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WO2011075564A1 - Procédés et chimies d'électroplaquage pour le dépôt de films minces à teneur en cuivre-indium-gallium - Google Patents

Procédés et chimies d'électroplaquage pour le dépôt de films minces à teneur en cuivre-indium-gallium Download PDF

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Publication number
WO2011075564A1
WO2011075564A1 PCT/US2010/060712 US2010060712W WO2011075564A1 WO 2011075564 A1 WO2011075564 A1 WO 2011075564A1 US 2010060712 W US2010060712 W US 2010060712W WO 2011075564 A1 WO2011075564 A1 WO 2011075564A1
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Prior art keywords
layer
copper
film
stack
indium
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PCT/US2010/060712
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English (en)
Inventor
Serdar Aksa
Mustafa Pinarbasi
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SoloPower Inc
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SoloPower Inc
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Priority claimed from US12/642,702 external-priority patent/US8425753B2/en
Priority claimed from US12/642,691 external-priority patent/US20100140098A1/en
Priority claimed from US12/642,709 external-priority patent/US8409418B2/en
Application filed by SoloPower Inc filed Critical SoloPower Inc
Priority to CN2010800573747A priority Critical patent/CN102741459A/zh
Publication of WO2011075564A1 publication Critical patent/WO2011075564A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • 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
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • C25D7/126—Semiconductors first coated with a seed layer or a conductive layer for solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • the present invention relates to manufacturing solar cell absorbers and, more particularly, manufacturing solar cell absorbers using electrodeposition processes. DESCRIPTION OF THE RELATED ART
  • 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.
  • silicon-based solar cells 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
  • 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 Figure 1.
  • the device 10 is fabricated on a base 20 including a substrate 1 1 and a conductive layer 13.
  • the substrate can be a sheet of glass, a sheet of metal, an insulating foil or web, or a conductive foil or web.
  • the absorber film 12, which includesa material in the family of Cu(In,Ga,Al)(S,Se,Te) 2 is grown over the conductive layer 13, which is previously deposited on the substrate 1 1 and which acts as the electrical contact to the device.
  • Various conductive layers comprising molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), and stainless steel etc. have been used in the solar cell structure of Figure 1. If the substrate itself is a properly selected conductive material, it is possible not to use a conductive layer 13, since the substrate 1 1 may then be used as the ohmic contact to the device.
  • a transparent layer 14 such as a cadmium sulfide (CdS), zinc oxide (ZnO) or CdS/ZnO stack is formed on the absorber film. Radiation 15 enters the device through the transparent layer 14.
  • Metallic grids may also be deposited over the transparent layer 14 to reduce the effective series resistance of the device.
  • Cu(In,Ga) means all compositions from Culn 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 that yielded high-quality Cu(In,Ga)Se 2 films for solar cell fabrication was co- evaporation of Cu, In, Ga and Se onto a heated substrate in a vacuum chamber.
  • 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 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.
  • thin layers of Cu and In may be first deposited on a substrate and then this stacked precursor layer may be reacted with Se at elevated temperature.
  • reaction atmosphere also contains sulfur
  • a Culn(S,Se) 2 layer can be grown.
  • Addition of Ga in the precursor layer allows the growth of a Cu(In,Ga)(S,Se) 2 absorber.
  • Patent 6,048,442 disclosed a method comprising sputter- depositing a stacked precursor film comprising a Cu-Ga alloy layer and an In layer to form a Cu- Ga/In stack on a metallic back electrode layer and then reacting this precursor stack film with one of Se and S to form the absorber layer.
  • Such techniques may yield good quality absorber layers and efficient solar cells, however, they suffer from the high cost of capital equipment, and relatively slow rate of production.
  • U.S. Patent 4,581 ,108 utilizes a low cost electrodeposition approach for metallic precursor preparation for a two-stage processing technique.
  • a Cu layer is first electrodeposited on a substrate. This is then followed by electrodeposition of an In layer forming a Cu/In stack during the first stage of the process.
  • the electrodeposited Cu/In stack is heated in a reactive atmosphere containing Se forming a CuInSeT compound layer.
  • Cu-In-S, Cu-In-Se and Cu-In-Ga-Se film depositions do not yield stable and repeatable electrodeposition process and high quality films that can be used in electronic device applications such as solar cell applications. Therefore, there is a need to develop efficient electrodeposition solutions and methods to deposit smooth and defect-free Group IB-Group IIIA alloy or mixture films in a repeatable manner with controlled composition.
