surface comprising at least one of Ru, Ir and Os can be soldered easily without the added step of removing a selenized or sulfidized surface layer because these materials do not appreciably selenize or sulfidize.
- the flexible foil base 22 passes through a conditioning unit 34 , and an optional cleaning unit 35 , before entering into the Cu electroplating unit 31 .
- the conditioning unit 34 the surface of the flexible foil base 22 (such as the free surface 46 A of the conductive layer 46 in FIG. 3A ) is conditioned to render it ready for electrodeposition with Cu.
- Such conditioning may involve exposing the free surface 46 A to an acidic or basic solution for etching and/or activation, applying a cathodic or anodic voltage to the free surface 46 A with respect to an electrode while both the electrode and the free surface 46 A are exposed to an electrolyte, electrodepositing a seed layer on the free surface 46 A, or simply rinsing and wetting the free surface 46 A before it moves into the Cu electroplating unit 31 . If only a rinsing process is carried out in the conditioning unit 34 , there would not be a need to the cleaning unit 35 . Otherwise cleaning unit 35 is needed to remove any residual chemicals left on both faces of the flexible foil base 22 before it moves into the Cu electroplating unit 31 .
- this seed layer may be a Cu layer that is 2-50 nm thick and it may be deposited from a bath that yields defect free uniform layers. Complexed Cu electrolytes with high pH are especially suitable for this purpose.
- Use of seed layers and various chemistries for electroplating are disclosed in Applicant's co-pending U.S. application Ser. No. 11/266,013 filed Nov. 2, 2005 entitled “Technique and Apparatus for Depositing Layers of Semiconductors For Solar Cell and Modular Fabrication”, and U.S. application Ser. No. 11/462,685 filed Aug. 4, 2004 entitled “Technique for Preparing Precursor Films and Compound Layers for Thin Film Solar Cell Fabrication and Apparatus Corresponding Thereto”, entire contents of these applications are incorporated herein by reference.
- the free surface 46 A of the conductive layer 46 is conditioned and cleaned it moves into the Cu electroplating unit 31 .
- the free surface 46 A (or the surface of the seed layer if a seed layer has been deposited in the conditioning unit 34 ) is exposed to a Cu plating bath 36 A which may be circulated between a first reservoir 36 AA and a first chemical cabinet 36 A′.
- the Cu plating bath 36 A may be filtered and replenished during circulation or while in the first chemical cabinet 36 A′.
- Measurement and control of various bath parameters, such as additive content, Cu content, temperature, pH etc. may be continuously or periodically carried out within the first chemical cabinet 36 A′ to assure stability of the Cu deposition process.
- Electrical connection to the conductive layer 46 may be achieved by various means including through rollers 39 which may be touching the flexible foil base 22 at, at least part of its back or front surfaces.
- front surface contacts are made at the two edges avoiding physical contact with most of the front surface which may be damaged or contaminated by contacts.
- a first anode 40 A is placed in the Cu plating bath 36 A and a potential difference is applied between the first anode 40 A and the portion of the conductive layer 46 within the Cu electroplating unit 31 , to deposit Cu on the portion of the free surface 46 A that is exposed to the Cu plating bath 36 A as the flexible foil base 22 is moved.
- the portion of the flexible foil base 22 processed in the Cu electroplating unit 31 passes through the Cu cleaning unit 37 A and enters into the Ga electroplating unit 32 .
- the surface of the already deposited Cu layer is exposed to a Ga plating bath 36 B which may be circulated between a second reservoir 36 BB and a second chemical cabinet 36 B′.
- the Ga plating bath 36 B may be filtered and replenished during circulation or while in the second chemical cabinet 36 B′.
- Measurement and control of various bath parameters, such as additive content, Ga content, temperature, pH etc. may be continuously or periodically carried out within the second chemical cabinet 36 B′ to assure stability of the Ga deposition process.
- Electrical connection to the conductive layer 46 may be achieved by various means including through rollers 39 which may be touching the base at, at least part of its back or front surfaces.
- front surface contacts are made at the two edges avoiding physical contact with most of the front surface which may be damaged or contaminated by contacts.
- a second anode 40 B is placed in the Ga plating bath 36 B and a potential difference is applied between the second anode 40 B and the portion of the conductive layer 46 within the Ga electroplating unit 32 , to deposit Ga on the portion of the Cu surface that is exposed to the Ga plating bath 36 B as the flexible foil base 22 is moved.
- the portion of the flexible foil base processed in the Ga electroplating unit 32 passes through the Ga cleaning unit 37 B and enters into the In electroplating unit 33 .
- the surface of the already deposited Ga layer is exposed to an In plating bath 36 C which may be circulated between a third reservoir 36 CC and a third chemical cabinet 36 C′.
- the In plating bath 36 C may be filtered and replenished during circulation or while in the third chemical cabinet 36 C′.
- Measurement and control of various bath parameters, such as additive content, In content, temperature, pH etc. may be continuously or periodically carried out within the third chemical cabinet 36 C′ to assure stability of the In deposition process.
- Electrical connection to the conductive layer 46 may be achieved by various means including through rollers 39 which may be touching the flexible foil base at, at least part of its back or front surfaces.
- front surface contacts are made at the two edges avoiding physical contact with most of the front surface which may be damaged or contaminated by contacts.
- a third anode 40 C is placed in the In plating bath 36 C and a potential difference is applied between the third anode 40 C and the portion of the conductive layer 46 within the In electroplating unit 33 , to deposit In on the portion of the Ga surface that is exposed to the In plating bath 36 C as the base 22 is moved.
- the portion of the flexible foil base comprising the all-electroplated Cu/Ga/In stack is passed through a cleaning/drying unit 38 and moved to the return spool 21 .
- additional process units may be added to the electroplating system 30 of FIG. 3 .
- another Cu electroplating unit and another cleaning unit may be inserted between the Ga cleaning unit 37 B and In electroplating unit 33 to fabricate a Cu/Ga/Cu/In stack.
- the anodes employed in the electroplating units may be inert anodes or they may be dissolvable anodes of Cu, In and Ga for Cu electrodeposition, In electrodeposition and Ga electrodeposition, respectively.
- the thicknesses of the Cu, In and Ga layers within the stack may range from 10 nm to 500 nm. Details of the cleaning or cleaning/drying units are not shown in FIG. 3 .
- established cleaning means such as spraying the cleaning solution onto the part to be cleaned or immersing the part in the cleaning solution
- Air knives directing high speed air or inert gas onto the part to be dried may be used as the drying means.
- the drying gas may be pre-filtered and warmed for effective and fast drying.
- FIG. 4 depicts a roll-to-roll processing system 50 comprising a Group IB-IIIA electroplating unit 51 and a Group VIA material electroplating unit 62 .
- the Group IB-IIIA plating unit 51 electrodeposits the Group IB materials and Group IIIA materials on the flexible foil base 22 forming a metallic precursor film and may, for example, comprise all or most of the components of the electroplating system 30 of FIG. 3 .
- the Group IB-IIIA plating unit 51 may deposit Cu, Ga and In layers and may comprise the conditioning unit 34 , the cleaning unit 35 , the Cu electroplating unit 31 , the Cu cleaning unit 37 A, the Ga electroplating unit 32 , the Ga cleaning unit 37 B, and the In electroplating unit 33 of FIG.
- the flexible foil base 22 coated or electrochemically coated with Cu, Ga and In moves into the Group VIA material electroplating unit 62 with a clean and wet surface.
- a layer of at least one of Se, S and Te, preferably Se is deposited onto the metallic precursor film.
- the flexible foil base with the “metallic precursor/Group VIA material” stack may then be passed through a final cleaning/drying module 63 and rolled onto the return spool 21 . Presence of a Group VIA material on the metallic precursor film comprising Cu, In and Ga has advantages.
- One such advantage is the protection provided by the Group VIA material to the surface of the metallic precursor film.
- Indium and Ga are soft, low melting materials and they are vulnerable to easy scratching during rolling and handling.
- a Group VIA material such as Se
- the thickness of the electroplated Group VIA material may be in the range of 10-2000 nm.
- the roll-to-roll processing system of FIG. 4 may accommodate an optional annealing unit 64 as shown in FIG. 4 .
- the annealing unit 64 will cause a reaction between the electrodeposited metallic precursor film and the electrodeposited Group VIA material and form a reacted precursor layer on the flexible foil base 22 .
- the reacted precursor layer may comprise phases such as Cu, In, Ga, Cu—Ga, Cu—In, In—Ga, Cu—Se, In—Se, Ga—Se, Cu—In—Se, Cu—Ga—Se, In—Ga—Se and Cu—In—Ga—Se, depending on the temperature applied in the annealing unit 64 and the time spent in the annealing unit 64 .
