US20130168825A1 - Fabrication of ionic liquid electrodeposited cu-sn-zn-s-se thin films and method of making - Google Patents

Fabrication of ionic liquid electrodeposited cu-sn-zn-s-se thin films and method of making Download PDF

Info

Publication number
US20130168825A1
US20130168825A1 US13/731,841 US201213731841A US2013168825A1 US 20130168825 A1 US20130168825 A1 US 20130168825A1 US 201213731841 A US201213731841 A US 201213731841A US 2013168825 A1 US2013168825 A1 US 2013168825A1
Authority
US
United States
Prior art keywords
semiconductor thin
layer
ionic compound
chloride
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/731,841
Inventor
Raghu Nath Bhattacharya
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alliance for Sustainable Energy LLC
Original Assignee
Alliance for Sustainable Energy LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alliance for Sustainable Energy LLC filed Critical Alliance for Sustainable Energy LLC
Priority to US13/731,841 priority Critical patent/US20130168825A1/en
Assigned to ALLIANCE FOR SUSTAINABLE ENERGY, LLC reassignment ALLIANCE FOR SUSTAINABLE ENERGY, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BHATTACHARYA, RAGHU
Assigned to ENERGY, UNITED STATES DEPARTMENT OF reassignment ENERGY, UNITED STATES DEPARTMENT OF CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
Publication of US20130168825A1 publication Critical patent/US20130168825A1/en
Priority to US14/323,651 priority patent/US9236511B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02491—Conductive materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • 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
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • 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
    • H01L31/03923—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 including AIBIIICVI compound materials, e.g. CIS, CIGS
    • 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
    • H01L31/03925—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 including AIIBVI compound materials, e.g. CdTe, CdS
    • 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
    • H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • 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

