WO1998048079A1 - Preparation de couches d'un precurseur constitue de diseleniure de cuivre-indium-gallium par electrodeposition pour fabriquer des photopiles a haut rendement - Google Patents

Preparation de couches d'un precurseur constitue de diseleniure de cuivre-indium-gallium par electrodeposition pour fabriquer des photopiles a haut rendement Download PDF

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Publication number
WO1998048079A1
WO1998048079A1 PCT/US1998/006212 US9806212W WO9848079A1 WO 1998048079 A1 WO1998048079 A1 WO 1998048079A1 US 9806212 W US9806212 W US 9806212W WO 9848079 A1 WO9848079 A1 WO 9848079A1
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Prior art keywords
electrodeposition
gallium
indium
voltage
copper
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PCT/US1998/006212
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English (en)
Inventor
Raghu N. Bhattacharya
Falah Hasoon
Holm Wiesner
James Keane
Kannan Ramanathan
Rommel Noufi
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Davis, Joseph & Negley
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Priority claimed from US08/870,081 external-priority patent/US5871630A/en
Application filed by Davis, Joseph & Negley filed Critical Davis, Joseph & Negley
Priority to CA002284826A priority Critical patent/CA2284826C/fr
Priority to EP98913276A priority patent/EP0977911A4/fr
Priority to AU67869/98A priority patent/AU6786998A/en
Publication of WO1998048079A1 publication Critical patent/WO1998048079A1/fr