- the temperature applied by the annealing unit may be in the range of 100-550 C, preferably in the range of 200-450 C.
- the flexible web comprising the reacted precursor layer may be rolled onto the return spool 21 safely.
- a packing sheet may also be rolled along with it as described with reference to FIG. 2 .
- the Group VIA material electroplating unit 62 may be similar to the electroplating units described with reference to FIG. 3 .
- the annealing unit 64 may be similar to a design described in co-pending U.S. patent application Ser. No. 11/549,590 filed Oct. 13, 2006 entitled “Method and Apparatus For Converting Precursor Layers Into Photovoltaic Absorbers”, entire contents of which are incorporated herein by reference.
- the examples above employed a flexible foil base 22 such as the one depicted in FIG. 3A .
- the conductive layer 46 and the optional secondary layer 47 may be deposited on the flexible foil substrate 45 by various deposition techniques such as evaporation, sputtering etc. in a separate system. It is, however, possible to integrate another electroplating or electroless plating module to the systems of FIGS. 3 and 4 so that the flexible foil substrate 45 gets electroplated with at least one of a conductive layer or contact layer and a secondary layer before it moves into other process units such as the Group IB-IIIA electroplating unit of FIG. 4 .
- the contact layer for this approach needs to comprise materials that can be electroplated or electroless plated and at the same time be a good ohmic contact to CIGS(S) material and not react extensively with S and/or Se.
- Such layers are disclosed in Applicant's co-pending U.S. application Ser. No. 11/266,013 filed Nov. 2, 2005 entitled “Technique and Apparatus for Depositing Layers of Semiconductors For Solar Cell and Modular Fabrication”, and U.S. application Ser. No. 11/462,685 filed Aug.
- the power supply controlling that thickness may be sent a signal by the XRF tool to increase or decrease the plating current density to keep the film thickness within a targeted window.
- reaction or further reaction of these layers with Group VIA materials may be achieved by various means.
- these layers may be exposed to Group VIA vapors at elevated temperatures.
- These techniques are well known in the field and they involve heating the layers to a temperature range of 350-600° C. in the presence of at least one of Se vapors, S vapors, and Te vapors provided by sources such as solid Se, solid S, solid Te, H 2 Se gas, H 2 S gas etc. for periods ranging from 5 minutes to 1 hour.
- a layer or multi layers of Group VIA materials may be deposited on the metallic precursor layers and then heated up in a furnace or in a rapid thermal annealing furnace and like.
- Group VIA materials may be evaporated on, sputtered on or plated on the metallic precursor layers in a separate process unit.
- inks comprising Group VIA nano particles may be prepared and these inks may be deposited on the metallic precursor layers to form a Group VIA material layer comprising Group VIA nano particles. Dipping, spraying, doctor-blading or ink writing techniques may be employed to deposit such layers. Reaction may be carried out at elevated temperatures for times ranging from 1 minute to 30 minutes depending upon the temperature. As a result of reaction, the Group IBIIIAVIA compound is formed.
- reaction chambers may also be added to the apparatus of FIG. 4 or the annealing unit 64 may be a reaction unit to carry out the whole process in-line so that the flexible foil base with a fully formed CIGS(S) layer on its surface may be rolled onto the return spool 21 .
- Solar cells may be fabricated on the Group IBIIIAVIA compound layers of the present invention using materials and methods well known in the field. For example a thin ( ⁇ 0.1 microns) CdS layer may be deposited on the surface of the compound layer using the chemical dip method. A transparent window of ZnO may be deposited over the CdS layer using MOCVD or sputtering techniques. A metallic finger pattern is optionally deposited over the ZnO to complete the solar cell.
Abstract
Description
- This application claims priority to Provisional Application Ser. No. 60/862,164 filed on Oct. 19, 2006.
- The present invention relates to methods and apparatus for preparing thin films of Group IBIIIAVIA compound semiconductor films for radiation detector and photovoltaic applications.
- Solar cells are photovoltaic devices that convert sunlight directly into electrical power. The most common solar cell material is silicon, which is in the form of single or polycrystalline wafers. However, the cost of electricity generated using silicon-based solar cells is higher than the cost of electricity generated by the more traditional methods. Therefore, since early 1970's there has been an effort to reduce cost of solar cells for terrestrial use. One way of reducing the cost of solar cells is to develop low-cost thin film growth techniques that can deposit solar-cell-quality absorber materials on large area substrates and to fabricate these devices using high-throughput, low-cost methods.
- Group IBIIIAVIA compound semiconductors comprising some of the Group IB (Cu, Ag, Au), Group IIIA (B, Al, Ga, In, Tl) and Group VIA (O, S, Se, Te, Po) materials or elements of the periodic table are excellent absorber materials for thin film solar cell structures. Especially, compounds of Cu, In, Ga, Se and S which are generally referred to as CIGS(S), or Cu(In,Ga)(S,Se)2 or CuIn1-xGax (SySe1-y)k, where 0≦x≦1, 0≦y≦1 and k is approximately 2, have already been employed in solar cell structures that yielded conversion efficiencies approaching 20%. Absorbers containing Group IIIA element Al and/or Group VIA element Te also showed promise. Therefore, in summary, compounds containing: i) Cu from Group IB, ii) at least one of In, Ga, and Al from Group IIIA, and iii) at least one of S, Se, and Te from Group VIA, are of great interest for solar cell applications.
- The structure of a conventional Group IBIIIAVIA compound photovoltaic cell such as a Cu(In,Ga,Al)(S,Se,Te)2 thin film solar cell is shown in
FIG. 1 . Thedevice 10 is fabricated on asubstrate 11, such as a sheet of glass, a sheet of metal (such as aluminum or stainless steel), an insulating foil or web, or a conductive foil or web. Theabsorber film 12, which comprises a material in the family of Cu(In,Ga,Al)(S,Se,Te)2, is grown over aconductive layer 13, which is previously deposited on thesubstrate 11 and which acts as the electrical contact to the device. Various conductive layers comprising Mo, Ta, W, Ti, and stainless steel etc. have been used in the solar cell structure ofFIG. 1 . If the substrate itself is a properly selected conductive material, it is possible not to use aconductive layer 13, since thesubstrate 11 may then be used as the ohmic contact to the device. After theabsorber film 12 is grown, atransparent layer 14 such as a CdS, ZnO or CdS/ZnO stack is formed on the absorber film.Radiation 15 enters the device through thetransparent layer 14. Metallic grids (not shown) may also be deposited over thetransparent layer 14 to reduce the effective series resistance of the device. It should be noted that the structure ofFIG. 1 may also be inverted if substrate is transparent. In that case light enters the device from the substrate side of the solar cell. - In a thin film solar cell employing a Group IBIIIAVIA compound absorber, the cell efficiency is a strong function of the molar ratio of IB/IIIA. If there are more than one Group IIIA materials in the composition, the relative amounts or molar ratios of these IIIA elements also affect the properties. For a Cu(In,Ga)(S,Se)2 absorber layer, for example, the efficiency of the device is a function of the molar ratio of Cu/(In+Ga). Furthermore, some of the important parameters of the cell, such as its open circuit voltage, short circuit current and fill factor vary with the molar ratio of the IIIA elements, i.e. the Ga/(Ga+In) molar ratio. In general, for good device performance Cu/(In+Ga) molar ratio is kept at around or below 10.0. As the Ga/(Ga+In) molar ratio increases, on the other hand, the optical bandgap of the absorber layer increases and therefore the open circuit voltage of the solar cell increases while the short circuit current typically may decrease. It is important for a thin film deposition process to have the capability of controlling both the molar ratio of IB/IIIA, and the molar ratios of the Group IIIA components in the composition. It should be noted that although the chemical formula is often written as Cu(In,Ga)(S,Se)2, a more accurate formula for the compound is Cu(In,Ga)(S,Se)k, where k is typically close to 2 but may not be exactly 2. For simplicity we will continue to use the value of k as 2. It should be further noted that the notation “Cu(X,Y)” in the chemical formula means all chemical compositions of X and Y from (X=0% and Y=100%) to (X=100% and Y=0%). For example, Cu(In,Ga) means all compositions from CuIn to CuGa. Similarly, Cu(In,Ga)(S,Se)2 means the whole family of compounds with Ga/(Ga+In) molar ratio varying from 0 to 1, and Se/(Se+S) molar ratio varying from 0 to 1.
- The first technique used to grow Cu(In,Ga)Se2 layers was the co-evaporation approach which involves evaporation of Cu, In, Ga and Se from separate evaporation boats onto a heated substrate, as the deposition rate of each component is carefully monitored and controlled.