  • PV Photovoltaic
  • a promising pathway to reducing PV cost is the use of thin-film technologies in which thin layers of photoactive materials are deposited inexpensively on large-area substrates.
  • the primary chalcogenide semiconductor absorber materials currently used for thin-film PV device applications are Cu(In,Ga)Se 2 and CdTe.
  • GWP Global Warming Potential
  • FIG. 1 is a block diagram illustrating one embodiment of a Cu—Zn—Sn—S—Se (CZTSS) semiconductor thin film.
  • FIG. 2 illustrates X-ray diffraction patterns for several films with varying atomic ratios.
  • FIG. 3 a illustrates dark and light current response curves of an electrodeposited CZTSS device.
  • FIG. 3 b illustrates the external quantum efficiency (EQE) spectrum of the CZTSS device.
  • FIG. 4 illustrates the SEM results of the thin films.
  • FIG. 4 a illustrates the SEM surface morphology and
  • FIG. 4 b illustrates the SEM cross-section of annealed CZTSS thin films.
  • FIG. 5 is a flowchart of a method of forming chalcogen-based semiconductor thin films within an electrochemical device.
  • CZTSS copper, zinc, tin, sulfur and selenium
  • Ionic liquids have wide electrodeposition potential windows and high thermal stability, resulting in higher deposition efficiencies for electronegative species and allowing higher deposition temperatures to promote in-situ crystallization, thereby avoiding the need for post-deposition thermal annealing.
  • This solvent system permits depositing CTZSS that is free of impurities (including oxides and hydroxides).
  • electrodeposition may be performed using non-aqueous solvents with a large electrochemical window like ionic liquids (ILs).
  • FIG. 1 illustrates an electrochemical structure 100 having a substrate 110 , a three-layered thin film comprising a first layer 120 deposited onto the substrate 110 , a second layer 130 deposited onto the first layer 120 and a third layer 140 deposited onto the second layer 130 .
  • the thin-film that is deposited on a substrate comprises at least one copper salt, tin salt, zinc salt, or any combination thereof.
  • the substrate 110 may comprise glass, chromium, molybdenum, silicon, silicon dioxide, aluminum oxide, sapphire, germanium, an alloy of silicon and germanium, indium phosphide (InP), glass coated with a Molybdenum film 115 , or any combination thereof.
  • Exemplary electrochemical structure 100 may comprise a metallic salt, a chalcogen and an ionic compound in a non-aqueous solution mixed with a solvent within the first layer 120 , second layer 130 and third layer 140 .
  • the first layer 120 and second layer 130 may comprise a metallic salt.
  • the metallic salt may comprise copper sulfate, stannous chloride (SnCl 2 ), stannic chloride (SnCl 4 ), zinc sulfate, zinc chloride or any combination thereof.
  • the chalcogen may comprise selenium, sulfur, telluride, polonium and combinations thereof.
  • the third layer 140 may comprise an ionic compound in a non-aqueous solution mixed with a solvent such as choline chloride-ethylene glycol solution or a sulfonate-based solution.
  • a solvent such as choline chloride-ethylene glycol solution or a sulfonate-based solution.
  • the sulfonate-based solution is mixed with a surfactant.
  • Suitable ionic compounds or supporting electrolyte/complexing ions comprise salts such as sodium sulfate, sodium fluoride, potassium fluoride, potassium bifluoride, sodium bifluoride, sodium chloride, zinc chloride, potassium chloride, or choline chloride (C 5 H 14 ClNO).
  • the ionic compound may be mixed with a surfactant.
  • the sulfonate may comprise mesylate, triflate, tosylate, or besylate.
  • Exemplary solvents for dissolving the ionic compounds or supporting electrolyte/complexing ions are provided in the examples, such as water or choline chloride mixed with ethylene glycol, HCl or boric acid, but any solvent that dissolves an ionic compound may be used.
  • the plating current density is in the range of approximately 1 to 8 mA/cm 2 .
  • the pH of the solution may be in the range of approximately 1-5.
  • This p-type CTZSS semiconductor has optical band gap energy of about 1.2 eV with a tremendous potential for commercial production of low-cost, high-efficiency PV modules. All CTZSS materials (Cu—Sn—Zn—S—Se) are earth abundant and have a cell efficiency of approximately 20%.
  • FIG. 2 shows the X-ray diffraction (XRD) patterns of three annealed CZTS thin films (D 1 , D 2 and D 3 ).
  • the precursor electrodeposited Cu/Sn/Zn stacked layers were annealed in a tube furnace at 550° C. in elemental S atmosphere for 60 minutes. All samples were prepared at same condition to check the reproducibility of the deposition conditions.
  • the precursor film compositions of the films, as analyzed by ICP-MS, were Cu:47-49 at %; Zn:27-25 at %, and Sn:26-24 at %.
  • the XRD patterns are almost identical for all three samples representing Kesterite CZTS structure [joint committee on powder diffraction standards (JCPDS) #26-0575].
  • FIGS. 3 a and 3 b show the device efficiency of 3.6% of an annealed electrodeposited CZTSS film.
  • FIG. 3 a the dark and light current response curves of an electrodeposited CZTSS device.
  • FIG. 3 b shows the external quantum efficiency (EQE) spectrum of a representative CZTSS device.
  • the device efficiency ( FIG. 3 a ) that resulted from the processed electrodeposited precursor film in Se and S atmosphere was 3.6% with a respectable V oc (0.54 V).
  • FIG. 3 b displays the external quantum efficiency (EQE) spectrum of a representative device. This EQE spectrum reveals that the optical band gap of the CZTSS thin film is ⁇ 1.55 eV (800 nm).
  • EQE external quantum efficiency
  • FIGS. 4 a and 4 b The surface morphology and cross-sectional view (SEM) of a representative annealed film is shown in FIGS. 4 a and 4 b .
  • the SEM as shown in FIG. 4 a and FIG. 4 b indicate that films are crack-free and have a compact dense morphology.
  • the cross-sectional view ( FIG. 4 b ) of the film shows the film thickness is about 1.3 ⁇ m and it has a very rough surface morphology.
  • the grain size determined from the top-view and cross-sectional images ranged from about 100 to 500 nm, and the grains exhibit sharp facets. This result indicates that we need to further optimize the deposition and processing conditions to obtain smooth and uniform films. Solar cell devices were fabricated from these absorber materials.
  • All depositions may be accomplished galvanostatically at rates of approximately 3-8 mA cm ⁇ 2 s ⁇ 1 for between approximately 40-180 seconds.
  • the above stacked metal films may be sulfurized/selenized in a quartz tube furnace.
  • the thin films and approximately 200-800 mg of the chalcogen (sometimes both) may be inserted into the furnace under flowing nitrogen.
  • the furnace may be ramped to approximately 400-600° C. in approximately 20-120 minutes, held at temperature for approximately 20-40 minutes, and cooled slowly. In other embodiments, the furnace may be ramped to about 500-600° C. in approximately 20-120 minutes, held at temperature for about 20-30 minutes, and cooled slowly.
  • the annealed samples may be built into devices.
  • CdS may be deposited via a chemical bath 150 , on top of which a bilayer comprising ZnO may be deposited via RF sputter 160 , followed by an electron beam sputtering process of Ni/Al to form grids 170 .
  • the annealed samples may be analyzed via X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • the ratio of Cu:Zn:Sn may be determined via ICP and X-ray fluorescence.
  • the crystal structure of films with atomic ratios between 2.0:1.2:1.0 to 1.2:0.8:1.0 reveal some differences, namely copper-poor films have much stronger peaks, but also have peaks from other phases.