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    • 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
    • H01L21/02367—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
    • H01L21/02612—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
    • 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
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • 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
    • 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 field of the present invention relates to the preparation of thin film semiconductor devices. More particularly, the present invention relates to electrodeposition of copper-indium-gallium-diselenide films for solar cells.
  • the p-type CIGS layer is combined with an n-type CdS layer to form a p-n heterojunction CdS/CIGS device.
  • the direct energy gap of CIGS results in a large optical absorption coefficient, which in turn permits the use of thin layers on the order of 1-2 ⁇ m.
  • Eberspacher et al. disclose depositing copper and indium films by magnetron sputtering, and depositing a selenium film by thermal evaporation, followed by heating in the presence of various gases.
  • Other methods for producing CIS films have included Molecular Beam Epitaxy, electrodeposition either in single or multiple steps, and vapor deposition of single crystal and polycrystalline films.
  • vapor deposition techniques have been used to yield solar cells with efficiencies as high as seventeen percent (17%), vapor deposition is costly. Accordingly, solar cells made by vapor deposition have generally been limited to devices for laboratory experimentation, and are not suitable for large scale production. On the other hand, thin film solar cells made by electrodeposition techniques are generally much less expensive.
  • Electrodeposition baths containing 0.1-0.2 molar (M) copper ions, 0.05-0.15 M indium ions obtained from indium chloride, 0.05-0.15 M gallium ions obtained from gallium chloride, 0.01-0.03 M selenium ions, and at least 0.3 M lithium chloride were found to produce simultaneous co-electrodeposition of copper, indium, selenium, and appreciable amounts of gallium with a good morphology, when an electrodeposition potential having a high frequency alternating current superimposed upon a DC current was applied.
  • additional material was vapor deposited to adjust the final composition of the deposited film very close to stoichiometric Cu(In 1 _ x Ga x )Se 2 .
  • This unique two-step film deposition process allows precursor metal films to be deposited by inexpensive electrodeposition, and then adjusted using the more expensive but more precise technique of physical vapor deposition to bring the final film into the desired stoichiometric range.
  • Solar cells may then be completed as for example by chemical bath deposition (CBD) of CdS followed by sputtering of ZnO, and addition of bi-layer metal contacts as well as optional anti- reflective coating.
  • CBD chemical bath deposition
  • a solar cell made according to the process disclosed herein achieved a device conversion efficiency of 13.6%. This represents a significant improvement over the 9.4% conversion efficiency device disclosed in U.S. Patent application serial number 08/571,150, now U.S. Patent No. [to be assigned], of which this application is a continuation-in-part.
  • the present invention also includes electrodeposition solutions and process parameters whereby gallium may be co-electrodeposited in appreciable amounts along with copper, indium, and selenium, while still obtaining a densely packed, uniform morphology film suitable for processing into a photovoltaic cell.
  • This co-electrodeposition of gallium further decreases the amount of stoichiometry adjustment that must be made by the later PVD step.
  • FIG. 1 is a cross sectional view of a CIGS photovoltaic device prepared according to the present invention.
  • FIG. 2 is a cross sectional view of the conducting zinc oxide layer 28 shown in FIG. 1.
  • FIG. 3 is a scanning electron miscroscope photograph of the electrodeposited precursor film of Example 1 of the present invention.
  • FIG. 4 is a graph of the Auger electron spectroscopy analysis for the cell of Example 1.
  • FIG. 5 is a graph of the Auger electron spectroscopy analysis for the cell of Example 2.
  • FIG. 6 is a graph of the Auger electron spectroscopy analysis for the cell of Example 3.
  • FIG. 7 is the x-ray analysis results for the electrodeposited film, and the finished films of Examples 1-3.
  • FIG. 8 is a graph of the relative quantum efficiency verses wavelength for the cells of Examples 1-3.
  • FIG. 9 is a graph showing the Current versus Voltage characteristics of the cells of Examples 1-3.