  • the present invention provides a method and precursor structure to form a solar cell absorber layer.
  • a precursor stack comprising:
  • Figure 1 is a schematic view of a prior art solar cell structure
  • Figure 2 A is a schematic view of a precursor stack electrodeposited on a base.
  • Figure 2B is a schematic view of a CIGS absorber layer formed when the precursor stack shown in Figure 2A is reacted.
  • the present invention provides various methods to form Cu(In, Ga) (Se, S) 2 absorber layers (CIGS) from electrodeposited precursors of the present invention.
  • a precursor of the present invention may be formed as a stack having three layers.
  • a first layer, which is copper poor, may be deposited over a base and a second layer, which is copper rich, deposited onto the first layer.
  • a third layer including selenium is deposited onto the second layer before reacting the precursor to form the CIGS absorber layer.
  • the first layer may include a Group IB- Group IIIA alloy or mixture of stacked films where the Group IB material is preferably Cu and the Group IIIA material is at least one of In and Ga.
  • Such films may include (Cu-In), (Cu-Ga) and (Cu-In-Ga) alloy films or mixture such films.
  • the first layer may include a mixture of stacked single element films, i.e., Cu, In, Ga films, or a mixture of such single element films and (Cu-In), (Cu-Ga) and (Cu-In-Ga) alloy films.
  • the second layer also includes Group IB-Group IIIA alloy or mixture films.
  • the second layer may include at least one of a copper-indium-gallium-ternary alloy film, a copper-indium binary alloy film, a copper- gallium binary alloy film and a copper-selenium binary alloy film.
  • the embodiments provide methods using electrodeposition solutions or electrolytes to co-electrodeposit uniform, smooth and compositionally repeatable "Group IB-Group II1A" alloy or mixture films.
  • the stoichiometry or composition of such films e.g. Group IB/Group IIIA atomic ratio, may be controlled or varied into desired compositions by varying the appropriate plating conditions to vary the amount of Group IB and Group IIIA or VIA materials in the first layer and the second layer.
  • Figure 2A shows a precursor stack 100 or layer formed on a base 101 according to the principles of the present invention.
  • the precursor stack 100 may be made of a multilayer structure including a first layer 102, a second layer 104 and a third layer 106.
  • the precursor stack 100 is preferably formed using an electrodeposition process.
  • the first layer 102 may be electrodeposited over the base 102 which may include a substrate 101 A and a contact layer 101 B formed over the substrate.
  • the second layer 104 is electrodeposited on the first layer 102 and the third layer 106 may be electrodeposited on the second layer.
  • Principles of the electrodeposition process are well known and will not be repeated here for the sake of clarity.
  • the contact layer 101B may be made of a molybdenum (Mo) layer deposited over the substrate 101 A or a multiple layers or films of metals stacked on a Mo layer; for example, molybdenum and ruthenium multilayer (Mo/Ru), or molybdenum, ruthenium and copper multilayer (Mo Ru/Cu).
  • Mo molybdenum
  • Ru molybdenum and ruthenium multilayer
  • Mo Ru/Cu molybdenum, ruthenium and copper multilayer
  • Ru layer may be electrodeposited on the Mo layer, and similarly the Cu layer may be electrodeposited on the Ru layer to form the contact layer.
  • the substrate 101 A may be a flexible substrate, for example a stainless steel foil, or an aluminum foil, or a polymer.
  • the substrate may also be a rigid and transparent substrate such as glass.
  • the first layer 104 of the precursor stack 100 comprise Group IB and Group IIIA materials, i.e., Cu, In and Ga.
  • the second layer 104 may also include a Group VIA material, such as Se.
  • the first layer 104 may be configured as a stack including a Cu-film, an In-film and a Ga-film, which will be shown with Cu/In/Ga insignia hereinbelow. This and similar insignia will be used throughout the application to depict various stack configurations, where the first material (element or alloy) symbol is the first film, the second material symbol is the second film deposited on the first film and so on.
  • the Cu-film as being the first film of the stack, may be electrodeposited over the contact layer or another stack; the In- film (the second film) is electrodeposited onto the Cu-film; and the Ga-film (the third film) is deposited onto the In-film.
  • the order of such films 102 may be changed, and the first layer 102 may be formed as a Ga Cu/In stack or In Cu/Ga stack.
  • the first layer 102 may be formed as a stack of four films, such as Cu/Ga Cu/In or Cu In Cu Ga.