  • FIG. 5 illustrates one method 500 for fabricating an electrochemical device with a three-tiered thin film layers comprising copper, zinc, tin, sulfur and selenium described herein.
  • the method 500 begins at 510 such as by designing of a particular device to be fabricated such as lithium-ion battery or the like.
  • the method 500 continues with selecting material for the substrate 520 , first layer 521 , second layer 522 , and third layer 523 .
  • the method 500 may include the deposition application of the three layers.
  • the method 500 continues with depositing the first layer onto the substrate 540 , followed by depositing the second layer onto the first layer 550 and depositing the third layer onto the second layer 560 .
  • the device is completed by annealing the stacked electrodeposited layers 570 in chalcogen, followed by depositing CdS 580 , RF sputtering of ZnO layers 581 , depositing top contacts 582 and depositing an antireflective coating 583 .
  • the method 500 then may end at 590 .
  • Exemplary methods for electrodepositing thin films are provided in the examples, but any method suitable for moving metal ions in a solution by an electric field to coat an electrode may be used.
  • An exemplary embodiment may involve films electrodeposited by potentiostatic methods.
  • the ionic compound may comprise sodium sulfate, sodium fluoride, potassium fluoride, potassium bifluoride, sodium bifluoride, sodium chloride, zinc chloride, potassium chloride, or choline chloride (C 5 H 14 ClNO).
  • the ionic compound may be mixed with a surfactant.
  • the sulfonate may comprise mesylate, triflate, tosylate, or besylate.
  • a first layer comprising copper may be electrodeposited on a molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath comprising CuSO 4 (100 mM) and Na 2 SO 4 (100 mM). A second layer comprising tin may be electrodeposited from an aqueous bath comprising SnCl 2 (150 mM), SnCl 4 (5-10 mM), NaF (800 mM), NaCl (450 mM) and KF (550 mM); HCl may be used to acidify the bath to a pH of approximately 5. A third layer comprising zinc may be electrodeposited from an aqueous bath comprising ZnSO 4 (100 mM), ZnCl 2 (100 mM), and H 3 BO 3 (215 mM).
  • a first layer comprising copper may be electrodeposited on a molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath of CuSO 4 (100 mM) and Na 2 SO 4 (100 mM).
  • a second layer comprising tin may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG). Approximately 626 g of ChCl and 500 mL of EG may be heated at approximately 90° C. to prepare the ionic liquid solution.
  • a tin plating bath may be prepared by dissolving approximately 0.1 M SnCl 2 in ChCl:EG solvent.
  • a third layer comprising zinc may be electrodeposited from an aqueous bath comprising ZnSO 4 (100 mM), ZnCl 2 (100 mM), and H 3 BO 3 (215 mM).
  • a first layer comprising copper may be electrodeposited on molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath of CuSO 4 (100 mM) and Na 2 SO 4 (100 mM).
  • a second layer comprising tin may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG). About 626 g of ChCl and 500 mL of EG may be heated at about 90° C. to prepare the ionic liquid solution.
  • a tin plating bath may be prepared by dissolving approximately 0.1 M SnCl 2 in ChCl:EG solvent.
  • a third layer comprising zinc may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG). About 626 g of ChCl and 500 mL of EG may be heated at about 90° C. to prepare the ionic liquid solution.
  • IL ionic liquid
  • a Zinc plating bath may be prepared by dissolving approximately 0.1 M ZnCl 2 in ChCl:EG solvent.
  • a first layer comprising copper may be electrodeposited on a molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath comprising CuSO 4 (100 mM) and Na 2 SO 4 (100 mM). A second layer comprising tin may be electrodeposited from a sulfonate-based electrodeposition bath with surfactant (Empigen BB). Tin may be used as a counter electrode. The Faradic efficiency of anode reaction (i.e. Sn dissolution) is as high as cathodic reaction (both close to 100%). A third layer comprising zinc may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG).
  • IL ionic liquid
  • Zinc plating bath is prepared by dissolving about 0.1 M ZnCl 2 in ChCl:EG solvent.
  • Zn may be used as a counter electrode.
  • the Faradic efficiency of anode reaction i.e. Zn dissolution
  • cathodic reaction both close to 100%.
  • Thin film Cu—Zn—Sn—(Se,S) was prepared by annealing the stacked electrodeposited Cu/Sn/Zn layer in a tube furnace in the presence of elemental sulfur and selenium at about 550° C.
  • First a Cu layer was electroplated on Mo/glass substrate from a solution containing 25 gm CuSO 4 .5H 2 O and 14 gm Na 2 SO 4 dissolved in 1000 ml water. The pH of the solution was adjusted to 1.65 by adding 2.6 ml H 2 SO 4 .
  • Second Sn layer was deposited on Cu/Mo/glass from a solution containing 17.5 SnCl 2 .2H 2 O dissolved in 500 ml ionic liquid solvent.
  • Ionic liquid solvent was prepared by dissolving 313 gm choline chloride in 500 ml ethylene glycol.
  • Third Zn layer was prepared from 90 gm ZnSO 4 .4H 2 O, 7.5 gm ZnCl 2 , 6.2 gm H 3 BO 3 and 5 ml Epigen BB dissolved in 500 ml water.
  • Photovoltaic devices were completed by chemical-bath deposition of about 50 nm CdS, followed by RF sputtering of 60 nm of intrinsic ZnO and 120 nm of Al 2 O 3 -doped conducting ZnO.
  • Bilayer Ni (50 nm)/Al (3 ⁇ m) top contacts were deposited in an e-beam system.
  • the final step in the fabrication sequence was the deposition of an antireflection coating (100 nm of MgF 2 ).
  • the current-voltage (I-V) of the devices is shown in FIG. 2 .
  • the cell parameters are 0.54 V open-circuit voltage, 16.9 mA/cm 2 short-circuit current density, 40% fill factor, and 3.6% efficiency.
  • the device efficiency before antireflection coating MgF 2 is 3.4% (open-circuit voltage: 0.53 V, short-circuit current density: 16.1 mA/cm 2 , fill factor: 40%).
  • Electrodeposition of Cu—Sn—Zn was performed sequentially from a Cu-plating solution, Sn-plating solution, and Zn-plating solution, respectively.
  • a Cu layer was electrodeposited on a Mo/glass substrate from a Cu-plating solution
  • the second Sn layer was electrodeposited from a Sn-plating solution
  • the third Zn layer was electrodeposited from a Zn-plating solution.
  • the solution concentrations of each deposition solutions were 0.1 M. Fisher Scientific (FB300) and VWR (300V) power supplies were used to electrodeposit Cu—Sn—Zn thin films. All films were electrodeposited by applying constant current.
  • Cu was plated at ⁇ 4.2 mA/cm 2 for 3 minutes
  • Sn was plated at ⁇ 2.0 mA/cm 2 for 22 minutes
  • Zn was plated at ⁇ 1.7 mA/cm 2 for 4 minutes.
  • the desired film composition was obtained by adjusting the film thickness of Cu, Sn and Zn.
  • the films were electrodeposited in a vertical cell in which the electrodes (both working and counter) were suspended vertically from the top of the cell.
  • Precursor films were prepared by employing a two-electrode cell in which the counter electrode was Pt gauze and the working electrode (substrate) was glass/Mo.
  • the Mo film was about 1 ⁇ m thick and was deposited by direct current (dc) sputtering. All chemicals were of Analar- or Puratronic-grade purity and were used as received.
  • the film compositions were analyzed using Agilent Technologies 7700 Series ICP-MS system.
  • PV devices were completed by chemical-bath deposition of about 50 nm CdS, followed by radio frequency (RF) sputtering of 50 nm of intrinsic ZnO and 350 nm of Al 2 O 3 -doped conducting ZnO.
  • RF radio frequency