  • the present invention includes an essentially two-step process for fabricating high quality, low cost thin film CIGS semiconductor devices that exhibit photovoltaic characteristics and are especially adaptable for solar cell applications.
  • This first step may include a unique process and electrodeposition bath for electrodepositing gallium concurrently with other elements, as well as the unique use of an alternating current in conjunction with a direct current.
  • the second step is physical vapor deposition of copper, indium, gallium, and/or selenium. In this second step the composition of the overall film is carefully controlled so that the resulting thin film is very close to stoichiometric
  • CdS/CIGS photovoltaic device 10 includes a substrate 12 which may be, for example, soda-lime silica glass or amorphous 7059 glass.
  • Substrate 12 further includes a back contact layer 14 of molybdenum, about 1-2 ⁇ m thick.
  • the molybdenum may be deposited using DC sputtering from a rotating cylindrical magnetron target (CMAG).
  • CMAG rotating cylindrical magnetron target
  • an additional adhesion layer 16 of copper may also be deposited as by electrodeposition.
  • the substrate should be degreased as for example with propanol and dried in flowing nitrogen gas.
  • a metallic precursor film 18 is then deposited by electrodeposition.
  • the precursor film contains one or more of the elements copper, indium, gallium, and selenium. Electrodeposition is generally a less expensive method of depositing these metals than vapor deposition. However, it is not possible to control the ratios of metals deposited during electrodeposition as precisely as desired.
  • the electrodeposition step is integrated with the vapor deposition step that follows. This allows precursor metal to be deposited in bulk using an economical electrodeposition step, followed by a vapor deposition step to carefully control the final metal ratios.
  • the metal precursor film 18 should be deposited to about 1-3 ⁇ m thick, with thickness being controlled by coulometric measurements.
  • an AC voltage improves the morphology of the film. It is also believed that the AC voltage improves nucleation (growth) of the thin film by allowing additional nucleation centers to be created.
  • the applicable DC voltage range is approximately 1-5 VDC, with a preferred voltage of approximately 3 VDC. Improved results may be obtained by superimposing an AC voltage of 0.2-5.0 VAC at 1-100 Khz, with preferred values of approximately 3.5 VAC at 10-30 KHz.
  • the plating solution is adjusted to have a pH of approximately 1.0 to 4.0, and more preferably to about 1.4 to 2.4.
  • the plating solution should preferably be at about 10 °C to 80 °C, and more preferably at about 24 °C. Adding a supporting electrolyte to the plating bath can additionally increase the conductivity of the plating solution, allowing for a further increase in the electrodeposition rate. Salts such as NaCl, LiCl, or Na 2 SO 4 have been found to be suitable supporting electrolytes for use with certain embodiments of the present invention. In completely aqueous solutions, electrolysis of water molecules begins to occur to an undesirable extent at voltage legels that are too high. The resulting O " and OH " ions combine with deposition metal ions or deposited metal to form unwanted metal oxides and hydroxides on the precursor film 18.
  • the water in the plating solution may be either partially or completely replaced by one or more organic solvents such as dimethyl sulf ⁇ xide (DMSO).
  • DMSO dimethyl sulf ⁇ xide
  • Increasing the organic solvent content of the electrodeposition solution allows the cathodic potential to be increased without unacceptable increases in metal oxide and hydroxide formation rates.
  • the increased cathodic potential increases the deposition rate of the precursor films.
  • An additional advantage is that increasing the cathodic potential increases the deposition rate of gallium relative to the deposition rates of other deposited metals. Therefore, using a solution containing one or more organic solvents allows the cathodic potential to be selected from a wider range so as to achieve a more desired stoichiometry of the as-deposited precursor film 18.
  • the preferred cathodic potential is approximately 3-10 VDC and 0.2-5.0 VAC at approximately 1-100 KHz. Value of approximately 5 VDC and 0.45 VAC at approximately 18.1 KHz were found to yield good results.
  • the parameters that must be simultaneously adjusted include but are not limited to: total solution molarity, relative molarities of constituents, from which compounds to obtain the desired constituent elements, pH, temperature, voltage, waveform characteristics, and electrolytic fluid.
  • the present invention includes solutions and process parameters whereby gallium may be co-electrodeposited in appreciable amounts along with the other three constituent elements of CIGS.