  • the first layer 102 may be formed as a (Cu-In-Ga) ternary alloy film or as a stack including (Cu-In) binary alloy film and (Cu-Ga) binary alloy film. Such alloy binary or ternary alloy films may have any desired compositions.
  • the first layer 102 may be formed by any possible combinations of the above given stacks of films, binary films and ternary alloy films. Regardless of what combination is used to form it, the first layer 102 includes 35%-49% of the total molar amount of Cu of the precursor stack 100.
  • the rest of the copper which may be about 51%-65% of the total molar amount of Cu in the precursor layer 100, may be included in the second layer 104.
  • the Cu/(In+Ga) molar ratio for the first layer 102 may be in the range of 0.25 to 0.49.
  • the second layer 104 of the precursor stack 100 may include at least one of a (Cu-In-Ga) ternary alloy film, a (Cu-In) binary alloy film and (Cu-Ga) binary alloy film or the mixtures of such films.
  • the second layer 104 may include a (Cu-Se) binary alloy film.
  • the second layer 104 may have a Cu/(In+Ga) molar ratio in the range of 0.51 to 4.
  • the amount of copper may be graded vertically between a bottom surface of the second layer 104 (adjacent the top of the first layer 102) and the top surface of the second layer 104 (adjacent the bottom of the third layer 106).
  • the top portion of the second layer 104 may be made more copper rich than the bottom portion of it.
  • the bottom portion of the second layer 104 may also be made copper rich with the same approach.
  • the third layer 106 may include Se.
  • the first layer 102 may be a Cu/Ga/Cu/In stack
  • the second layer 104 may be one of (Cu-In-Ga) ternary alloy film, (Cu-In) binary alloy film, (Cu-Ga) binary alloy film and (Cu-Se) binary alloy film
  • the third layer 106 is a selenium layer.
  • the first layer 102 may be replaced with one of Ga/Cu/In stack, In/Cu/Ga stack and Cu/In/Cu/Ga stack.
  • each layer of the precursor stack 100 is electrodeposited from selected electrodeposition solutions or electrolytes.
  • single element electrolytes such as a Cu electrolyte, In electrolyte, Ga electrolyte or Se electrolyte, are used to deposit films of these elements.
  • Such electrodeposition solutions includes Cu, In and Ga material sources and complexing agents for each elements. Copper in the electrolyte may be provided by a Cu source such as dissolved Cu metal or a Cu salt such as Cu- sulfate, Cu-chloride, Cu-acetate, Cu-nitrate, and the like.
  • Indium and gallium sources comprise dissolved In and Ga metals, and dissolved In and Ga salts.
  • the In salts may include In-chloride, In-sulfate, In-sulfamate, In-acetate, In-carbonate, In-nitrate, In-phosphate, In-oxide, In- perchlorate, and In-hydroxide, and the like
  • the Ga salts may include Ga-chloride, Ga-sulfate, Ga-sulfamate, Ga-acetate, Ga-carbonate, Ga-nitrate, Ga-perchlorate, Ga-phosphate, Ga-oxide, and Ga-hydroxide, and the like.
  • Ethylenediaminetetraacetic acid, tartrate and citrate were selected as suitable complexing agents for Cu, In and Ga, respectively.
  • the pH regime used in the single element electrodeposition solutions is neutral to alkaline pH regime (pH >7). This pH regime was chosen to realize the full potential of the complexation. Deprotonated forms of complexing agents become more predominant with increasing pH, allowing formation of more stable soluble metal-complex species.
  • the preferred electrodeposition solutions comprise a Cu source material, at least one Group IIIA (Ga and In) material, from the above given source materials, and a blend of at least two complexing agents that have the ability to complex with Cu and both or one of the Group IIIA metals to keep them from precipitating in the non-acidic electrolyte which has a pH value of larger than or equal to 7.
  • complexing agents are soluble species that combine with metal ions in solution to form soluble complexes or complex ions.