- Another technique for growing Cu(In,Ga)(S,Se)2 type compound thin films for solar cell applications is a two-stage process where at least two of the components of the Cu(In,Ga)(S,Se)2 material are first deposited onto a substrate, and then reacted with S and/or Se in a high temperature annealing process. For example, for CuInSe2 growth, thin sub-layers of Cu and In are first deposited on a substrate to form a precursor layer and then this stacked precursor layer is reacted with Se at elevated temperature. If the reaction atmosphere contains sulfur, then a CuIn(S,Se)2 layer can be grown. Addition of Ga in the precursor layer, i.e. use of a Cu/In/Ga stacked film precursor, allows the growth of a Cu(In,Ga)(S,Se)2 absorber. Other prior-art techniques include deposition of Cu—Se/In—Se, Cu—Se/Ga—Se, or Cu—Se/In—Se/Ga—Se stacks and their reaction to form the compound. Mixed precursor stacks comprising compound and elemental sub-layers, such as a Cu/In—Se stack or a Cu/In—Se/Ga—Se stack, have also been used, where In—Se and Ga—Se represent selenides of In and Ga, respectively.
- Sputtering and evaporation techniques have been used in prior art approaches to deposit the sub-layers containing the Group IB and Group IIIA components of metallic precursor stacks. In the case of CuInSe2 growth, for example, Cu and In sub-layers were sequentially sputter-deposited from Cu and In targets on a substrate and then the stacked precursor film thus obtained was heated in the presence of gas containing Se at elevated temperatures as described in U.S. Pat. No. 4,798,660. More recently U.S. Pat. No. 6,048,442 disclosed a method comprising sputter-depositing a stacked precursor film comprising a Cu—Ga alloy sub-layer and an In sub-layer to form a Cu—Ga/In stack on a metallic back electrode and then reacting this precursor stack film with one of Se and S to form the compound absorber layer. U.S. Pat. No. 6,092,669 described sputtering-based equipment and method for producing such absorber layers.
- One prior art method described in U.S. Pat. No. 4,581,108 utilizes an electrodeposition approach for metallic precursor preparation. In this method a Cu sub-layer is first electrodeposited on a substrate. This is then followed by electrodeposition of an In sub-layer and heating of the deposited Cu/In precursor stack in a reactive atmosphere containing Se. This technique was found to require very high plating current densities resulting in non-uniformities and problems of adhesion to the substrate as discussed in reference publications (Kapur et al., “Low Cost Thin Film Chalcopyrite Solar Cells, Proceedings of 18th IEEE Photovoltaic Specialists Conf., 1985, p. 1429; “Low Cost Methods for the Production of Semiconductor Films for CIS/CdS Solar Cells”, Solar Cells, vol. 21, p. 65, 1987).
- As the brief review above demonstrates there is still a need to develop high-throughput, low cost techniques to manufacture thin film solar cells and modules.
- The present invention provides a roll to roll system to form solar cell absorbers by continuously processing a surface of a flexible foil as the flexible foil is advanced through processing units of the roll to roll system.
- An aspect of the present invention provides a system for forming an absorber structure for solar cells on a front surface of a continuous flexible workpiece as the continuous flexible workpiece is advanced through units of the system. The system includes a conditioning unit to condition the front surface of the continuous flexible workpiece to form activated surface portions.
- The system further includes a first electroplating unit to form a first layer of a precursor stack by electroplating a metal belonging to one of Group IB and Group IIIA of the periodic table on an activated surface portion of the continuous flexible workpiece as the continuous flexible workpiece is advanced through the first electroplating station. A first cleaning unit of the system is to clean the first layer deposited in the first electroplating unit.
- The system further includes a second electroplating unit to form a second layer of the precursor stack by electroplating a metal belonging to one of Group IB and Group IIIA of the periodic table onto the first layer as the continuous flexible foil is advanced through the first and the second electroplating units and while the first layer is continued to be electroplated onto a following activated surface portion of the surface of the continuous flexible foil in the first electroplating unit. The first layer is different from the second layer. A second cleaning unit of the system is to clean the second layer deposited in the second electroplating unit.
- The system further includes a third electroplating unit to form a third layer by electroplating a metal belonging to one of Group IB and Group IIIA of the periodic table onto the second layer to complete the precursor stack as the flexible foil is advanced through the first, second and third electroplating stations and while the second layer is continued to be electroplated in the second electroplating station on the first layer that is electroplated on the following activated portion of the surface of the flexible foil, and while the first layer is continued to be electroplated onto another following activated portion of the surface of the flexible foil in the first electroplating station. The third layer is different from the first and second layers. The system further includes a moving assembly to hold and linearly move the continuous flexible workpiece through the units of the system, wherein the moving assembly comprises a feed spool to unwrap and feed unprocessed portions of the continuous flexible workpiece into the system and a take-up spool to receive the processed portions and wrap them around.
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FIG. 1 is a cross-sectional view of a solar cell employing a Group IBIIIAVIA absorber layer. -
FIG. 2 shows a roll to roll electrodeposition system of the present invention. -
FIG. 3 shows another roll to roll electrodeposition system of the present invention comprising multiple electroplating units and cleaning units. -
FIG. 3A shows a structure of the flexible foil base. -
FIG. 4 shows a roll to roll processing system comprising additional processing units including a Group VIA material electroplating unit. -
FIG. 5 shows a flow chart of an embodiment of a process using roll to roll system - Present invention provides a low-cost, high throughput two-stage process for fabrication of CIGS(S) type absorber layers for manufacturing of solar cells.
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FIG. 2 schematically shows an embodiment of the process and the tool of the present invention. In this embodiment, a roll-to-roll processing technique is used to electrodeposit a Group IB material (preferably Cu) and a Group IIIA material (preferably at least one of In and Ga) in a continuous manner on a continuousflexible workpiece 22 such as a flexible foil base including a flexible substrate and a contact layer. Thetool 19 has asupply spool 20 and areturn spool 21 and theflexible foil base 22 is directed from thesupply spool 20 to thereturn spool 21 through a series ofelectroplating units 23. Theprocess units 23 may include at least one Group IB material electroplating unit, and at least one Group IIIA material electroplating unit. After eachelectroplating unit 23, there may preferably be cleaningunits electroplating units 23. For example, after a section of thebase 22 is electroplated or electrocoated with Cu in an electroplating unit, the section passes through a cleaning unit where the chemical residues of the Cu plating bath on the section are rinsed off and the section moves into a Group IIIA electroplating unit such as a Ga electroplating unit. It should be noted that the section may also be dried after the rinsing step; however, in general it is preferable to keep the surface of the already plated material layer wet as it goes into another electroplating bath. There is a need to provide a rinse/dry unit 25 at the end of thetool 19 to assure that theflexible foil base 22 comprising electroplated Group IB and Group IIIA materials is completely clean and dry before being rolled onto thereturn spool 21. To avoid damage to the electroplated layers, apacking sheet 26 may be fed from a packingspool 27, to between the layers of theflexible foil base 22 comprising the electroplated Group IB and Group IIIA materials on thereturn spool 21. The packingsheet 26 may be a paper or thin polymeric sheet. -
Flow chart 100 shown inFIG. 5 provides an exemplary process flow for an embodiment of the roll to roll system of the present invention. Initially, as shown inbox 101, a contact layer may be formed on the continuous flexible substrate to form a continuous flexible workpiece on which a precursor stack of the present invention would be built using the system of this invention. Next, as shown inbox 102, in a surface activation step, surface of the contact layer is conditioned to form an activated surface for the following electrodeposition process. As shown inbox 103, the surface of the conditioned contact layer may be cleaned, e.g., rinsed with a cleaning solution before an electrodeposition process to remove possible chemical residues and particles from the surface of the contact layer. - It should be noted that the surface activation step is very important because electrodeposition efficiency on a surface depends on the nature of that surface on which a material is deposited. An activated surface is a material surface that is electrochemically active and can be electroplated with efficiency. If the surface is electrochemically passive, electrodeposition efficiency is generally low and adhesion is poor. However, on an active, or activated, surface electrodeposition efficiency is higher and more consistent. Consistent electrodeposition efficiency yields consistent thickness for the electrodeposited material. In the present invention CIGS type absorber layers are formed employing precursor stacks such as Cu/Ga/In or Cu/Ga/Cu/In stacks. The thicknesses of the layers within the stack need to be tightly controlled to be able to control the Cu/(In+Ga) and Ga/(In+Ga) molar ratios which are typically below 1 and which are important for the quality of the resulting absorbers and the performance of solar cells fabricated on such absorbers. A typical target ratio for Cu/(In+Ga) may be in the range of 0.8-0.95. In a roll-to-roll system the contact layer on which a first layer such as a Cu layer would be deposited may be exposed to the atmosphere for different periods of time depending on the location on the roll. For example, in a roll that may be 5000 ft long, the contact layer at the beginning of the roll may be coated with Cu within a few minutes whereas a portion of the contact layer at the end of the roll may be coated after 41 hours if the continuous flexible workpiece moves at a rate of 2 ft/minute. Such variation in exposure of the contact layer to atmosphere may induce differences in the condition of the contact layer surface due to oxidation, exposure to chemical fumes etc. Plating efficiency of the Cu layer on the contact layer may then be different on portions of the contact layer at the beginning of the roll and at the end of the roll. Such differences in efficiency, in turn, cause differences in the thickness of the Cu layer throughout the flexible workpiece and thus cause a change in the Cu/(In+Ga) molar ratio. As a result, process yields are reduced, and manufacturability of high efficiency solar cells at high yields cannot be achieved. By employing an activation chamber and activation process step before the electrodeposition of the first layer on the contact layer, consistence of electrodeposition efficiency of the first layer on the contact layer is assured throughout the roll and yield for consistent Cu/(In+Ga) ratio is assured.