Abstract

A semiconductor thin-film and method for producing a semiconductor thin-films comprising a metallic salt, an ionic compound in a non-aqueous solution mixed with a solvent and processing the stacked layer in chalcogen that results in a CZTS/CZTSS thin films that may be deposited on a substrate is disclosed.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • The present application claims priority from U.S. Provisional Patent Application No. 61/581,962, filed Dec. 30, 2012; the subject matter of which hereby is specifically incorporated herein by reference for all that it discloses and teaches.
    • CONTRACTUAL ORIGIN
  • The United States Government has rights in this invention under Contract No. DE-AC36-08GO28308 between the United States Department of Energy and the Alliance for Sustainable Energy, LLC, the Manager and Operator of the National Renewable Energy Laboratory.
    • BACKGROUND
  • Photovoltaic (PV) solar electric technology will be a significant contributor to world energy supplies when reliable, efficient PV power products are manufactured in large volumes at low cost. A promising pathway to reducing PV cost is the use of thin-film technologies in which thin layers of photoactive materials are deposited inexpensively on large-area substrates. The primary chalcogenide semiconductor absorber materials currently used for thin-film PV device applications are Cu(In,Ga)Se2 and CdTe. Despite the promise of these technologies, the toxicity of Cd and supply limitations for In and Te are projected to limit the production capacity of these existing chalcogen-based technologies to less than 100 Global Warming Potential (GWP) per year. This represents a small fraction of the world's growing energy needs, which are expected to double to 27 Terrawat by 2050.
  • The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tools and methods that are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting.
  • FIG. 1 is a block diagram illustrating one embodiment of a Cu—Zn—Sn—S—Se (CZTSS) semiconductor thin film.
  • FIG. 2 illustrates X-ray diffraction patterns for several films with varying atomic ratios.
  • FIG. 3 a illustrates dark and light current response curves of an electrodeposited CZTSS device.
  • FIG. 3 b illustrates the external quantum efficiency (EQE) spectrum of the CZTSS device.
  • FIG. 4 illustrates the SEM results of the thin films. FIG. 4 a illustrates the SEM surface morphology and FIG. 4 b illustrates the SEM cross-section of annealed CZTSS thin films.
  • FIG. 5 is a flowchart of a method of forming chalcogen-based semiconductor thin films within an electrochemical device.
    •  DETAILED DESCRIPTION
  • In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following descriptions.
  • The inventors of the present application realized that combining the use of electrodeposition and ionic liquids in the fabrication of chalcogen-based semiconductor thin films, such has copper, zinc, tin, sulfur and selenium (CZTSS), produced unexpected results that provide alternatives to copper indium gallium diselenide (CIGS). Low-cost, non-vacuum electrodeposition of CZTSSe thin film from aqueous and also ionic liquid electrolytes circumvents the toxicity typically associated with the use of hydrazine. Ionic liquids have wide electrodeposition potential windows and high thermal stability, resulting in higher deposition efficiencies for electronegative species and allowing higher deposition temperatures to promote in-situ crystallization, thereby avoiding the need for post-deposition thermal annealing. This solvent system permits depositing CTZSS that is free of impurities (including oxides and hydroxides). In order to avoid the water reduction, electrodeposition may be performed using non-aqueous solvents with a large electrochemical window like ionic liquids (ILs).
  • Disclosed herein are metallic salts that may be used in a solution for a semiconductor thin-film. In certain embodiments, the solvent comprises ethylene glycol mixed with the ionic compound, water, HCl or boric acid (H3BO3). FIG. 1 illustrates an electrochemical structure 100 having a substrate 110, a three-layered thin film comprising a first layer 120 deposited onto the substrate 110, a second layer 130 deposited onto the first layer 120 and a third layer 140 deposited onto the second layer 130. In some embodiments the thin-film that is deposited on a substrate comprises at least one copper salt, tin salt, zinc salt, or any combination thereof. In some embodiments the substrate 110 may comprise glass, chromium, molybdenum, silicon, silicon dioxide, aluminum oxide, sapphire, germanium, an alloy of silicon and germanium, indium phosphide (InP), glass coated with a Molybdenum film 115, or any combination thereof.
  • Exemplary electrochemical structure 100 may comprise a metallic salt, a chalcogen and an ionic compound in a non-aqueous solution mixed with a solvent within the first layer 120, second layer 130 and third layer 140. In some embodiments the first layer 120 and second layer 130 may comprise a metallic salt. The metallic salt may comprise copper sulfate, stannous chloride (SnCl2), stannic chloride (SnCl4), zinc sulfate, zinc chloride or any combination thereof. In some embodiments, the chalcogen may comprise selenium, sulfur, telluride, polonium and combinations thereof. In other embodiments, the third layer 140 may comprise an ionic compound in a non-aqueous solution mixed with a solvent such as choline chloride-ethylene glycol solution or a sulfonate-based solution. In certain embodiments, the sulfonate-based solution is mixed with a surfactant.
  • Suitable ionic compounds or supporting electrolyte/complexing ions comprise salts such as sodium sulfate, sodium fluoride, potassium fluoride, potassium bifluoride, sodium bifluoride, sodium chloride, zinc chloride, potassium chloride, or choline chloride (C5H14ClNO). In some embodiments, where the ionic compound comprise sulfonate, it may be mixed with a surfactant. The sulfonate may comprise mesylate, triflate, tosylate, or besylate. Exemplary solvents for dissolving the ionic compounds or supporting electrolyte/complexing ions are provided in the examples, such as water or choline chloride mixed with ethylene glycol, HCl or boric acid, but any solvent that dissolves an ionic compound may be used.
  • In certain embodiments, the plating current density is in the range of approximately 1 to 8 mA/cm2. The pH of the solution may be in the range of approximately 1-5. This p-type CTZSS semiconductor has optical band gap energy of about 1.2 eV with a tremendous potential for commercial production of low-cost, high-efficiency PV modules. All CTZSS materials (Cu—Sn—Zn—S—Se) are earth abundant and have a cell efficiency of approximately 20%.
  • FIG. 2 shows the X-ray diffraction (XRD) patterns of three annealed CZTS thin films (D1, D2 and D3). The precursor electrodeposited Cu/Sn/Zn stacked layers were annealed in a tube furnace at 550° C. in elemental S atmosphere for 60 minutes. All samples were prepared at same condition to check the reproducibility of the deposition conditions. The precursor film compositions of the films, as analyzed by ICP-MS, were Cu:47-49 at %; Zn:27-25 at %, and Sn:26-24 at %. As shown in FIG. 2, the XRD patterns are almost identical for all three samples representing Kesterite CZTS structure [joint committee on powder diffraction standards (JCPDS) #26-0575].
  • FIGS. 3 a and 3 b show the device efficiency of 3.6% of an annealed electrodeposited CZTSS film. As shown in FIG. 3 a, the dark and light current response curves of an electrodeposited CZTSS device. FIG. 3 b shows the external quantum efficiency (EQE) spectrum of a representative CZTSS device. The device efficiency (FIG. 3 a) that resulted from the processed electrodeposited precursor film in Se and S atmosphere was 3.6% with a respectable Voc (0.54 V). FIG. 3 b displays the external quantum efficiency (EQE) spectrum of a representative device. This EQE spectrum reveals that the optical band gap of the CZTSS thin film is ˜1.55 eV (800 nm). To improve the device efficiency, one can optimize the electrodeposition and processing conditions of the stacked layer in Se and S at high temperature.
  • The surface morphology and cross-sectional view (SEM) of a representative annealed film is shown in FIGS. 4 a and 4 b. The SEM as shown in FIG. 4 a and FIG. 4 b, indicate that films are crack-free and have a compact dense morphology. The cross-sectional view (FIG. 4 b) of the film shows the film thickness is about 1.3 μm and it has a very rough surface morphology. The grain size determined from the top-view and cross-sectional images ranged from about 100 to 500 nm, and the grains exhibit sharp facets. This result indicates that we need to further optimize the deposition and processing conditions to obtain smooth and uniform films. Solar cell devices were fabricated from these absorber materials.
