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.
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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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US11/875,784 US20080093221A1 (en) | 2006-10-19 | 2007-10-19 | Roll-To-Roll Electroplating for Photovoltaic Film Manufacturing |
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EP (1) | EP2087151A4 (ko) |
JP (1) | JP2010507909A (ko) |
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CN101974772B (zh) * | 2010-08-11 | 2012-06-27 | 中国科学院半导体研究所 | 氮化镓基垂直结构发光二极管转移衬底的二次电镀方法 |
KR101154774B1 (ko) * | 2011-04-08 | 2012-06-18 | 엘지이노텍 주식회사 | 태양전지 및 이의 제조방법 |
KR101257819B1 (ko) | 2011-06-20 | 2013-05-06 | 성안기계 (주) | 롤투롤 CdS 증착 방법 및 시스템 |
KR101885821B1 (ko) | 2011-06-21 | 2018-09-10 | 삼성디스플레이 주식회사 | 유기 발광 표시 장치 및 그 제조 방법 |
KR20180078674A (ko) * | 2016-12-30 | 2018-07-10 | (주) 다쓰테크 | 다층 금속박막 형성을 위한 다층 금속박막 형성 장치 및 방법 |
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Also Published As
Publication number | Publication date |
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WO2008049103A2 (en) | 2008-04-24 |
EP2087151A2 (en) | 2009-08-12 |
TW200832732A (en) | 2008-08-01 |
EP2087151A4 (en) | 2012-03-28 |
KR20090098962A (ko) | 2009-09-18 |
WO2008049103A3 (en) | 2008-07-03 |
CN101583741A (zh) | 2009-11-18 |
CN101583741B (zh) | 2011-09-28 |
JP2010507909A (ja) | 2010-03-11 |
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