- Conditioning process of the present invention results in an electroplating efficiency of more than 90% when a subsequent electroplating process is performed and the first metal layer such as a copper layer is electroplated onto the activated surface. For example, an activated surface formed on the contact layer by a cathodic conditioning process provides more than 90% electroplating efficiency for the subsequent electroplating process, such as copper electroplating. However, if the surface is electrochemically passive, the electroplating efficiency is low, less than 90%, maybe even as low as 20-50%.
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Boxes 104 through 108 show a process sequence to form a precursor stack of the present invention. As shown inbox 104, in a first electrodeposition step, a Group IB material such as copper, may be electrodeposited on the conditioned and cleaned surface of the contact layer. This step is followed by a cleaning step to clean the surface of the electrodeposited Group IB material,box 105. As shown inbox 106, in a second electrodeposition step, a first Group IIIA material, such as gallium, may be electrodeposited on the surface of the cleaned Group IB material layer. This step is followed by a cleaning step to clean the surface of the electrodeposited first Group IIIA material layer,box 107. As shown inbox 108, in a third electrodeposition step, a second Group IIIA material, such as indium, may be electrodeposited on the surface of the cleaned first Group IIIA material layer, which completes the precursor stack. The precursor stack may be cleaned and dried following step,box 109. The precursor stack may be reacted in presence of Group VIA materials, such as selenium and sulfur with gas phase delivery, to form an absorber,box 10. - Alternately, the precursor layer in
box 108 may be just cleaned without drying, as shown inbox 111, to electrodeposit a Group VIA material onto the precursor stack as shown inbox 112. Following the electrodeposition process, the precursor stack with the Group VIA layer is cleaned,box 113, and reacted to form an absorber,box 114. During the reaction, optionally, additional Group VIA materials may be introduced to the forming absorber. - The roll-to-roll processing approach of the present invention offers several advantages. Electrodeposition is a surface sensitive process. Defects in electrodeposited layers mostly originate from the surface they are plated on. Therefore, it is preferable to minimize handling of substrates in an electroplating approach. Surfaces to be plated need to be protected from physical contact, particles etc. that may later cause defectivity in the films deposited on such surfaces. Plating efficiency and the thickness uniformity of electroplated layers are also affected by the condition of the surface they are plated on. For example, electrodeposition of Cu, Ga or In on a chemically active, fresh surface is a much more repeatable process compared to electrodeposition on a surface that may be exposed to air, chemical vapors or, in general, to outside environment for varying amounts of time. In a roll-to-roll process all depositions are done in a controlled environment (enclosure for the roll not shown in figures) and the time between depositions are minimized unlike a batch process that requires several loading and unloading steps to deposit a stack of materials on a base. In the present roll-to-roll process a material, such as Cu is plated on a section of the base. The surface of this plated material is fresh and active after plating and after the water rinse step. Therefore, when section moves into the next plating bath, for example a Ga or In plating bath, within a few seconds or minutes, deposition initiates on this active surface. If the velocity of the foil base is constant, then the Ga or In plating always operates on the same Cu surface in terms of activity. This provides highly repeatable results in terms of thickness and uniformity of the In and Ga layers. Same is true for the Cu layer also.
- If the Cu layer is first to be deposited on the flexible foil base, the surface of the flexible foil base may first be activated by passing it through a pre-deposition electrolyte and applying a pre-deposition process step or conditioning to the surface. The predeposition process step may be an etching step or an electrotreating step such as a cathodic conditioning step comprising applying a cathodic voltage to the base with respect to an electrode in the pre-deposition electrolyte or an anodic conditioning step comprising applying an anodic voltage to the base with respect to an electrode in the pre-deposition electrolyte. Conditioning step may also include a pickling step; or a deposition step comprising depositing a fresh layer on the base before the deposition of Cu. In all such cases, an active surface may be provided to the Cu electrodeposition step so that this step yields repeatable results in terms of Cu layer thickness and uniformity. As described before, thickness and uniformity control for deposited Cu, In and/or Ga layers are of utmost importance since Cu/(In+Ga) and Ga/(In+Ga) molar ratios need to be controlled throughout the base.
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FIG. 3 shows an exemplary roll-to-roll electroplating system 30 with capability to produce, on aflexible foil base 22, metallic stacks comprising Cu, In and Ga with excellent thickness control and uniformity. Theelectroplating system 30 comprises a series of process units, asupply spool 20, areturn spool 21 and a mechanism (not shown) to direct theflexible foil base 22 from thesupply spool 20 to thereturn spool 21 through the series of process units. The series of process units comprises at least oneCu electroplating unit 31, at least oneGa electroplating unit 32, and at least one Inelectroplating unit 33. It should be noted that the order of these electroplating units may be changed to obtain various stacks on the base. For example, the order of the electroplating units shown inFIG. 3 would yield a stack of Cu/Ga/In on the base. Changing this order and optionally adding other electroplating units one may obtain stacks such as Cu/In/Ga, In/Cu/Ga, Ga/Cu/In, Cu/Ga/Cu/In, Cu/Ga/Cu/In/Cu, Cu/In/Cu/Ga, Cu/In/Cu/Ga/Cu etc. It should be noted that many more iterations of such stacks are possible. However, stacks initiating with a Cu layer are preferred because Cu plating yields highly controlled, good morphology coatings at high plating efficiency, and Cu is a good base on which Ga and/or In films can be electroplated. In the following, the present invention will be described using the configuration inFIG. 3 with theelectroplating system 30 comprising one of each of a Cu electroplating unit, a Ga electroplating unit and an In electroplating unit. - In the
electroplating system 30 ofFIG. 3 there is, preferably, aconditioning unit 34 that conditions the surface of theflexible foil base 22 on which a Cu layer will be deposited in theCu electroplating unit 31. A typical structure of theflexible foil base 22 is shown inFIG. 3A . Theflexible foil base 22 comprises aflexible foil substrate 45 and aconductive layer 46 or a contact layer deposited on afirst surface 45A of theflexible foil substrate 45. Theflexible foil substrate 45 may be made of any polymeric or metallic foil, but preferably it is a metallic foil such as a 20-250 um thick stainless steel foil, Ti foil, Al foil or aluminum alloy foil. Various metallic foil substrates (such as Cu, Ti, Mo, Ni, Al) have previously been identified for CIGS(S) solar cell applications (see for example, B. M. Basol et al., “Status of flexible CIS research at ISET”, NASA Document ID: 19950014096, accession No: 95N-20512, available from NASA Center for AeroSpace Information). Theconductive layer 46 may be in the form of a single layer or alternately it may comprise a stack of various sublayers (not shown). Preferably, the conductive layer comprises at least one diffusion barrier layer that prevents diffusion of impurities from theflexible foil substrate 45 into the layers to be electrodeposited and into the CIGS(S) layer during its formation. Materials of theconductive layer 46 include but are not limited to Ti, Mo, Cr, Ta, W, Ru, Ir, Os, and nitrides and oxy-nitrides of these materials. Preferably, thefree surface 46A of theconductive layer 46 comprises at least one of Ru, Ir and Os for better nucleation of the electroplated layers. - In this example, electrodeposition is carried out on the