  • a second electroplating solution may be employed to adjust the stoichiometry of the electrodeposited film prior to the vapor deposition phase.
  • a first electrodeposition step may produce a CIGS precursor film with less gallium than optimally desired.
  • the gallium content can be increased during the vapor deposition phase, it may be less expensive to deposit a certain amount of gallium using a second electrodeposition solution to make a coarse stoichiometric adjustment prior to proceeding to fine stoichiometric adjustment at the vapor deposition step.
  • Another potential motivation for using a second electrodeposition solution is to achieve a composition gradient in the deposited film, as suggested by U.S. Patent No. 4,335,266 issued to Michelsen et al. which is hereby incorporated by reference for its teachings of composition- graded CIGS thin films for solar cell and other applications.
  • Yet another way of achieving composition grading during electrodeposition is to vary process parameters such as cathodic potential, ionic concentrations, pH, or temperature, as electrodeposition proceeds.
  • electrodeposited precursor films fabricated according to the present invention include Cu-In-Ga-Se, In-Se, Cu-Se, and Cu-In-Se, precursor films.
  • the solution for co-depositing all four elements includes ions of each of the elements of copper, indium, gallium, and selenium.
  • the metal ions may be supplied in the form of dissolved metal salts.
  • gallium should be added to raise the energy gap.
  • electrodeposition potential is expressed in terms of a voltage without specifying positive or negative voltage. It is to be understood that the substrate or working electrode on which the thin film is to be deposited is to be connected as the electrodeposition cathode, with the counter electrode being connected as the anode. Accordingly, the electrodeposition voltages discussed herein are to be understood as negative voltages. In accordance with this convention, where electrodeposition voltages are expressed as, e.g., "at least 1.0 volt", this indicates that an electrodeposition voltage that is at least as negative as -1.0 volt with respect to the counter electrode is to be applied to the substrate. Discussing the electrodeposition voltages as unsigned voltages is to be understood as merely a shorthand way of referring to the absolute potential difference between the electrodes.
  • a suitable method is to rinse precursor film 18 with deionized water and dry it in flowing nitrogen gas.
  • By controlling the ratio of In/Ga the energy gap between the CdS and the CIGS layers can be adjusted to the optimal or nearly optimal value.
  • An energy gap of approximately 1.45 eV is considered optimal for terrestrial solar energy conversion, and is achieved by an In Ga ratio of approximately 3: 1.
  • a Ga/(In+Ga) atomic ratio of 0.34 - 0.50 is preferred, with a ratio of 0.39 producing the highest observed efficiency.
  • the substrate (precursor film) temperature should be 300 °C to 600 °C during PVD, and preferably about 550 °C.
  • the films should then be annealed. Annealing improves the homogeneity and quality of the films.
  • a high quality CIGS film is one that does not exhibit an excessive amount of copper nodules, voids, or vacancies in the film which would reduce conversion efficiencies.
  • Annealing the films at 250 °C to 500 °C in a vacuum, followed by slow cooling at a rate of approximately 3 °C/min to avoid thermal shock was found to yield good results. Because selenium has a much higher vapor pressure than either copper, indium, or gallium, selenium may be lost from the film during the high temperature steps of vapor deposition and annealing. To compensate, the atmosphere during these steps may contain a moderate overpressure of selenium.
  • the film is selenized at a rate of 5-100 A/s during cool-down from PVD temperature to annealing temperature.
  • a thin layer 22 of n-type semiconductor comprising cadmium sulfide is deposited next.
  • CdS layer 22 is preferably deposited by chemical bath deposition (CBD) to a thickness of approximately 200-1000 A.
  • CBD bath may be prepared from 0.08 gm CdSO 4 , 2.5 gm thiourea, and 27.5 gm NH 4 OH dissolved in 200 ml water.
  • the deposition temperature should be approximately 40-80° C.
  • a layer 28 of conducting wide bandgap n-type semiconductor materials is deposited next.
  • layer 28 comprises two zinc oxide layers 24 and 26 as shown in FIG. 2.
  • First zinc oxide layer 24 is deposited with RF sputtering at approximately 0.62 watts/cm 2 in an argon plasma at 10 millitorrs pressure.
  • Second zinc oxide layer 26, comprising approximately 1-5% Al 2 O 3 -doped zinc oxide, is also prepared using RF sputtering at approximately 1.45 watts/cm in an argon plasma at 10 millitorrs pressure.