  • All depositions may be accomplished galvanostatically at rates of approximately 3-8 mA cm−2 s−1 for between approximately 40-180 seconds. The above stacked metal films may be sulfurized/selenized in a quartz tube furnace. The thin films and approximately 200-800 mg of the chalcogen (sometimes both) may be inserted into the furnace under flowing nitrogen. The furnace may be ramped to approximately 400-600° C. in approximately 20-120 minutes, held at temperature for approximately 20-40 minutes, and cooled slowly. In other embodiments, the furnace may be ramped to about 500-600° C. in approximately 20-120 minutes, held at temperature for about 20-30 minutes, and cooled slowly. The annealed samples may be built into devices. CdS may be deposited via a chemical bath 150, on top of which a bilayer comprising ZnO may be deposited via RF sputter 160, followed by an electron beam sputtering process of Ni/Al to form grids 170.
  • The annealed samples may be analyzed via X-ray diffraction (XRD). The ratio of Cu:Zn:Sn may be determined via ICP and X-ray fluorescence. The crystal structure of films with atomic ratios between 2.0:1.2:1.0 to 1.2:0.8:1.0 reveal some differences, namely copper-poor films have much stronger peaks, but also have peaks from other phases.
  • FIG. 5 illustrates one method 500 for fabricating an electrochemical device with a three-tiered thin film layers comprising copper, zinc, tin, sulfur and selenium described herein. The method 500 begins at 510 such as by designing of a particular device to be fabricated such as lithium-ion battery or the like. The method 500 continues with selecting material for the substrate 520, first layer 521, second layer 522, and third layer 523. At 530, the method 500 may include the deposition application of the three layers. The method 500 continues with depositing the first layer onto the substrate 540, followed by depositing the second layer onto the first layer 550 and depositing the third layer onto the second layer 560. The device is completed by annealing the stacked electrodeposited layers 570 in chalcogen, followed by depositing CdS 580, RF sputtering of ZnO layers 581, depositing top contacts 582 and depositing an antireflective coating 583. The method 500 then may end at 590.
  • Exemplary methods for electrodepositing thin films are provided in the examples, but any method suitable for moving metal ions in a solution by an electric field to coat an electrode may be used. An exemplary embodiment may involve films electrodeposited by potentiostatic methods.
  • Further provided are methods for producing a thin-film on a substrate comprising a metallic salt, a chalcogen and an ionic compound in a non-aqueous solution mixed with a solvent. In some embodiments, the ionic compound may comprise sodium sulfate, sodium fluoride, potassium fluoride, potassium bifluoride, sodium bifluoride, sodium chloride, zinc chloride, potassium chloride, or choline chloride (C5H14ClNO). In some embodiments, where the ionic compound comprises sulfonate, it may be mixed with a surfactant. The sulfonate may comprise mesylate, triflate, tosylate, or besylate.
    • EXAMPLES
  • The foregoing examples of the related art and limitations related therewith are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent to those of skill in the art upon a reading of the specification and a study of the drawings.
    • Example #1
  • A first layer comprising copper may be electrodeposited on a molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath comprising CuSO4 (100 mM) and Na2SO4 (100 mM). A second layer comprising tin may be electrodeposited from an aqueous bath comprising SnCl2 (150 mM), SnCl4 (5-10 mM), NaF (800 mM), NaCl (450 mM) and KF (550 mM); HCl may be used to acidify the bath to a pH of approximately 5. A third layer comprising zinc may be electrodeposited from an aqueous bath comprising ZnSO4 (100 mM), ZnCl2 (100 mM), and H3BO3 (215 mM).
    • Example #2
  • A first layer comprising copper may be electrodeposited on a molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath of CuSO4 (100 mM) and Na2SO4 (100 mM). A second layer comprising tin may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG). Approximately 626 g of ChCl and 500 mL of EG may be heated at approximately 90° C. to prepare the ionic liquid solution. A tin plating bath may be prepared by dissolving approximately 0.1 M SnCl2 in ChCl:EG solvent. A third layer comprising zinc may be electrodeposited from an aqueous bath comprising ZnSO4 (100 mM), ZnCl2 (100 mM), and H3BO3 (215 mM).
    • Example #3
  • A first layer comprising copper may be electrodeposited on molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath of CuSO4 (100 mM) and Na2SO4 (100 mM). A second layer comprising tin may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG). About 626 g of ChCl and 500 mL of EG may be heated at about 90° C. to prepare the ionic liquid solution. A tin plating bath may be prepared by dissolving approximately 0.1 M SnCl2 in ChCl:EG solvent. A third layer comprising zinc may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG). About 626 g of ChCl and 500 mL of EG may be heated at about 90° C. to prepare the ionic liquid solution. A Zinc plating bath may be prepared by dissolving approximately 0.1 M ZnCl2 in ChCl:EG solvent.
    • Example #4
  • A first layer comprising copper may be electrodeposited on a molybdenum/chromium/glass substrate. Copper may be electrodeposited from an aqueous bath comprising CuSO4 (100 mM) and Na2SO4 (100 mM). A second layer comprising tin may be electrodeposited from a sulfonate-based electrodeposition bath with surfactant (Empigen BB). Tin may be used as a counter electrode. The Faradic efficiency of anode reaction (i.e. Sn dissolution) is as high as cathodic reaction (both close to 100%). A third layer comprising zinc may be electrodeposited from an ionic liquid (IL) solution comprising choline chloride-ethylene glycol (ChCl:EG). About 626 g of ChCl and 500 mL of EG may be heated at about 90° C. to prepare the ionic liquid solution. Zinc plating bath is prepared by dissolving about 0.1 M ZnCl2 in ChCl:EG solvent. Zn may be used as a counter electrode. The Faradic efficiency of anode reaction (i.e. Zn dissolution) is as high as cathodic reaction (both close to 100%).
    • Example #5
  • Thin film Cu—Zn—Sn—(Se,S) was prepared by annealing the stacked electrodeposited Cu/Sn/Zn layer in a tube furnace in the presence of elemental sulfur and selenium at about 550° C. First a Cu layer was electroplated on Mo/glass substrate from a solution containing 25 gm CuSO4.5H2O and 14 gm Na2SO4 dissolved in 1000 ml water. The pH of the solution was adjusted to 1.65 by adding 2.6 ml H2SO4. Second Sn layer was deposited on Cu/Mo/glass from a solution containing 17.5 SnCl2.2H2O dissolved in 500 ml ionic liquid solvent. Ionic liquid solvent was prepared by dissolving 313 gm choline chloride in 500 ml ethylene glycol. Third Zn layer was prepared from 90 gm ZnSO4.4H2O, 7.5 gm ZnCl2, 6.2 gm H3BO3 and 5 ml Epigen BB dissolved in 500 ml water.
  • Photovoltaic devices were completed by chemical-bath deposition of about 50 nm CdS, followed by RF sputtering of 60 nm of intrinsic ZnO and 120 nm of Al2O3-doped conducting ZnO. Bilayer Ni (50 nm)/Al (3 μm) top contacts were deposited in an e-beam system. The final step in the fabrication sequence was the deposition of an antireflection coating (100 nm of MgF2). The current-voltage (I-V) of the devices is shown in FIG. 2. The cell parameters are 0.54 V open-circuit voltage, 16.9 mA/cm2 short-circuit current density, 40% fill factor, and 3.6% efficiency. The device efficiency before antireflection coating MgF2 is 3.4% (open-circuit voltage: 0.53 V, short-circuit current density: 16.1 mA/cm2, fill factor: 40%).
    • Example #6
  • Electrodeposition of Cu—Sn—Zn was performed sequentially from a Cu-plating solution, Sn-plating solution, and Zn-plating solution, respectively. First, a Cu layer was electrodeposited on a Mo/glass substrate from a Cu-plating solution, the second Sn layer was electrodeposited from a Sn-plating solution, and the third Zn layer was electrodeposited from a Zn-plating solution. The solution concentrations of each deposition solutions were 0.1 M. Fisher Scientific (FB300) and VWR (300V) power supplies were used to electrodeposit Cu—Sn—Zn thin films. All films were electrodeposited by applying constant current. Cu was plated at −4.2 mA/cm2 for 3 minutes, Sn was plated at −2.0 mA/cm2 for 22 minutes and Zn was plated at −1.7 mA/cm2 for 4 minutes.
  • The desired film composition was obtained by adjusting the film thickness of Cu, Sn and Zn. The films were electrodeposited in a vertical cell in which the electrodes (both working and counter) were suspended vertically from the top of the cell. Precursor films were prepared by employing a two-electrode cell in which the counter electrode was Pt gauze and the working electrode (substrate) was glass/Mo. The Mo film was about 1 μm thick and was deposited by direct current (dc) sputtering. All chemicals were of Analar- or Puratronic-grade purity and were used as received. The film compositions were analyzed using Agilent Technologies 7700 Series ICP-MS system. X-ray diffraction (XRD) was performed by a Scintag X-ray machine using a Copper Kα1 radiation at λ=0.5456 Å. PV devices were completed by chemical-bath deposition of about 50 nm CdS, followed by radio frequency (RF) sputtering of 50 nm of intrinsic ZnO and 350 nm of Al2O3-doped conducting ZnO. Bilayer Ni/Al top contacts were deposited in an e-beam system.
  • The Examples discussed above are provided for purposes of illustration and are not intended to be limiting. Still other embodiments and modifications are also contemplated. While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are within their true spirit and scope.