free surface 46A of theconductive layer 46. Theback surface 45B of theflexible foil substrate 45 may optionally be covered with a secondary layer 47 (shown with dotted line) to protect theflexible foil substrate 45 during annealing/reaction steps that will follow to form the CIGS(S) compound, or to avoid buckling of theflexible foil substrate 45. It is important that the material of thesecondary layer 47 be stable in chemistries of the Cu, In and Ga plating baths, i.e. not dissolve into and contaminate such baths, and also be resistant to reaction with Group VIA elements. Materials that can be used in thesecondary layer 47 include but are not limited to Ru, Os, Ir, Ta, W etc. Use of asecondary layer 47 comprising at least one of Ru, Ir and Os has an added benefit. Such materials are very resistant to reaction with Se, S and Te. Therefore, after any reaction step that forms CIGS(S) compound layer on thefree surface 46A of theconductive layer 46, the secondary layer protects theflexible foil substrate 45 from reaction with Se, S or Te and leaves a surface that can be soldered easily. In prior art devices Mo was used as thesecondary layer 47. During selenization and/or sulfidation processes or during the growth of the CIGS(S) absorber, this Mo layer reacted with Se and/or S forming a Mo(S,Se) surface layer. After solar cells are completed, they need to be interconnected to form modules. Interconnection involves soldering or otherwise attaching back surface of each cell to the front surface of the adjacent cell. A Mo(S,Se) layer on the back of the cell cannot be soldered effectively, therefore physical removal of the selenized and/or sulfidized Mo surface is needed. However, a surface comprising at least one of Ru, Ir and Os can be soldered easily without the added step of removing a selenized or sulfidized surface layer because these materials do not appreciably selenize or sulfidize. - Referring back to
FIG. 3 , theflexible foil base 22 passes through aconditioning unit 34, and anoptional cleaning unit 35, before entering into theCu electroplating unit 31. In theconditioning unit 34, the surface of the flexible foil base 22 (such as thefree surface 46A of theconductive layer 46 inFIG. 3A ) is conditioned to render it ready for electrodeposition with Cu. Such conditioning may involve exposing thefree surface 46A to an acidic or basic solution for etching and/or activation, applying a cathodic or anodic voltage to thefree surface 46A with respect to an electrode while both the electrode and thefree surface 46A are exposed to an electrolyte, electrodepositing a seed layer on thefree surface 46A, or simply rinsing and wetting thefree surface 46A before it moves into theCu electroplating unit 31. If only a rinsing process is carried out in theconditioning unit 34, there would not be a need to thecleaning unit 35. Otherwise cleaningunit 35 is needed to remove any residual chemicals left on both faces of theflexible foil base 22 before it moves into theCu electroplating unit 31. In the present invention, if a seed layer is electrodeposited on thefree surface 46A in theconditioning unit 34, this seed layer may be a Cu layer that is 2-50 nm thick and it may be deposited from a bath that yields defect free uniform layers. Complexed Cu electrolytes with high pH are especially suitable for this purpose. Use of seed layers and various chemistries for electroplating are disclosed in Applicant's co-pending U.S. application Ser. No. 11/266,013 filed Nov. 2, 2005 entitled “Technique and Apparatus for Depositing Layers of Semiconductors For Solar Cell and Modular Fabrication”, and U.S. application Ser. No. 11/462,685 filed Aug. 4, 2004 entitled “Technique for Preparing Precursor Films and Compound Layers for Thin Film Solar Cell Fabrication and Apparatus Corresponding Thereto”, entire contents of these applications are incorporated herein by reference. - Once a section of the
free surface 46A of theconductive layer 46 is conditioned and cleaned it moves into theCu electroplating unit 31. Within theCu electroplating unit 31, thefree surface 46A (or the surface of the seed layer if a seed layer has been deposited in the conditioning unit 34) is exposed to aCu plating bath 36A which may be circulated between a first reservoir 36AA and afirst chemical cabinet 36A′. TheCu plating bath 36A may be filtered and replenished during circulation or while in thefirst chemical cabinet 36A′. Measurement and control of various bath parameters, such as additive content, Cu content, temperature, pH etc. may be continuously or periodically carried out within thefirst chemical cabinet 36A′ to assure stability of the Cu deposition process. Electrical connection to the conductive layer 46 (or to theflexible foil substrate 45 if the foil substrate itself is conductive) may be achieved by various means including throughrollers 39 which may be touching theflexible foil base 22 at, at least part of its back or front surfaces. Preferably, front surface contacts are made at the two edges avoiding physical contact with most of the front surface which may be damaged or contaminated by contacts. Afirst anode 40A is placed in theCu plating bath 36A and a potential difference is applied between thefirst anode 40A and the portion of theconductive layer 46 within theCu electroplating unit 31, to deposit Cu on the portion of thefree surface 46A that is exposed to theCu plating bath 36A as theflexible foil base 22 is moved. - The portion of the
flexible foil base 22 processed in theCu electroplating unit 31, passes through theCu cleaning unit 37A and enters into theGa electroplating unit 32. Within the Ga electroplating unit, the surface of the already deposited Cu layer is exposed to a Ga plating bath 36B which may be circulated between a second reservoir 36BB and a second chemical cabinet 36B′. The Ga plating bath 36B may be filtered and replenished during circulation or while in the second chemical cabinet 36B′. Measurement and control of various bath parameters, such as additive content, Ga content, temperature, pH etc. may be continuously or periodically carried out within the second chemical cabinet 36B′ to assure stability of the Ga deposition process. Electrical connection to the conductive layer 46 (or to theflexible foil substrate 45 if the flexible foil substrate itself is conductive) may be achieved by various means including throughrollers 39 which may be touching the base at, at least part of its back or front surfaces. Preferably, front surface contacts are made at the two edges avoiding physical contact with most of the front surface which may be damaged or contaminated by contacts. A second anode 40B is placed in the Ga plating bath 36B and a potential difference is applied between the second anode 40B and the portion of theconductive layer 46 within theGa electroplating unit 32, to deposit Ga on the portion of the Cu surface that is exposed to the Ga plating bath 36B as theflexible foil base 22 is moved. - The portion of the flexible foil base processed in the
Ga electroplating unit 32, passes through the Ga cleaning unit 37B and enters into theIn electroplating unit 33. Within the In electroplating unit, the surface of the already deposited Ga layer is exposed to an Inplating bath 36C which may be circulated between a third reservoir 36CC and a thirdchemical cabinet 36C′. The Inplating bath 36C may be filtered and replenished during circulation or while in thethird chemical cabinet 36C′. Measurement and control of various bath parameters, such as additive content, In content, temperature, pH etc. may be continuously or periodically carried out within thethird chemical cabinet 36C′ to assure stability of the In deposition process. Electrical connection to the conductive layer 46 (or to theflexible foil substrate 45 if the flexible foil substrate itself is conductive) may be achieved by various means including throughrollers 39 which may be touching the flexible foil base at, at least part of its back or front surfaces. Preferably, front surface contacts are made at the two edges avoiding physical contact with most of the front surface which may be damaged or contaminated by contacts. A third anode 40C is placed in theIn plating bath 36C and a potential difference is applied between the third anode 40C and the portion of theconductive layer 46 within theIn electroplating unit 33, to deposit In on the portion of the Ga surface that is exposed to the In platingbath 36C as thebase 22 is moved. After In electrodeposition the portion of the flexible foil base comprising the all-electroplated Cu/Ga/In stack is passed through a cleaning/dryingunit 38 and moved to thereturn spool 21. - It should be noted that additional process units may be added to the
electroplating system 30 ofFIG. 3 . For example, another Cu electroplating unit and another cleaning unit may be inserted between the Ga cleaning unit 37B and Inelectroplating unit 33 to fabricate a Cu/Ga/Cu/In stack. The anodes employed in the electroplating units may be inert anodes or they may be dissolvable anodes of Cu, In and Ga for Cu electrodeposition, In electrodeposition and Ga electrodeposition, respectively. The thicknesses of the Cu, In and Ga layers within the stack may range from 10 nm to 500 nm. Details of the cleaning or cleaning/drying units are not shown inFIG. 3 . However, established cleaning means, such as spraying the cleaning solution onto the part to be cleaned or immersing the part in the cleaning solution, may be used in these units. Air knives directing high speed air or inert gas onto the part to be dried may be used as the drying means. The drying gas may be pre-filtered and warmed for effective and fast drying. - We so far described an example of a system and process for roll-to-roll electrodeposition of stacks comprising Group IB and Group IIIA materials. Other processing units may be added to the electroplating system of
FIG. 3 to extend its functionality as will be described next. -