  • the resistivity of the first layer was 50-200 ohm/cm 2
  • resistivity of the second layer was 15-20 ohm/cm 2 .
  • the transmissivity of the overall ZnO layer was 80-85%.
  • Bi-layer metal contacts 30 may then be prepared with an e-beam system or other techniques.
  • a first metal contact layer was 500-1000 A thick Ni and the second metal contact layer was 1-3 ⁇ m thick Al.
  • Metal contacts 30 will generally be laid out in fine grid lines across the collecting surface of the device and connected to a suitable current collecting electrode (not shown).
  • the efficiency of the resulting device can be further increased by adding an antireflection coating 32, such as a 600-1000 A layer of MgF 2 by electron beam.
  • a device prepared according to Example 3 below exhibited a conversion efficiency of 13.6%.
  • Example 1 A thin film containing copper, indium, gallium, and selenium was deposited onto a glass substrate coated with approximately 500 A Mo, and processed into a photovoltaic cell.
  • the thin film was obtained by preparing a solution containing ions of copper, indium, and selenium, and further including ions of gallium in a concentration of at least 0.05 molar, and at least 0.3 molar LiCl.
  • the electrodeposition bath comprised 2.1286 gm Cu(NO 3 ) 2 -H 2 0, 7.9625 gm InCl 3 , 1.3929 gm H 2 SeO 3 , and 9.2063 gm Ga(No 3 ) 3 , and 14.08 gm LiCl dissolved in 450 ml of water.
  • the resulting bath comprised approximately 0.014 M copper, 0.08 M indium, 0.08 M gallium, and 0.023 M selenium ions.
  • the pH was adjusted to 1-2. Deposition proceeded at 24 °C.
  • the substrate was employed as the working electrode, and platinum gauze was used as the counter electrode in a two electrode system.
  • the electrodeposition voltage comprised a DC component of at least 0.5 volt. More particularly, the electrodeposition voltage comprised a DC voltage of at least 1.0 volt and an AC voltage of at least 0.5 V at a frequency of at least 1.0 KHz superimposed thereon. Still more particularly, the electrodeposition voltage comprised a DC component of 3.0 volts, and an AC component of 3.5 volts pulsed at 20 KHz superimposed thereon.
  • the voltage was supplied by a power source obtained from Team Specialty Products Corporation of Albuquerque, New
  • the AC component is nominally a square wave. However, due to the complex impedances of the power supply and the remainder of the electrodeposition equipment operating at 20 KHz, it will be understood that the voltage as measured at the substrate will not be a perfect square wave. Thus, the applied voltage is more properly described using the broader term of AC
  • FIG. 3 is a scanning electron miscroscope photograph of the as-deposited film. The photograph shows the film to be tight, densely packed, and uniform.
  • FIG. 7 is the X-ray analysis results for the electrodeposited film, and the finished films of Examples 1-3.
  • the X-ray analysis of the as-deposited precursor film indicates the presence of both the CIGS phase and the Cu 2 Se phase.
  • the X- ray analysis of the film after final film composition adjustment shows only the CIGS phase.
  • the shifts in 2-theta values are due to different Ga concentrations in the absorber layers.
  • Photovoltaic devices were completed by chemical bath deposition of approximately 500 A CdS followed by radio frequency sputtering of 500 A intrinsic ZnO and 3500 A of Al 2 O 3 -doped ZnO.
  • Bilayer Ni/Al top contacts were deposited using an e-beam system.
  • An anti-reflection coating of 100 nm of MgF 2 was applied as the final step.
  • FIG. 4 is the AES analysis results for the finished photovoltaic cell showing the atomic distribution of the film at varying depths within the film.
  • FIG. 8 shows the relative quantum efficiency of the cell as a function of wavelength.
  • FIG. 9 shows the Current versus Voltage characteristics of the finished cell. The cell exhibited an overall efficiency of 12.4% . Other performance parameters for this cell are listed in Table 1 below.
  • a cell was prepared according to Example 1, but the PVD step was conducted to adjust the final Ga/(In+Ga) ratio to 0.26 rather than 0.16.
  • the device efficiency improved from 12.4% to 13.2% .
  • the AES analysis is shown in
  • FIG. 5 The relative quantum efficiency is shown in FIG. 8.
  • Example 3 A cell was prepared according to Example 1, but the PVD step was conducted to adjust the final Ga(In+Ga) ratio to 0.39. The overall device efficiency improved to 13.6%. The AES analysis is shown in FIG. 6. The relative quantum efficiency is shown in FIG. 8. The Current vs. Voltage performance is shown in FIG. 9. Performance parameters for the cells of Examples 1-3 are given in Table 1 below.