Claims (27)

We claim:
1. A semiconductor thin-film comprising:
a substrate;
a first layer deposited onto the substrate, comprising a metallic salt;
a second layer deposited onto the first layer, comprising a metallic salt; and
a third layer deposited onto the second layer, comprising an ionic compound in a non-aqueous solution mixed with a solvent, wherein the first, second and third layers are stacked and annealed in chalcogen.
2. The semiconductor thin-film according to claim 1, wherein the metallic salt consists of a group selected from copper sulfate, stannous chloride (SnCl2), stannic chloride (SnCl4), zinc sulfate, or zinc chloride.
3. The semiconductor thin-film according to claim 1, wherein the chalcogen is selected from a group consisting of selenium, sulfur, telluride or polonium.
4. The semiconductor thin-film according to claim 1, wherein the ionic compound is selected from a group consisting of sodium sulfate, sodium fluoride, potassium fluoride, potassium bifluoride, sodium bifluoride, sodium chloride, zinc chloride, or potassium chloride.
5. The semiconductor thin-film according to claim 1, wherein the ionic compound comprises choline chloride (C5H14ClNO).
6. The semiconductor thin-film according to claim 1, wherein the solvent comprises ethylene glycol mixed with the ionic compound.
7. The semiconductor thin-film according to claim 1, wherein the solvent comprises water, HCl or boric acid (H3BO3).
8. The semiconductor thin-film according to claim 1, wherein the ionic compound comprises sulfonate.
9. The semiconductor thin-film according to claim 1, wherein the solvent comprises a surfactant mixed with the ionic compound.
10. The semiconductor thin-film according to claim 1, wherein the sulfonate is selected from a group consisting of mesylate, triflate, tosylate, or besylate.
11. A method for producing a semiconductor thin-film comprising the steps of:
(a) electrodepositing a first layer of a metallic salt from an aqueous bath onto a substrate;
(b) electrodepositing a second layer comprising a metallic salt onto the first layer;
(c) electrodepositing a third layer comprising an ionic compound in a non-aqueous solution mixed with a solvent onto the second layer; and
(d) annealing the first, second and third stacked layers in chalcogen.
12. The method of claim 11, wherein the metallic salt is selected from a group consisting of copper sulfate, stannous chloride (SnCl2), stannic chloride (SnCl4), zinc sulfate, or zinc chloride.
13. The method of claim 11, wherein the chalcogen is selected from a group consisting of selenium, sulfur, telluride or polonium.
14. The method of claim 11, wherein the ionic compound is selected from a group consisting of sodium sulfate, sodium fluoride, potassium fluoride, potassium bifluoride, sodium bifluoride, sodium chloride, zinc chloride, or potassium chloride.
15. The method of claim 11, wherein the ionic compound comprises choline chloride (C5H14ClNO).
16. The method of claim 15, wherein the solvent comprises ethylene glycol mixed with the ionic compound.
17. The method of claim 11, wherein the solvent comprises water, HCl or boric acid (H3BO3).
18. The method of claim 11, wherein the ionic compound comprises sulfonate.
19. The method of claim 18, wherein the solvent comprises a surfactant mixed with the ionic compound.
20. The method of claim 18, wherein the sulfonate is selected from a group consisting of mesylate, triflate, tosylate, or besylate.
21. The method of claim 11, wherein the semiconductor thin-film is deposited on a substrate comprising at least one copper salt.
22. The method of claim 11, wherein the semiconductor thin-film is deposited on a substrate comprising at least one tin salt.
23. The method of claim 11, wherein the semiconductor thin-film is deposited on a substrate comprising at least one zinc salt.
24. The method of claim 11, further comprising a plating current density in the range of approximately 1 to 8 mA/cm2.
25. The method of claim 11, wherein the substrate is selected from a group consisting of glass, chromium, molybdenum, silicon, silicon dioxide, aluminum oxide, sapphire, germanium, an alloy of silicon and germanium, indium phosphide (InP) or any combination thereof.
26. The method of claim 11, wherein the substrate comprises glass coated with a Molybdenum film.
27. The method of claim 11, wherein the electroplating solution comprises a pH in the range of approximately 1-5.
US13/731,841 2011-12-30 2012-12-31 Fabrication of ionic liquid electrodeposited cu-sn-zn-s-se thin films and method of making Abandoned US20130168825A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/731,841 US20130168825A1 (en) 2011-12-30 2012-12-31 Fabrication of ionic liquid electrodeposited cu-sn-zn-s-se thin films and method of making
US14/323,651 US9236511B2 (en) 2011-12-30 2014-07-03 Fabrication of ionic liquid electrodeposited Cu—Sn—Zn—S—Se thin films and method of making