  • exemplary electrodeposition solutions for (Cu-Ga) binary films preferably comprise citric acid or a citrate
  • exemplary electrodeposition solutions for (Cu-In) binary films preferably comprise tartaric acid or a tartrate
  • Exemplary electrodeposition solutions for (Cu-In-Ga) ternary films preferably comprise a blend of complexing agents including both citrate and tartrate. Using such specific blend of complexing agents at the neutral and high pH ranges improves the plating efficiencies of these Group IB-IIIA materials. Citrates in the blend efficiently complex with the Ga species, tartrates in the blend efficiently complex with the In species. Both tartrates and citrates, on the other hand, complex well with Cu species. In order to enhance the complexation of Cu, EDTA could also be included in the (Cu-In-Ga)
  • electrodeposition solution because EDTA may form more stable complexes with Cu. Therefore, in electrodeposition solutions comprising Cu and both In and Ga species, it is beneficial to include a blend of complexing agents comprising tartrates (or tartaric acid), citrates (or citric acid) and possibly EDTA (in either its acidic form or in the form of alkali and alkali earth metal salts of EDTA) to obtain high plating efficiencies and good compositional control, i.e. Cu/In, Cu/Ga, In Ga, Cu (In+Ga) molar ratios. It should be noted that other complexing agents may additionally be included in the solution formulation.
  • the electrodeposition solutions or electrolytes used in the embodiments herein preferably have pH values of 7 or higher.
  • a more preferred pH range is above 9.
  • These basic pH values are suitable for large scale manufacturing and provide good complexation for all of the Cu, In and Ga species in the electrolyte and bring their plating potentials close to each other for better repeatability and control of the plated alloy film compositions. It is for this reason that the Ga content of the (Cu-In-Ga) films of the embodiments may be controlled at will in a range from 0% to 100%. This is unlike prior art electrodeposition solutions and methods which generally had difficulty to include appreciable amount of Ga in the electroplated layers due to excessive hydrogen generation due to high negative plating potential of Ga out of acidic electrolytes.
  • the pH values of the prior art plating solutions for the above mentioned group of materials is acidic and less than 7.
  • the embodiments described herein use a neutral (7) to basic (greater than 7) range for the pH values of the electrodeposition solutions and employ at least one complexing agent to effectively complex one of Cu, In and Ga at this pH range.
  • the benefits of such high pH ranges and use of specific complexing agents for the electrodeposition of Ga containing metallic layers see for example, U.S. Patent Application Serial No. 1 1/535,927, filed September 27, 2006, entitled “Efficient Gallium Thin Film Electroplating Methods and Chemistries", (In, Ga)-Se containing layers (see for example, U.S. Patent Application Serial No.
  • the preferred complexing agents are tartaric acid or a tartrate, such as potassium sodium tartrate (KNaC4H 4 C»6) and citric acid or a citrate such as sodium citrate, lithium citrate, ammonium citrate, potassium citrate, and an organically modified citrate.
  • tartaric acid or a tartrate such as potassium sodium tartrate (KNaC4H 4 C»6)
  • citric acid or a citrate such as sodium citrate, lithium citrate, ammonium citrate, potassium citrate, and an organically modified citrate.
  • Se material source may comprise at least one of dissolved elemental
  • Se acids of Se and dissolved Se compounds
  • the Se compounds include oxides, chlorides, sulfates, sulfides, nitrates, perchlorides and phosphates of Se.
  • Some of the preferred sources include but are not limited to selenous acid (also known as selenious acid) (H 2 Se0 3 ), selenium dioxide (Se0 2 ), selenic acid (F ⁇ SeC ), selenium sulfides (Se 4 S 4 , SeS 2 , Se 2 S6 ) sodium selenite (Na 2 Se0 3 ), telluric acid (H 6 TeOe), tellurium dioxide (Te0 2 ), selenium sulfides (Se 4 S 4 , SeS 2 , Se 2 S 6 ), thiourea (CSN 2 H 4 ), and sodium thiosulfate (Na 2 S 2 0 3 ).
  • selenous acid also known as selenious acid
  • Se0 2
  • the preferred complexing agent for the electrolytes used for electroplating Cu-Se binary alloy containing films comprises EDTA, citrates and tartrates. Using such complexing agents, it is possible to prepare plating solutions at both acidic and alkaline regime.
  • An exemplary Cu-Se electrodeposition solution, which operates at low pH regime is provided in SP- 103 (CIP of SP- 101) and incoiporated herein by reference.
  • the present invention provides a method to deposit Se containing layers under precursor stacks comprising films of Group IB, Group IIIA and Group VIA materials.
  • Ga and In cannot be directly plated on a selenium-containing layer without dissolving a large portion of Se during the electrodeposition.
  • Se dissolves due to its reduction to H 2 Se, HSe " or Se 2" at the large negative cathodic potentials needed for the deposition of In and Ga.
  • Such undesirable dissolution of Se from the Se-containing layer also occurs during Cu deposition over a Se-containing layer when the plating potential in this process falls below the reduction potential of Se to H 2 Se, HSe " or Se 2" .
  • Se dissolution problem from the Se-containing layer becomes more dramatic if there is a high resistance in the Se-containing layer for passing the desired electrical current during the electrodeposition of next layer.
  • Se dissolution could be minimized or completely eliminated by plating a Cu-rich Cu-Se alloy layer of the present invention and then this layer is covered with a Cu cap layer deposited preferably from an acidic bath.
  • a stacking of (Cu-Se)/Cu is formed in this way, other layers can be advantageously electrodeposited on Cu without dissolving the Se in the (Cu-Se) layer. Since molar ratio of Cu in such copper rich Cu-Se layer is more than 50%.
  • the copper cap film in the thickness range of 100 to 3000 Angstrom is deposited on the (Cu-Se) layer from a low pH (acidic) Cu electrodeposition solution to prevent low reduction potentials in which Se is prone to dissolve in the form of l3 ⁇ 4Se or HSe " .
  • films of Cu, Ga, and In, or their above described binary or ternary alloy films are electrodeposited on the (Cu-Se)/Cu stack. Absorber layers manufactured from such precursors including Se under other metallic films may improve overall solar cell efficiency.
  • the following film stacks show various examples of precursor stacks including such (Cu-Se)/Cu layering structures, but not limited to: Cu/In/(Cu-Se)/Cu/Ga/Se; Cu/Ga (Cu-Se)/Cu/In/Cu/In/(Cu-Se)/Cu/In/Se; Cu/In/(Cu-Se)/Cu/Ga/ Cu/In/(Cu-Se)/Cu/In/Se; Cu/Ga/(Cu-Se)/Cu/Ga Cu/(Cu-In)/(Cu-Se)/Cu/In/(Cu-Se)/CLi/Ga Se; (Cu-In-Ga)/(Cu-Se)/ Cu/Ga/Se; (Cu-Ga)/(Cu-Se)/ Cu/In/Se; (Cu-In-Ga)/(Cu-Se)/Cu/Ga/Se; (Cu- Ga)/(Cu-SeyCu/In/Se and

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Abstract

La présente invention porte sur un procédé et sur une structure de précurseur pour former une couche d'absorbeur pour cellule solaire. Le procédé consiste à effectuer une électrodéposition d'une première couche comprenant un empilement de couches comprenant au moins un premier film comprenant du cuivre, un second film comprenant de l'indium et un troisième film comprenant du gallium, la première couche comprenant une première quantité de cuivre, à effectuer une électrodéposition d'une seconde couche sur la première couche, la seconde couche comprenant au moins l'un d'un second film d'alliage ternaire cuivre-indium-gallium, un film d'alliage binaire cuivre-indium, un film d'alliage binaire cuivre-gallium et un film d'alliage binaire cuivre-sélénium, la seconde couche comprenant une seconde quantité de cuivre, qui est supérieure à la première quantité de cuivre, et à effectuer une électrodéposition d'une troisième couche sur la seconde couche, la troisième couche comprenant le sélénium ; et à faire réagir l'empilement de précurseur pour former une couche absorbante sur la base.
PCT/US2010/060712 2009-12-18 2010-12-16 Procédés et chimies d'électroplaquage pour le dépôt de films minces à teneur en cuivre-indium-gallium Ceased WO2011075564A1 (fr)

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Application Number Priority Date Filing Date Title
CN2010800573747A CN102741459A (zh) 2009-12-18 2010-12-16 用于沉积含铜-铟-镓的薄膜的电镀方法和化学物

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US12/642,702 US8425753B2 (en) 2008-05-19 2009-12-18 Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films
US12/642,709 2009-12-18
US12/642,702 2009-12-18
US12/642,691 US20100140098A1 (en) 2008-05-15 2009-12-18 Selenium containing electrodeposition solution and methods
US12/642,709 US8409418B2 (en) 2009-02-06 2009-12-18 Enhanced plating chemistries and methods for preparation of group IBIIIAVIA thin film solar cell absorbers
US12/642,691 2009-12-18

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PCT/US2010/060712 Ceased WO2011075564A1 (fr) 2009-12-18 2010-12-16 Procédés et chimies d'électroplaquage pour le dépôt de films minces à teneur en cuivre-indium-gallium

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US9410259B2 (en) 2011-09-02 2016-08-09 Alliance For Sustainable Energy, Llc Electrodeposition of gallium for photovoltaics
WO2015099755A1 (fr) * 2013-12-27 2015-07-02 Colgate-Palmolive Company Méthodes de soins buccaux prébiotiques utilisant un saccharide
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