  • a bath containing approximately 0.016 M Cu(NO 3 ) 2 ⁇ 2 0 3 , 0.08 M InCl 3 , 0.08 M H 2 SeO 3 , and 0.024 M Ga(No 3 ) 3 (ratios of approximately 1, 5, 5, and 1.5, respectively) was prepared at a pH of 1.6. Electrodeposition proceeded at at least 2.0 volts DC and at least 2.0 volts AC at a frequency of at least 10 KHz superimposed thereon. More particularly, electrodeposition proceeded at 3.0 VDC with a pulsed AC voltage of 3.5 volts at a frequency of 20 KHz superimposed thereon. ICP compositional analysis revealed the following film compositions before and after the precursor film was finished:
  • the as-deposited film contains the highest gallium content of any of the examples presented herein.
  • a photovoltaic device was completed as before, with the final Ga/(In+Ga) ratio adjusted to approximately 0.3. The final efficiency of the device was 12.3%.
  • An electrodeposition bath was prepared by dissolving 1.9956 gm Cu(NO 3 ) 2 -H 2 0, 9.9531 gm InCl 3 , 1.7411 gm H 2 SeO 3 , and 12.0832 gm Ga(No 3 ) 3 , and 15 gm LiCl in 450 ml of water (0.18 M copper ions, 0.10 Indium ions, 0.105 M gallium ions, and 0.29 M selenium ions). Electrodeposition proceeded at a voltage of 3.00 VDC and 3.53 VAC superimposed thereon. The composition of the as-deposited precursor layer, expressed as 10 atoms/cm , was The precursor layer was completed by PVD. The finished device exhibited a conversion efficiency of 12.3%.
  • a metallic precursor film of In ⁇ Se ⁇ was electrodeposited on glass substrates coated with a Mo or Mo/Cu layer approximately 500 A thick.
  • the precursor film was deposited using an electroplating solution containing 2.25 gm InCl 3 and 0.41 gm H 2 SeO 3 dissolved in 200 ml of water. The pH of the solution was adjusted between 1.4 and 2.4 using dilute HC1 (10% by volume).
  • the films were deposited by applying a 2-5 V direct current voltage in combination with an alternating current voltage of 0.45 V at 18.1 KHz frequency. The films were 1-3 ⁇ m thick and adhered to the substrate.
  • a metallic precursor film of Cu 1 _ 2 Se 1 _ 3 was electrodeposited on a substrate using an electroplating solution containing 6.21 gm Cu(NO 3 ) 2 -6H 2 O and 1.16 gm H 2 SeO 3 dissolved in 300 ml water. The pH was adjusted between 1.4 and 2.4 using dilute HC1 (10% by volume). The films were deposited by applying a 2-5 V direct current voltage in combination with an alternating current voltage of 0.45 V at 18.1 KHz frequency. As deposited layers were 1-3 ⁇ m thick and adhered to the substrate.
  • Example 8 A metallic precursor film of Cu 1-2 In 1-2 Se 1 - 3 was electrodeposited on a substrate using an electroplating solution containing 4.47 gm CuCl 2 , 5.67 gm InCl 3 and 3.39 gm H 2 SeSO 3 dissolved in 1050 ml water. The pH was adjusted between 1.4 and 2.4 using dilute HC1 (10% by volume). The films were deposited by applying a 2-5 V direct current voltage in combination with an alternating current voltage of 0.45 V at 18.1 KHz frequency. As deposited layers were 1-3 ⁇ m thick and adhered to the substrate. The electrodeposited film was slightly indium poor. Indium was then added by vapor deposition to adjust the final content to approximately CuInSe 2 .
  • the device contained only Cu-In-Se, without any gallium.
  • the device exhibited an efficiency of 8.76% without antireflective coating, and 9.44% after an antireflective coating was added.
  • a precursor film of Cu 1 . 2 In 1 _ 2 Ga 0 .o ⁇ - 1 Se 1 _ 3 was electrodeposited using a solution containing 1.12 gm Cu(NO 3 ) 2 -6H 2 O, 12.0 gm InCl 3 , 4.60 gm Ga(NO 3 ) 3 xH 2 O and 1.80 gm H 2 SeO 3 dissolved in 450 ml of water. This is equivalent to approximately 2.49 gm/1 Cu(NO 3 ) 2 -6H 2 O, 26.7 gm/1 InCl 3 , 10.2 gm/1 Ga(NO 3 ) 3 xH 2 O and 4.0 gm/1 H 2 SeO 3 , and approximately 0.0084, 0.12,
  • Example 10 A precursor film of Cu 1 . 2 In 1 . 2 Gao . o 1 - 1 Se 1 _ 3 was electrodeposited using a solution containing 1.496 gm Cu(No 3 )-5H 2 O, 14.929 gm InCl 3 , 1.523 gm H 2 SeO 3 , and 7.192 gm Ga(NO 3 ) 3 dissolved in 450 ml of DMSO. The films were deposited at 25 °C and also at 50 °C at an applied voltage of 5 VDC.
  • a precursor film of Cu ⁇ In ⁇ Gao . o . - . Se ⁇ was electrodeposited using a solution containing 1.496 gm Cu(No 3 )-5H 2 O, 14.929 gm InCl 3 , 1.523 gm
  • a precursor film of Cu 1 _ 2 In 1 . 2 Ga 001-1 Se 1-3 was electrodeposited using a solution containing 1.496 gm Cu(No 3 )-5H 2 O, 14.929 gm InCl 3 , 1.523 gm
  • the present invention as described above may be incorporated in a variety of applications, as for example the conversion of solar energy to electric energy for baseline power generation.
  • Other applications include appliances such as solar-powered calculators, battery charges such as those used with freeway emergency call boxes, photoelectric eyes, night security light activators, light meters for photographic and other purposes, and the like.

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Abstract

On prépare une photopile (10) ayant un rendement de conversion global de 13,6 % à partir d'une couche (18) d'un précurseur constitué d'un diséléniure de cuivre-indium-gallium. Pour fabriquer ladite couche (18), on revêt un substrat constitué de verre/molybdène (12, 14) par électrodéposition simultanée de cuivre, d'indium, de gallium et de sélénium. La tension d'électrodéposition est une tension en courant alternatif haute fréquence superposée à une tension en courant continu, ce qui améliore la morphologie et la vitesse de croissance de la couche (18). L'électrodéposition est suivie d'un procédé physique de dépôt en phase gazeuse, ce qui permet de régler la stoechiométrie finale de la couche mince (18) sur approximativement Cu(In1-x,Gax)Se2, le rapport Ga/(In+Ga) étant de 0,39 environ.
PCT/US1998/006212 1997-04-21 1998-03-30 Preparation de couches d'un precurseur constitue de diseleniure de cuivre-indium-gallium par electrodeposition pour fabriquer des photopiles a haut rendement WO1998048079A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002284826A CA2284826C (fr) 1997-04-21 1998-03-30 Preparation de couches d'un precurseur constitue de diseleniure de cuivre-indium-gallium par electrodeposition pour fabriquer des photopiles a haut rendement
EP98913276A EP0977911A4 (fr) 1997-04-21 1998-03-30 Preparation de couches d'un precurseur constitue de diseleniure de cuivre-indium-gallium par electrodeposition pour fabriquer des photopiles a haut rendement
AU67869/98A AU6786998A (en) 1997-04-21 1998-03-30 Preparation of copper-indium-gallium-diselenide precursor films by electrodeposition for fabricating high efficiency solar cells

Applications Claiming Priority (4)

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US4450697P 1997-04-21 1997-04-21
US60/044,506 1997-04-21
US08/870,081 US5871630A (en) 1995-12-12 1997-06-05 Preparation of copper-indium-gallium-diselenide precursor films by electrodeposition for fabricating high efficiency solar cells
US08/870,081 1997-06-05

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EP (1) EP0977911A4 (fr)
AU (1) AU6786998A (fr)
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003043096A2 (fr) * 2001-11-10 2003-05-22 Sheffield Hallam University Dispositifs photovoltaiques a film mince a base de cuivre-induium et procedes de fabrication
WO2010043200A1 (fr) * 2008-10-13 2010-04-22 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Procédé pour produire une couche de cristal texturée (001) à partir d'un semi-conducteur en réseau à couches sur une couche métalliquement conductrice avec participation d'un promoteur métallique
WO2011115894A1 (fr) * 2010-03-17 2011-09-22 Dow Global Technologies Llc Matériaux à base de chalcogénures et procédés améliorés pour la fabrication de ces matériaux
WO2013164248A1 (fr) * 2012-05-02 2013-11-07 Umicore Précurseur de sélénite et encre pour la fabrication de cellules photovoltaïques cigs
US8927392B2 (en) 2007-11-02 2015-01-06 Siva Power, Inc. Methods for forming crystalline thin-film photovoltaic structures
EP2475809A4 (fr) * 2009-09-08 2016-05-18 Chengdu Ark Eternity Photovoltaic Technology Company Ltd Procédé électrochimique de production de piles solaires au diséléniure de cuivre-indium-gallium (cigs)

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US5221660A (en) * 1987-12-25 1993-06-22 Sumitomo Electric Industries, Ltd. Semiconductor substrate having a superconducting thin film
US5441897A (en) * 1993-04-12 1995-08-15 Midwest Research Institute Method of fabricating high-efficiency Cu(In,Ga)(SeS)2 thin films for solar cells