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161581962P 2011-12-30 2011-12-30
US13/731,841 US20130168825A1 (en) 2011-12-30 2012-12-31 Fabrication of ionic liquid electrodeposited cu-sn-zn-s-se thin films and method of making

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/323,651 Division US9236511B2 (en) 2011-12-30 2014-07-03 Fabrication of ionic liquid electrodeposited Cu—Sn—Zn—S—Se thin films and method of making

Publications (1)

Publication Number Publication Date
US20130168825A1 true US20130168825A1 (en) 2013-07-04

Family

ID=48694183

Family Applications (2)

Application Number Title Priority Date Filing Date
US13/731,841 Abandoned US20130168825A1 (en) 2011-12-30 2012-12-31 Fabrication of ionic liquid electrodeposited cu-sn-zn-s-se thin films and method of making
US14/323,651 Expired - Fee Related US9236511B2 (en) 2011-12-30 2014-07-03 Fabrication of ionic liquid electrodeposited Cu—Sn—Zn—S—Se thin films and method of making

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/323,651 Expired - Fee Related US9236511B2 (en) 2011-12-30 2014-07-03 Fabrication of ionic liquid electrodeposited Cu—Sn—Zn—S—Se thin films and method of making

Country Status (1)

Country Link
US (2) US20130168825A1 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130217211A1 (en) * 2012-02-21 2013-08-22 Aqt Solar, Inc. Controlled-Pressure Process for Production of CZTS Thin-Films
US8809113B2 (en) * 2012-11-10 2014-08-19 Sharp Laboratories Of America, Inc. Solution-processed metal-selenide semiconductor using selenium nanoparticles
US8871560B2 (en) * 2012-08-09 2014-10-28 International Business Machines Corporation Plasma annealing of thin film solar cells
US20150027896A1 (en) * 2013-07-25 2015-01-29 Korea Institute Of Science And Technology METHOD FOR PRODUCING Cu2ZnSnS4-xSex (0 LESS THAN-EQUAL TO X LESS THAN-EQUAL TO 4) THIN FILM BY ONE STEP ELECTRODEPOSITION IN ELECTROLYTIC BATH CONTAINING IONIC LIQUID
WO2015071189A1 (en) * 2013-11-14 2015-05-21 Basf Se Process for producing tin nanowires
US9236511B2 (en) 2011-12-30 2016-01-12 Alliance For Sustainable Energy, Llc Fabrication of ionic liquid electrodeposited Cu—Sn—Zn—S—Se thin films and method of making
US20160312614A1 (en) * 2013-12-10 2016-10-27 Umited Technologies COrporation Nickel-chromium-aluminum composite by electrodeposition
US10003071B2 (en) 2015-07-14 2018-06-19 National Taiwan University Of Science And Technology Electrode structure, method of fabricating the same, and lithium battery
CN109671803A (en) * 2018-11-09 2019-04-23 南开大学 A kind of thin-film solar cells preparation method
CN110337508A (en) * 2017-12-22 2019-10-15 三菱综合材料株式会社 The manufacturing method of Cu-Ga alloy sputtering targets and Cu-Ga alloy sputtering targets
US10669867B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Electrodeposited nickel-chromium alloy
CN113979468A (en) * 2021-12-09 2022-01-28 山东中鸿新能源科技有限公司 Preparation method of CZTS (Se) nano powder for solar cell module
CN114956131A (en) * 2021-12-16 2022-08-30 昆明理工大学 Method for recovering metal lithium and cobalt from waste lithium cobalt oxide battery positive electrode material
US11732372B2 (en) 2013-12-11 2023-08-22 Raytheon Technologies Corporation Electroformed nickel-chromium alloy

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862753B (en) * 2015-04-18 2020-02-07 云南师范大学 Electrochemical preparation method of copper-zinc-tin-sulfur film absorption layer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7183433B2 (en) * 2000-09-27 2007-02-27 Scionix Limited Ionic liquids and their use as solvents
US20090118558A1 (en) * 2005-07-27 2009-05-07 Bp P.L.C. Dehydration Process
US20090194426A1 (en) * 2005-07-06 2009-08-06 University Of Leicester Eutectic mixtures based upon multivalent metal ions
US20090205714A1 (en) * 2006-05-24 2009-08-20 Kuehnlein Holger Metal Plating Composition and Method for the Deposition of Copper-Zinc-Tin Suitable for Manufacturing Thin Film Solar Cell
US8071779B2 (en) * 2006-12-18 2011-12-06 Inspire Pharmaceuticals, Inc. Cytoskeletal active rho kinase inhibitor compounds, composition and use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110132462A1 (en) 2010-12-28 2011-06-09 The University Of Utah Research Foundation Modified copper-zinc-tin semiconductor films, uses thereof and related methods
US20130168825A1 (en) 2011-12-30 2013-07-04 Alliance For Sustainable Energy, Llc Fabrication of ionic liquid electrodeposited cu-sn-zn-s-se thin films and method of making

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7183433B2 (en) * 2000-09-27 2007-02-27 Scionix Limited Ionic liquids and their use as solvents
US20090194426A1 (en) * 2005-07-06 2009-08-06 University Of Leicester Eutectic mixtures based upon multivalent metal ions
US20090118558A1 (en) * 2005-07-27 2009-05-07 Bp P.L.C. Dehydration Process
US20090205714A1 (en) * 2006-05-24 2009-08-20 Kuehnlein Holger Metal Plating Composition and Method for the Deposition of Copper-Zinc-Tin Suitable for Manufacturing Thin Film Solar Cell
US8071779B2 (en) * 2006-12-18 2011-12-06 Inspire Pharmaceuticals, Inc. Cytoskeletal active rho kinase inhibitor compounds, composition and use