FIG. 4 depicts a roll-to-roll processing system 50 comprising a Group IB-IIIA electroplating unit 51 and a Group VIAmaterial electroplating unit 62. The Group IB-IIIA plating unit 51 electrodeposits the Group IB materials and Group IIIA materials on theflexible foil base 22 forming a metallic precursor film and may, for example, comprise all or most of the components of theelectroplating system 30 ofFIG. 3 . As an example, the Group IB-IIIA plating unit 51 may deposit Cu, Ga and In layers and may comprise theconditioning unit 34, thecleaning unit 35, theCu electroplating unit 31, theCu cleaning unit 37A, theGa electroplating unit 32, the Ga cleaning unit 37B, and theIn electroplating unit 33 ofFIG. 3 . Instead of the cleaning/dryingunit 38 ofFIG. 3 , another cleaning unit (without drying) may be employed so that theflexible foil base 22 coated or electrochemically coated with Cu, Ga and In moves into the Group VIAmaterial electroplating unit 62 with a clean and wet surface. In the Group VIAmaterial electroplating unit 62, a layer of at least one of Se, S and Te, preferably Se, is deposited onto the metallic precursor film. The flexible foil base with the “metallic precursor/Group VIA material” stack may then be passed through a final cleaning/drying module 63 and rolled onto thereturn spool 21. Presence of a Group VIA material on the metallic precursor film comprising Cu, In and Ga has advantages. One such advantage is the protection provided by the Group VIA material to the surface of the metallic precursor film. Indium and Ga are soft, low melting materials and they are vulnerable to easy scratching during rolling and handling. By depositing a Group VIA material such as Se on the metallic precursor film this vulnerability is reduced or eliminated so that the flexible web may be rolled onto thereturn spool 21 safely. The thickness of the electroplated Group VIA material may be in the range of 10-2000 nm. - The roll-to-roll processing system of
FIG. 4 may accommodate anoptional annealing unit 64 as shown inFIG. 4 . When used, theannealing unit 64 will cause a reaction between the electrodeposited metallic precursor film and the electrodeposited Group VIA material and form a reacted precursor layer on theflexible foil base 22. If the Group VIA material is Se, the reacted precursor layer may comprise phases such as Cu, In, Ga, Cu—Ga, Cu—In, In—Ga, Cu—Se, In—Se, Ga—Se, Cu—In—Se, Cu—Ga—Se, In—Ga—Se and Cu—In—Ga—Se, depending on the temperature applied in theannealing unit 64 and the time spent in theannealing unit 64. The temperature applied by the annealing unit may be in the range of 100-550 C, preferably in the range of 200-450 C. After exiting theannealing unit 64, the flexible web comprising the reacted precursor layer may be rolled onto thereturn spool 21 safely. A packing sheet may also be rolled along with it as described with reference toFIG. 2 . It should be noted that the Group VIAmaterial electroplating unit 62 may be similar to the electroplating units described with reference toFIG. 3 . Theannealing unit 64 may be similar to a design described in co-pending U.S. patent application Ser. No. 11/549,590 filed Oct. 13, 2006 entitled “Method and Apparatus For Converting Precursor Layers Into Photovoltaic Absorbers”, entire contents of which are incorporated herein by reference. - The examples above employed a
flexible foil base 22 such as the one depicted inFIG. 3A . In theflexible foil base 22 ofFIG. 3A , theconductive layer 46 and the optionalsecondary layer 47 may be deposited on theflexible foil substrate 45 by various deposition techniques such as evaporation, sputtering etc. in a separate system. It is, however, possible to integrate another electroplating or electroless plating module to the systems ofFIGS. 3 and 4 so that theflexible foil substrate 45 gets electroplated with at least one of a conductive layer or contact layer and a secondary layer before it moves into other process units such as the Group IB-IIIA electroplating unit ofFIG. 4 . This way defects in the electroplated Cu, In and Ga layers that are due to defects in or on the contact layers (such as scratches, pinholes and other defects) are avoided since contact layers are freshly deposited and then get coated with Cu, Ga and In. The contact layer for this approach needs to comprise materials that can be electroplated or electroless plated and at the same time be a good ohmic contact to CIGS(S) material and not react extensively with S and/or Se. Such layers are disclosed in Applicant's co-pending U.S. application Ser. No. 11/266,013 filed Nov. 2, 2005 entitled “Technique and Apparatus for Depositing Layers of Semiconductors For Solar Cell and Modular Fabrication”, and U.S. application Ser. No. 11/462,685 filed Aug. 4, 2004 entitled “Technique for Preparing Precursor Films and Compound Layers for Thin Film Solar Cell Fabrication and Apparatus Corresponding Thereto” and they comprise materials such as Ru, Ir and Os. It should be noted that by exposing the back side of the flexible foil substrate to a contact electroplating solution and deposition current, it is possible to electroplate a secondary layer on the back side of the substrate as the front face is plated by a contact layer. - In two-stage techniques, which involve deposition of a metallic precursor film comprising Cu, In and Ga and then reaction of the metallic precursor film with at least one of Se and S, individual thicknesses of the Cu, In and Ga layers need to be well controlled because they determine the final stoichiometry or composition of the compound layer after the reaction step. The roll-to-roll deposition approach of the present invention lends itself well for smart process control so that these thicknesses may be monitored and controlled using in-situ measurement devices such as X-ray fluorescence (XRF). XRF probes may be placed at various positions in the systems of
FIG. 2 ,FIG. 3 andFIG. 4 and these probes may monitor the deposited thicknesses of Cu, In, Ga and optionally Se layers. If there is any discrepancy between the target and deposited thickness of any of the Cu, In, Ga layers, the power supply controlling that thickness may be sent a signal by the XRF tool to increase or decrease the plating current density to keep the film thickness within a targeted window. Such approaches are described in more detail in Applicant's co-pending U.S. Provisional Application Ser. No. 60/744,252 filed Apr. 4, 2006 entitled “Composition Control for Photovoltaic Thin Film Manufacturing”. - Once the metallic precursor films, or the “metallic precursor/Group VIA material” stacks, or the reacted precursor layers of the present invention are formmed, reaction or further reaction of these layers with Group VIA materials may be achieved by various means. For example, these layers may be exposed to Group VIA vapors at elevated temperatures. These techniques are well known in the field and they involve heating the layers to a temperature range of 350-600° C. in the presence of at least one of Se vapors, S vapors, and Te vapors provided by sources such as solid Se, solid S, solid Te, H2Se gas, H2S gas etc. for periods ranging from 5 minutes to 1 hour. In another embodiment a layer or multi layers of Group VIA materials may be deposited on the metallic precursor layers and then heated up in a furnace or in a rapid thermal annealing furnace and like. Group VIA materials may be evaporated on, sputtered on or plated on the metallic precursor layers in a separate process unit. Alternately inks comprising Group VIA nano particles may be prepared and these inks may be deposited on the metallic precursor layers to form a Group VIA material layer comprising Group VIA nano particles. Dipping, spraying, doctor-blading or ink writing techniques may be employed to deposit such layers. Reaction may be carried out at elevated temperatures for times ranging from 1 minute to 30 minutes depending upon the temperature. As a result of reaction, the Group IBIIIAVIA compound is formed. It should be noted that reaction chambers may also be added to the apparatus of
FIG. 4 or theannealing unit 64 may be a reaction unit to carry out the whole process in-line so that the flexible foil base with a fully formed CIGS(S) layer on its surface may be rolled onto thereturn spool 21. - In the examples above, systems with horizontal web geometry have been discussed. It should be noted that the concepts of the present invention may be applied to systems where the flexible foil base travels in a vertical position or at any angle with respect to the horizontal plane. Depositions may be carried out on the horizontal web in either “deposit up” or “deposit down” manner. The flexible foil substrate may move from left to right or vice-versa. It may move continuously or in a stepwise manner. It may also move with an oscillating “back-and-forth” motion. It is possible to deposit some layers onto the flexible foil base as it is moved in one direction and then deposit more layer(s) as the foil is moved back in the reverse direction. DC, AC, pulsed or pulse-reverse type power supplies, among others, may be used for the electrodeposition steps.
- Solar cells may be fabricated on the Group IBIIIAVIA compound layers of the present invention using materials and methods well known in the field. For example a thin (<0.1 microns) CdS layer may be deposited on the surface of the compound layer using the chemical dip method. A transparent window of ZnO may be deposited over the CdS layer using MOCVD or sputtering techniques. A metallic finger pattern is optionally deposited over the ZnO to complete the solar cell.
- Although the present invention is described with respect to certain preferred embodiments, modifications thereto will be apparent to those skilled in the art.
Claims (24)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US11/875,784 US20080093221A1 (en) | 2006-10-19 | 2007-10-19 | Roll-To-Roll Electroplating for Photovoltaic Film Manufacturing |
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US86216406P | 2006-10-19 | 2006-10-19 | |
US11/875,784 US20080093221A1 (en) | 2006-10-19 | 2007-10-19 | Roll-To-Roll Electroplating for Photovoltaic Film Manufacturing |
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US11/875,784 Abandoned US20080093221A1 (en) | 2006-10-19 | 2007-10-19 | Roll-To-Roll Electroplating for Photovoltaic Film Manufacturing |
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US (1) | US20080093221A1 (en) |
EP (1) | EP2087151A4 (en) |
JP (1) | JP2010507909A (en) |
KR (1) | KR20090098962A (en) |
CN (1) | CN101583741B (en) |
TW (1) | TW200832732A (en) |
WO (1) | WO2008049103A2 (en) |
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US20070227633A1 (en) * | 2006-04-04 | 2007-10-04 | Basol Bulent M | Composition control for roll-to-roll processed photovoltaic films |
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US20100178716A1 (en) * | 2008-11-17 | 2010-07-15 | Solopower, Inc. | Method and apparatus to remove a segment of a thin film solar cell structure for efficiency improvement |
US7979969B2 (en) | 2008-11-17 | 2011-07-19 | Solopower, Inc. | Method of detecting and passivating a defect in a solar cell |
US20110177622A1 (en) * | 2009-12-28 | 2011-07-21 | Global Solar Energy, Inc. | Apparatus and methods of mixing and depositing thin film photovoltaic compositions |
US8021905B1 (en) | 2009-02-05 | 2011-09-20 | Ascent Solar Technologies, Inc. | Machine and process for sequential multi-sublayer deposition of copper indium gallium diselenide compound semiconductors |
WO2011142804A1 (en) * | 2010-05-10 | 2011-11-17 | The University Of Toledo | Flexible photovoltaic cells and modules having an improved adhesion characteristic |
CN102388437A (en) * | 2009-02-11 | 2012-03-21 | 联合太阳能奥佛有限公司 | Solution based non-vacuum method and apparatus for preparing oxide materials |
US20120264255A1 (en) * | 2009-10-07 | 2012-10-18 | Nexcis | Production of thin films having photovoltaic properties and containing a i-iii-vi2-type alloy, comprising successive electrodeposits and thermal post-treatment |
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2377550A (en) * | 1940-12-02 | 1945-06-05 | Hanson Van Winkle Munning Co | Apparatus for electrogalvanizing |
US2895888A (en) * | 1957-10-07 | 1959-07-21 | Industrial Nucleonics Corp | Electrolytic plating apparatus and process |
US4282073A (en) * | 1979-08-22 | 1981-08-04 | Thomas Steel Strip Corporation | Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates |
US4318938A (en) * | 1979-05-29 | 1982-03-09 | The University Of Delaware | Method for the continuous manufacture of thin film solar cells |
US4581108A (en) * | 1984-01-06 | 1986-04-08 | Atlantic Richfield Company | Process of forming a compound semiconductive material |
US4798660A (en) * | 1985-07-16 | 1989-01-17 | Atlantic Richfield Company | Method for forming Cu In Se2 films |
US4859287A (en) * | 1984-11-22 | 1989-08-22 | Kawasaki Steel Corporation | Method for producing colored stainless steel stock |
US5804466A (en) * | 1996-03-06 | 1998-09-08 | Canon Kabushiki Kaisha | Process for production of zinc oxide thin film, and process for production of semiconductor device substrate and process for production of photoelectric conversion device using the same film |
US6048442A (en) * | 1996-10-25 | 2000-04-11 | Showa Shell Sekiyu K.K. | Method for producing thin-film solar cell and equipment for producing the same |
US6753272B1 (en) * | 1998-04-27 | 2004-06-22 | Cvc Products Inc | High-performance energy transfer method for thermal processing applications |
US6881671B2 (en) * | 2000-08-14 | 2005-04-19 | Ipu, Instituttet For Produktudvikling | Process for depositing metal contacts on a buried grid solar cell and solar cell obtained by the process |
US20050202589A1 (en) * | 2004-03-15 | 2005-09-15 | Basol Bulent M. | Technique and apparatus for depositing thin layers of semiconductors for solar cell fabrication |
US20060121701A1 (en) * | 2004-03-15 | 2006-06-08 | Solopower, Inc. | Technique and apparatus for depositing layers of semiconductors for solar cell and module fabrication |
US20070093006A1 (en) * | 2005-10-24 | 2007-04-26 | Basol Bulent M | Technique For Preparing Precursor Films And Compound Layers For Thin Film Solar Cell Fabrication And Apparatus Corresponding Thereto |
US20070111367A1 (en) * | 2005-10-19 | 2007-05-17 | Basol Bulent M | Method and apparatus for converting precursor layers into photovoltaic absorbers |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09321326A (en) * | 1996-05-30 | 1997-12-12 | Yazaki Corp | Manufacturing cis thin film solar cell and forming copper-indium-selenium alloy |
US20020011419A1 (en) * | 1998-02-17 | 2002-01-31 | Kozo Arao | Electrodeposition tank, electrodeposition apparatus, and electrodeposition method |
AU2001240599A1 (en) * | 2000-02-07 | 2001-08-14 | Cis Solartechnik Gmbh | Flexible metal substrate for cis solar cells, and method for producing the same |
JP2002083917A (en) * | 2000-06-28 | 2002-03-22 | Noge Denki Kogyo:Kk | Lead frame having protrusions on surface, method of manufacturing the same, semiconductor device and manufacturing method thereof |
JP2002212779A (en) * | 2001-01-10 | 2002-07-31 | Hitachi Ltd | Surface treatment process and method for manufacturing thin film magnetic head using this process, and thin film magnetic head |
JP2003183877A (en) * | 2001-12-11 | 2003-07-03 | Nagoya Plating Co Ltd | Partial plating method |
-
2007
- 2007-10-19 EP EP07854221A patent/EP2087151A4/en not_active Withdrawn
- 2007-10-19 CN CN200780044723XA patent/CN101583741B/en not_active Expired - Fee Related
- 2007-10-19 US US11/875,784 patent/US20080093221A1/en not_active Abandoned
- 2007-10-19 JP JP2009533561A patent/JP2010507909A/en active Pending
- 2007-10-19 KR KR1020097010132A patent/KR20090098962A/en active IP Right Grant
- 2007-10-19 TW TW096139256A patent/TW200832732A/en unknown
- 2007-10-19 WO PCT/US2007/081912 patent/WO2008049103A2/en active Application Filing
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2377550A (en) * | 1940-12-02 | 1945-06-05 | Hanson Van Winkle Munning Co | Apparatus for electrogalvanizing |
US2895888A (en) * | 1957-10-07 | 1959-07-21 | Industrial Nucleonics Corp | Electrolytic plating apparatus and process |
US4318938A (en) * | 1979-05-29 | 1982-03-09 | The University Of Delaware | Method for the continuous manufacture of thin film solar cells |
US4282073A (en) * | 1979-08-22 | 1981-08-04 | Thomas Steel Strip Corporation | Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates |
US4581108A (en) * | 1984-01-06 | 1986-04-08 | Atlantic Richfield Company | Process of forming a compound semiconductive material |
US4859287A (en) * | 1984-11-22 | 1989-08-22 | Kawasaki Steel Corporation | Method for producing colored stainless steel stock |
US4798660A (en) * | 1985-07-16 | 1989-01-17 | Atlantic Richfield Company | Method for forming Cu In Se2 films |
US5804466A (en) * | 1996-03-06 | 1998-09-08 | Canon Kabushiki Kaisha | Process for production of zinc oxide thin film, and process for production of semiconductor device substrate and process for production of photoelectric conversion device using the same film |
US6048442A (en) * | 1996-10-25 | 2000-04-11 | Showa Shell Sekiyu K.K. | Method for producing thin-film solar cell and equipment for producing the same |
US6092669A (en) * | 1996-10-25 | 2000-07-25 | Showa Shell Sekiyu K.K. | Equipment for producing thin-film solar cell |
US6753272B1 (en) * | 1998-04-27 | 2004-06-22 | Cvc Products Inc | High-performance energy transfer method for thermal processing applications |
US6881671B2 (en) * | 2000-08-14 | 2005-04-19 | Ipu, Instituttet For Produktudvikling | Process for depositing metal contacts on a buried grid solar cell and solar cell obtained by the process |
US20050202589A1 (en) * | 2004-03-15 | 2005-09-15 | Basol Bulent M. | Technique and apparatus for depositing thin layers of semiconductors for solar cell fabrication |
US20060121701A1 (en) * | 2004-03-15 | 2006-06-08 | Solopower, Inc. | Technique and apparatus for depositing layers of semiconductors for solar cell and module fabrication |
US20070111367A1 (en) * | 2005-10-19 | 2007-05-17 | Basol Bulent M | Method and apparatus for converting precursor layers into photovoltaic absorbers |
US20070093006A1 (en) * | 2005-10-24 | 2007-04-26 | Basol Bulent M | Technique For Preparing Precursor Films And Compound Layers For Thin Film Solar Cell Fabrication And Apparatus Corresponding Thereto |
Cited By (59)
Publication number | Priority date | Publication date | Assignee | Title |
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US10961635B2 (en) | 2005-08-12 | 2021-03-30 | Modumetal, Inc. | Compositionally modulated composite materials and methods for making the same |
US7713773B2 (en) * | 2005-11-02 | 2010-05-11 | Solopower, Inc. | Contact layers for thin film solar cells employing group IBIIIAVIA compound absorbers |
US20070145507A1 (en) * | 2005-11-02 | 2007-06-28 | Basol Bulent M | Contact Layers For Thin Film Solar Cells Employing Group IBIIIAVIA Compound Absorbers |
US20070227633A1 (en) * | 2006-04-04 | 2007-10-04 | Basol Bulent M | Composition control for roll-to-roll processed photovoltaic films |
US20070232065A1 (en) * | 2006-04-04 | 2007-10-04 | Basol Bulent M | Composition Control For Photovoltaic Thin Film Manufacturing |
US7736913B2 (en) * | 2006-04-04 | 2010-06-15 | Solopower, Inc. | Composition control for photovoltaic thin film manufacturing |
US20090258444A1 (en) * | 2008-04-15 | 2009-10-15 | Global Solar Energy, Inc. | Apparatus and methods for manufacturing thin-film solar cells |
US7968353B2 (en) * | 2008-04-15 | 2011-06-28 | Global Solar Energy, Inc. | Apparatus and methods for manufacturing thin-film solar cells |
WO2009134799A1 (en) * | 2008-04-28 | 2009-11-05 | Solopower, Inc. | Metallic foil substrate and packaging technique for thin film solar cells and modules |
US20090269877A1 (en) * | 2008-04-28 | 2009-10-29 | Mustafa Pinarbasi | Method and apparatus for achieving low resistance contact to a metal based thin film solar cell |
US8207012B2 (en) * | 2008-04-28 | 2012-06-26 | Solopower, Inc. | Method and apparatus for achieving low resistance contact to a metal based thin film solar cell |
US20090266399A1 (en) * | 2008-04-28 | 2009-10-29 | Basol Bulent M | Metallic foil substrate and packaging technique for thin film solar cells and modules |
US20090266398A1 (en) * | 2008-04-28 | 2009-10-29 | Burak Metin | Method and Apparatus to Form Back Contacts to Flexible CIGS Solar Cells |
WO2009158408A1 (en) * | 2008-06-27 | 2009-12-30 | Solopower, Inc. | Method and apparatus for achieving low resistance contact to a metal based thin film solar cell |
US20130230933A1 (en) * | 2008-09-06 | 2013-09-05 | Soltrium Technology, Ltd. Shenzhen | Methods for fabricating thin film solar cells |
WO2010057102A1 (en) * | 2008-11-17 | 2010-05-20 | Solopower, Inc. | Method and apparatus for detecting and passivating defects in thin film solar cells |
US7979969B2 (en) | 2008-11-17 | 2011-07-19 | Solopower, Inc. | Method of detecting and passivating a defect in a solar cell |
US20100178716A1 (en) * | 2008-11-17 | 2010-07-15 | Solopower, Inc. | Method and apparatus to remove a segment of a thin film solar cell structure for efficiency improvement |
US20100124600A1 (en) * | 2008-11-17 | 2010-05-20 | Basol Bulent M | Method and apparatus for detecting and passivating defects in thin film solar cells |
US8318239B2 (en) | 2008-11-17 | 2012-11-27 | Solopower, Inc. | Method and apparatus for detecting and passivating defects in thin film solar cells |
US8318240B2 (en) | 2008-11-17 | 2012-11-27 | Solopower, Inc. | Method and apparatus to remove a segment of a thin film solar cell structure for efficiency improvement |
US8465589B1 (en) | 2009-02-05 | 2013-06-18 | Ascent Solar Technologies, Inc. | Machine and process for sequential multi-sublayer deposition of copper indium gallium diselenide compound semiconductors |
US9601650B1 (en) | 2009-02-05 | 2017-03-21 | Ascent Solar Technologies, Inc. | Machine and process for continuous, sequential, deposition of semiconductor solar absorbers having variable semiconductor composition deposited in multiple sublayers |
US8021905B1 (en) | 2009-02-05 | 2011-09-20 | Ascent Solar Technologies, Inc. | Machine and process for sequential multi-sublayer deposition of copper indium gallium diselenide compound semiconductors |
CN102388437A (en) * | 2009-02-11 | 2012-03-21 | 联合太阳能奥佛有限公司 | Solution based non-vacuum method and apparatus for preparing oxide materials |
US8418418B2 (en) | 2009-04-29 | 2013-04-16 | 3Form, Inc. | Architectural panels with organic photovoltaic interlayers and methods of forming the same |
US9076731B2 (en) | 2009-04-29 | 2015-07-07 | 3Form, Llc | Architectural panels with organic photovoltaic interlayers and methods of forming the same |
US11242613B2 (en) | 2009-06-08 | 2022-02-08 | Modumetal, Inc. | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
US8883547B2 (en) * | 2009-10-07 | 2014-11-11 | Nexcis | Production of thin films having photovoltaic properties, comprising depositing an alternate I/III or III/I multi-layer structure and annealing said structure |
US20120264255A1 (en) * | 2009-10-07 | 2012-10-18 | Nexcis | Production of thin films having photovoltaic properties and containing a i-iii-vi2-type alloy, comprising successive electrodeposits and thermal post-treatment |
US20110177622A1 (en) * | 2009-12-28 | 2011-07-21 | Global Solar Energy, Inc. | Apparatus and methods of mixing and depositing thin film photovoltaic compositions |
WO2011142804A1 (en) * | 2010-05-10 | 2011-11-17 | The University Of Toledo | Flexible photovoltaic cells and modules having an improved adhesion characteristic |
US9159851B2 (en) | 2010-05-26 | 2015-10-13 | The University Of Toledo | Photovoltaic structures having a light scattering interface layer and methods of making the same |
US8846440B2 (en) | 2010-07-02 | 2014-09-30 | International Business Machines Corporation | Germanium photodetector |
US8841162B2 (en) | 2010-07-02 | 2014-09-23 | International Business Machines Corporation | Germanium photodetector |
US8940149B2 (en) * | 2010-09-02 | 2015-01-27 | International Business Machines Corporation | Gallium electrodeposition processes and chemistries |
US9401443B2 (en) | 2010-09-02 | 2016-07-26 | International Business Machines Corporation | Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures |
US20120325668A1 (en) * | 2010-09-02 | 2012-12-27 | International Business Machines Corporation | Gallium Electrodeposition Processes and Chemistries |
US8648253B1 (en) | 2010-10-01 | 2014-02-11 | Ascent Solar Technologies, Inc. | Machine and process for continuous, sequential, deposition of semiconductor solar absorbers having variable semiconductor composition deposited in multiple sublayers |
US9147783B2 (en) | 2010-12-13 | 2015-09-29 | Ascent Solar Technologies, Inc. | Apparatus and method for hybrid photovoltaic device having multiple, stacked, heterogeneous, semiconductor junctions |
US8426725B2 (en) | 2010-12-13 | 2013-04-23 | Ascent Solar Technologies, Inc. | Apparatus and method for hybrid photovoltaic device having multiple, stacked, heterogeneous, semiconductor junctions |
US9112095B2 (en) * | 2012-12-14 | 2015-08-18 | Intermolecular, Inc. | CIGS absorber formed by co-sputtered indium |
EP2971266A4 (en) * | 2013-03-15 | 2017-03-01 | Modumetal, Inc. | A method and apparatus for continuously applying nanolaminate metal coatings |
US10808322B2 (en) | 2013-03-15 | 2020-10-20 | Modumetal, Inc. | Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes |
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Also Published As
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EP2087151A4 (en) | 2012-03-28 |
TW200832732A (en) | 2008-08-01 |
KR20090098962A (en) | 2009-09-18 |
CN101583741B (en) | 2011-09-28 |
CN101583741A (en) | 2009-11-18 |
EP2087151A2 (en) | 2009-08-12 |
JP2010507909A (en) | 2010-03-11 |
WO2008049103A3 (en) | 2008-07-03 |
WO2008049103A2 (en) | 2008-04-24 |
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