Family Cites Families (1)

* Cited by examiner, † Cited by third party
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US5730852A (en) * 1995-09-25 1998-03-24 Davis, Joseph & Negley Preparation of cuxinygazsen (X=0-2, Y=0-2, Z=0-2, N=0-3) precursor films by electrodeposition for fabricating high efficiency solar cells

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US5221660A (en) * 1987-12-25 1993-06-22 Sumitomo Electric Industries, Ltd. Semiconductor substrate having a superconducting thin film
US5441897A (en) * 1993-04-12 1995-08-15 Midwest Research Institute Method of fabricating high-efficiency Cu(In,Ga)(SeS)2 thin films for solar cells

Non-Patent Citations (1)

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See also references of EP0977911A4 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003043096A2 (fr) * 2001-11-10 2003-05-22 Sheffield Hallam University Dispositifs photovoltaiques a film mince a base de cuivre-induium et procedes de fabrication
WO2003043096A3 (fr) * 2001-11-10 2003-11-20 Univ Sheffield Hallam Dispositifs photovoltaiques a film mince a base de cuivre-induium et procedes de fabrication
GB2396868A (en) * 2001-11-10 2004-07-07 Univ Sheffield Hallam Copper-indium based thin film photovoltaic devices and methods of making the same
GB2396868B (en) * 2001-11-10 2005-06-15 Univ Sheffield Hallam Copper-indium based thin film photovoltaic devices and methods of making the same
US8927392B2 (en) 2007-11-02 2015-01-06 Siva Power, Inc. Methods for forming crystalline thin-film photovoltaic structures
WO2010043200A1 (fr) * 2008-10-13 2010-04-22 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Procédé pour produire une couche de cristal texturée (001) à partir d'un semi-conducteur en réseau à couches sur une couche métalliquement conductrice avec participation d'un promoteur métallique
EP2475809A4 (fr) * 2009-09-08 2016-05-18 Chengdu Ark Eternity Photovoltaic Technology Company Ltd Procédé électrochimique de production de piles solaires au diséléniure de cuivre-indium-gallium (cigs)
CN102893370A (zh) * 2010-03-17 2013-01-23 陶氏环球技术有限责任公司 整合连接层的光电活性的、基于硫属元素的薄膜结构
CN102893371A (zh) * 2010-03-17 2013-01-23 陶氏环球技术有限责任公司 基于硫属化物的材料及制备这种材料的改进方法
WO2011115887A1 (fr) * 2010-03-17 2011-09-22 Dow Global Technologies Llc Structures à couches minces photoélectroniquement actives, à base de chalcogénures, contenant des couches de liaison
US8969720B2 (en) 2010-03-17 2015-03-03 Dow Global Technologies Llc Photoelectronically active, chalcogen-based thin film structures incorporating tie layers
US8993882B2 (en) 2010-03-17 2015-03-31 Dow Global Technologies Llc Chalcogenide-based materials and improved methods of making such materials
CN102893370B (zh) * 2010-03-17 2015-12-16 陶氏环球技术有限责任公司 整合连接层的光电活性的、基于硫属元素的薄膜结构
WO2011115894A1 (fr) * 2010-03-17 2011-09-22 Dow Global Technologies Llc Matériaux à base de chalcogénures et procédés améliorés pour la fabrication de ces matériaux
US9911887B2 (en) 2010-03-17 2018-03-06 Dow Global Technologies Llc Chalcogenide-based materials and improved methods of making such materials
WO2013164248A1 (fr) * 2012-05-02 2013-11-07 Umicore Précurseur de sélénite et encre pour la fabrication de cellules photovoltaïques cigs

Also Published As

Publication number Publication date
CA2284826A1 (fr) 1998-10-29
EP0977911A4 (fr) 2002-05-22
CA2284826C (fr) 2007-06-05
EP0977911A1 (fr) 2000-02-09
AU6786998A (en) 1998-11-13

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