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9236511B2 (en) 2011-12-30 2016-01-12 Alliance For Sustainable Energy, Llc Fabrication of ionic liquid electrodeposited Cu—Sn—Zn—S—Se thin films and method of making
US20130217211A1 (en) * 2012-02-21 2013-08-22 Aqt Solar, Inc. Controlled-Pressure Process for Production of CZTS Thin-Films
US8871560B2 (en) * 2012-08-09 2014-10-28 International Business Machines Corporation Plasma annealing of thin film solar cells
US8809113B2 (en) * 2012-11-10 2014-08-19 Sharp Laboratories Of America, Inc. Solution-processed metal-selenide semiconductor using selenium nanoparticles
US20150027896A1 (en) * 2013-07-25 2015-01-29 Korea Institute Of Science And Technology METHOD FOR PRODUCING Cu2ZnSnS4-xSex (0 LESS THAN-EQUAL TO X LESS THAN-EQUAL TO 4) THIN FILM BY ONE STEP ELECTRODEPOSITION IN ELECTROLYTIC BATH CONTAINING IONIC LIQUID
WO2015071189A1 (en) * 2013-11-14 2015-05-21 Basf Se Process for producing tin nanowires
US20160312614A1 (en) * 2013-12-10 2016-10-27 Umited Technologies COrporation Nickel-chromium-aluminum composite by electrodeposition
US10669867B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Electrodeposited nickel-chromium alloy
US10669851B2 (en) * 2013-12-10 2020-06-02 Raytheon Technologies Corporation Nickel-chromium-aluminum composite by electrodeposition
US11732372B2 (en) 2013-12-11 2023-08-22 Raytheon Technologies Corporation Electroformed nickel-chromium alloy
US10003071B2 (en) 2015-07-14 2018-06-19 National Taiwan University Of Science And Technology Electrode structure, method of fabricating the same, and lithium battery
CN110337508A (en) * 2017-12-22 2019-10-15 三菱综合材料株式会社 The manufacturing method of Cu-Ga alloy sputtering targets and Cu-Ga alloy sputtering targets
CN109671803A (en) * 2018-11-09 2019-04-23 南开大学 A kind of thin-film solar cells preparation method
CN113979468A (en) * 2021-12-09 2022-01-28 山东中鸿新能源科技有限公司 Preparation method of CZTS (Se) nano powder for solar cell module
CN114956131A (en) * 2021-12-16 2022-08-30 昆明理工大学 Method for recovering metal lithium and cobalt from waste lithium cobalt oxide battery positive electrode material

Also Published As

Publication number Publication date
US9236511B2 (en) 2016-01-12
US20140322859A1 (en) 2014-10-30

Similar Documents

Publication Publication Date Title
US9236511B2 (en) Fabrication of ionic liquid electrodeposited Cu—Sn—Zn—S—Se thin films and method of making
US9041141B2 (en) Structure and method of fabricating a CZTS photovoltaic device by electrodeposition
Scragg et al. A 3.2% efficient Kesterite device from electrodeposited stacked elemental layers
US5871630A (en) Preparation of copper-indium-gallium-diselenide precursor films by electrodeposition for fabricating high efficiency solar cells
US10655237B2 (en) Method and chemistry for selenium electrodeposition
Mali et al. Synthesis and characterization of Cu2ZnSnS4 thin films by SILAR method
Wang Progress in thin film solar cells based on
JP5552026B2 (en) Method for forming a photovoltaic device
US8444842B2 (en) Electroplating methods and chemistries for deposition of group IIIA-group via thin films
US20130112564A1 (en) Electroplating Solutions and Methods For Deposition of Group IIIA-VIA Films
Wang et al. Influence of deposition potential on Cu2ZnSnS4 thin–film solar cells co–electrodeposited on fluorine–doped tin oxide substrates
CN104032336B (en) Manufacture the antivacuum method of the light absorbent for solar cell application
Mandati et al. Pulsed electrodeposition of CuInSe2 thin films with morphology for solar cell applications
US20130230933A1 (en) Methods for fabricating thin film solar cells
US20110132764A1 (en) Formation of a transparent conductive oxide film for use in a photovoltaic structure
US20150027896A1 (en) METHOD FOR PRODUCING Cu2ZnSnS4-xSex (0 LESS THAN-EQUAL TO X LESS THAN-EQUAL TO 4) THIN FILM BY ONE STEP ELECTRODEPOSITION IN ELECTROLYTIC BATH CONTAINING IONIC LIQUID
US9410259B2 (en) Electrodeposition of gallium for photovoltaics
Khalil et al. Co-electrodeposition of metallic precursors for the fabrication of CZTSe thin films solar cells on flexible Mo foil
US9243340B2 (en) Non-vacuum method of manufacturing light-absorbing materials for solar cell application
Yang et al. Improvement of the photovoltaic performance of Cu2ZnSn (SxSe1− x) 4 solar cells by adding polymer in the precursor solution
CN102859046A (en) Plating chemistries of group IB /IIIA / VIA thin film solar absorbers
Lee et al. Structural regulation of electrochemically deposited copper layers for fabrication of thin film solar cells with a CuInS2 photoabsorber
Ray Electrodeposition of thin films for low-cost solar cells
Bhattacharya 3.6%-CZTSS Device fabricated from ionic liquid electrodeposited Sn layer
EP0977911A1 (en) Preparation of copper-indium-gallium-diselenide precursor films by electrodeposition for fabricating high efficiency solar cells

Legal Events

Date Code Title Description
AS Assignment

Owner name: ALLIANCE FOR SUSTAINABLE ENERGY, LLC, COLORADO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BHATTACHARYA, RAGHU;REEL/FRAME:029550/0497

Effective date: 20121231

AS Assignment

Owner name: ENERGY, UNITED STATES DEPARTMENT OF, DISTRICT OF C

Free format text: CONFIRMATORY LICENSE;ASSIGNOR:ALLIANCE FOR SUSTAINABLE ENERGY, LLC;REEL/FRAME:030582/0673

Effective date: 20130107

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION