WO2012001094A1 - Selenide powders and manufacturing process - Google Patents

Selenide powders and manufacturing process Download PDF

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Publication number
WO2012001094A1
WO2012001094A1 PCT/EP2011/060996 EP2011060996W WO2012001094A1 WO 2012001094 A1 WO2012001094 A1 WO 2012001094A1 EP 2011060996 W EP2011060996 W EP 2011060996W WO 2012001094 A1 WO2012001094 A1 WO 2012001094A1
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Prior art keywords
oxygen
metal
mixture
precursor
selenides
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PCT/EP2011/060996
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French (fr)
Inventor
Hossein Aminian
Original Assignee
Umicore
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Publication date
Application filed by Umicore filed Critical Umicore
Priority to CA2803044A priority Critical patent/CA2803044A1/en
Priority to KR1020137000588A priority patent/KR20130098272A/en
Priority to EP11733611.5A priority patent/EP2588407A1/en
Priority to CN201180031937XA priority patent/CN102971254A/en
Priority to JP2013517292A priority patent/JP2013533841A/en
Publication of WO2012001094A1 publication Critical patent/WO2012001094A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to selenide powders for use in dispersions, pastes or inks suitable for the manufacture of photovoltaic cells such as CIGS or CIGSS based solar cells.
  • Copper indium gallium selenide is a compound semiconductor composed of Cu, In, Ga, and Se, with a chemical formula of CuIn x Ga(i_ x) Se 2 , where the value of x can vary from 1 (pure copper indium selenide) to 0 (pure copper gallium selenide). It is used as a light absorber material in thin film solar cells.
  • Selenium can be partly or totally substituted by sulfur, thereby obtaining copper indium gallium sulfo-selenide (CIGSS).
  • the most common process for making CIGS based solar cells is vacuum-based, whereby Cu, Ga and In are co-evaporated or co-sputtered on a substrate, the obtained film being then annealed and selenized in a selenium vapor to form the desired CIGS structure.
  • An alternative is to directly co-deposit Cu, Ga, In, and Se onto a heated substrate.
  • H 2 Se is used in the selenization step, either introduced as such or possibly formed in a Se (gas) and H 2 (gas) mixture.
  • H 2 Se is however highly toxic, and it entails a significant health risk even when the best precautionary measures are taken.
  • US-A-2009/214763 discloses the production of CIGS powder by reacting a CIG oxide powder with SeCl 4 and heating the resulting mixture under a reducing atmosphere. The reactions will however generate HCl, which is corrosive towards both the apparatus and the substrate, in particular at the temperature of about 400 °C needed to obtain the CIGS- based powder. There is also a risk for the formation of chlorides in the powder.
  • a less risky and cleaner process is therefore presented to synthesize selenides as fine powders suitable for incorporation in dispersions, pastes or inks.
  • heat-treatment is still needed to arrive at an annealed layer.
  • no additional selenization step is required and H 2 Se is completely avoided.
  • the invention particularly concerns a process for the synthesis of a submicron or nanoparticulate powders of selenides of a metal or metal mixture, comprising the steps of: selecting an oxygen-bearing precursor of said metal or metal mixture; mixing said oxygen- bearing precursor with an at least stoichiometric amount of selenium; and, reducing the mixture with H 2 at a temperature sufficient to ensure the reaction with the oxygen of the precursor, and the formation of selenides.
  • Said stoechiometric amount of selenium is related to the selenide to be synthesized, typically CuSe, Cu 2 Se, (In x Ga ( i_ x) ) 2 Se 3 , CuIn x Ga ( i_ x) Se 2 .
  • Oxides, hydroxides, and oxy-hydroxide are the preferred oxygen-bearing precursors, as residual reaction products other than water are avoided.
  • the above-defined oxygen-bearing precursor can be prepared by precipitating a salt of one or more of said metals, and calcining the precipitate. This step can be performed in air or in another 0 2 -bearing gas, at a temperature such as to decompose the salt and to oxidize its metals. Suitable salts should decompose and react at moderate temperatures; carbonates or organic salts such as oxalates are generally adequate.
  • Selenides are a preferred target, as they are widely applied for the manufacture of solar cells.
  • Binary e.g. CuSe, Cu 2 Se
  • ternary e.g. (In x Ga ( i_ x) ) 2 Se 3
  • quaternary selenides CuIn x Ga(i_ x) Se 2 or CIGS
  • the synthesis will in particular target powders according to the usual CIGS chemical formula, where the value of x can vary from 1 (pure copper indium selenide) to 0 (pure copper gallium selenide).
  • the process is also suitable for the preparation of mixtures of sulfides and selenides by adding sulfur to the mixture of oxygen-bearing metal precursor and selenium.
  • Such mixed selenides and sulfides are suitable for the preparation of copper indium gallium sulfo- selenide (CIGSS).
  • CGSS copper indium gallium sulfo- selenide
  • With CIGS powders rather high annealing temperatures are needed, up to 700 °C. Such a temperature is expected to cause metal and Se losses through vaporization. It would also deform the soda- lime glass substrates used in low cost solar cell structures. It is therefore advantageous to apply a mixture of selenides instead of CIGS as such.
  • Individual selenides, in particular CuSe could act as fluxing agents, thereby allowing for moderate sintering temperatures. Such temperatures are advantageous, as they may be compatible with lower-cost substrates such as plastic flexible substrates.
  • Se melts at a relatively low 221 °C and can act as a wetting and fluxing agent during annealing by filling the voids between the alloy particles, which have higher individual melting points.
  • the excess of Se will compensate the losses due to vaporization that may take place in the annealing step.
  • the excess could be of more than 1% of Se by weight. This excess can be provided by the addition of a proper amount of Se powder, either before or after the reduction step.
  • a mean particle size (d50) of less than 500 nm is suitable for incorporation in ink, and is compatible with the thickness of the envisaged layer. Finer particles, with a d50 of less than 200 nm, are however preferred, as this may help lowering the annealing temperature.
  • the above-defined process lends itself well for preparing such a product, in particular when starting from submicron or nanoparticulate precursors, such as oxide or hydroxides.
  • the admixed Se and/or S powders do not need to be particularly fine-grained, as these ingredients will melt at the temperature of more than 300 °C that is encountered during the reduction.
  • the above particles are used for the manufacture of a dispersion, paste or ink.
  • the so obtained composition is suitable for the manufacture of a photovoltaic cell.
  • Another embodiment of the invention concerns the particulate material obtainable according to the above process, in particular when a stoichiometric excess of Se is present.
  • the process according to the invention can typically be performed by precipitating hydroxides from an aqueous solution of the desired metals.
  • An aqueous nitrate solution containing 47.7 g/1 Cu, 18.4 g/1 Ga, and 56.1 g/1 In is precipitated at 55 °C, by slowly adding a solution of NaOH over the course of about 2 hours.
  • the pH varies from an initial value of 1.7 to about 12, whereby the recovery of the metals as hydroxides is nearly quantitative.
  • the precipitated hydroxide is then washed and dried in a conventional oven at 90 °C.
  • the dried powder is calcined in air at 550 °C for 2 hours. It is mixed with a stoichiometric amount of Se powder, and this mixture is reduced with 3 ⁇ 4 in an oven at about 300 °C.
  • the resulting powder is CIGS (CuIno. 6 5Ga 0 .35Se 2 ), which can be dispersed for further use.
  • A shows the corresponding crystallo graphic analysis, demonstrating the single-phase nature of the product.
  • the H 2 can successfully be substituted by forming gas.
  • the reduction temperature should be 300 °C or more to make a CIGS with only one phase present. Tests at 250 °C indeed result in the formation of multiple phases, which is undesirable as multiple phases may persist after annealing.

Abstract

This invention relates to selenide powders for use in dispersions, pastes or inks suitable for the manufacture of photovoltaic cells such as CIGS or CIGSS based solar cells. A synthesis process is proposed for the manufacture of submicron or nanoparticulate powder comprising selenides of a metal or a metal mixture, comprising the steps of: - selecting an oxygen-bearing precursor of said metal or metal mixture; - mixing said oxygen-bearing precursor with an at least stoichiometric amount of selenium; and, - reducing the mixture with H2 at a temperature sufficient to ensure the reaction with the oxygen of the precursor, and the formation of selenides. The powders can be deposited on a substrate and annealed without the need for a separate selenization step. The use of H2Se as a Se source, which is a most toxic gas, is thus avoided.

Description

Selenide powders, and manufacturing process
This invention relates to selenide powders for use in dispersions, pastes or inks suitable for the manufacture of photovoltaic cells such as CIGS or CIGSS based solar cells. Copper indium gallium selenide (CIGS) is a compound semiconductor composed of Cu, In, Ga, and Se, with a chemical formula of CuInxGa(i_x)Se2, where the value of x can vary from 1 (pure copper indium selenide) to 0 (pure copper gallium selenide). It is used as a light absorber material in thin film solar cells. Selenium can be partly or totally substituted by sulfur, thereby obtaining copper indium gallium sulfo-selenide (CIGSS). The most common process for making CIGS based solar cells is vacuum-based, whereby Cu, Ga and In are co-evaporated or co-sputtered on a substrate, the obtained film being then annealed and selenized in a selenium vapor to form the desired CIGS structure. An alternative is to directly co-deposit Cu, Ga, In, and Se onto a heated substrate.
The above methods are based on expensive low yield and low productivity vacuum deposition techniques. Therefore, new processes are being developed, based on non- vacuum techniques, such as printing using inks comprising a solvent and a colloidal suspension of nanoparticles of mixed oxides of Cu, In and Ga. The dried precursor layer is reduced under hydrogen to form a metallic alloy, which is then annealed and selenized using H2Se. Such a process is exemplified in e.g. EP-A-0978882.
A major drawback of the above method is that H2Se is used in the selenization step, either introduced as such or possibly formed in a Se (gas) and H2 (gas) mixture. H2Se is however highly toxic, and it entails a significant health risk even when the best precautionary measures are taken.
US-A-2009/214763 discloses the production of CIGS powder by reacting a CIG oxide powder with SeCl4 and heating the resulting mixture under a reducing atmosphere. The reactions will however generate HCl, which is corrosive towards both the apparatus and the substrate, in particular at the temperature of about 400 °C needed to obtain the CIGS- based powder. There is also a risk for the formation of chlorides in the powder.
A less risky and cleaner process is therefore presented to synthesize selenides as fine powders suitable for incorporation in dispersions, pastes or inks. After a deposit has been formed on a substrate, heat-treatment is still needed to arrive at an annealed layer. However, no additional selenization step is required and H2Se is completely avoided.
The invention particularly concerns a process for the synthesis of a submicron or nanoparticulate powders of selenides of a metal or metal mixture, comprising the steps of: selecting an oxygen-bearing precursor of said metal or metal mixture; mixing said oxygen- bearing precursor with an at least stoichiometric amount of selenium; and, reducing the mixture with H2 at a temperature sufficient to ensure the reaction with the oxygen of the precursor, and the formation of selenides.
Said stoechiometric amount of selenium is related to the selenide to be synthesized, typically CuSe, Cu2Se, (InxGa(i_x))2Se3, CuInxGa(i_x)Se2.
Oxides, hydroxides, and oxy-hydroxide are the preferred oxygen-bearing precursors, as residual reaction products other than water are avoided.
The above-defined oxygen-bearing precursor can be prepared by precipitating a salt of one or more of said metals, and calcining the precipitate. This step can be performed in air or in another 02-bearing gas, at a temperature such as to decompose the salt and to oxidize its metals. Suitable salts should decompose and react at moderate temperatures; carbonates or organic salts such as oxalates are generally adequate.
Selenides are a preferred target, as they are widely applied for the manufacture of solar cells. Binary (e.g. CuSe, Cu2Se), ternary (e.g. (InxGa(i_x))2Se3) or quaternary selenides (CuInxGa(i_x)Se2 or CIGS) can be synthesized. The synthesis will in particular target powders according to the usual CIGS chemical formula, where the value of x can vary from 1 (pure copper indium selenide) to 0 (pure copper gallium selenide). The process is also suitable for the preparation of mixtures of sulfides and selenides by adding sulfur to the mixture of oxygen-bearing metal precursor and selenium. Such mixed selenides and sulfides are suitable for the preparation of copper indium gallium sulfo- selenide (CIGSS). With CIGS powders, rather high annealing temperatures are needed, up to 700 °C. Such a temperature is expected to cause metal and Se losses through vaporization. It would also deform the soda- lime glass substrates used in low cost solar cell structures. It is therefore advantageous to apply a mixture of selenides instead of CIGS as such. Individual selenides, in particular CuSe, could act as fluxing agents, thereby allowing for moderate sintering temperatures. Such temperatures are advantageous, as they may be compatible with lower-cost substrates such as plastic flexible substrates.
It may be useful to provide a stoichiometric excess of Se with respect to the envisaged selenide. Indeed, Se melts at a relatively low 221 °C and can act as a wetting and fluxing agent during annealing by filling the voids between the alloy particles, which have higher individual melting points. Moreover, the excess of Se will compensate the losses due to vaporization that may take place in the annealing step. According to the annealing conditions (type of furnace, temperature, amount of material being processed, etc.), the excess could be of more than 1% of Se by weight. This excess can be provided by the addition of a proper amount of Se powder, either before or after the reduction step.
A mean particle size (d50) of less than 500 nm is suitable for incorporation in ink, and is compatible with the thickness of the envisaged layer. Finer particles, with a d50 of less than 200 nm, are however preferred, as this may help lowering the annealing temperature. The above-defined process lends itself well for preparing such a product, in particular when starting from submicron or nanoparticulate precursors, such as oxide or hydroxides.
The admixed Se and/or S powders do not need to be particularly fine-grained, as these ingredients will melt at the temperature of more than 300 °C that is encountered during the reduction.
In further embodiments, the above particles are used for the manufacture of a dispersion, paste or ink. The so obtained composition is suitable for the manufacture of a photovoltaic cell.
Another embodiment of the invention concerns the particulate material obtainable according to the above process, in particular when a stoichiometric excess of Se is present. Example
The process according to the invention can typically be performed by precipitating hydroxides from an aqueous solution of the desired metals.
An aqueous nitrate solution containing 47.7 g/1 Cu, 18.4 g/1 Ga, and 56.1 g/1 In is precipitated at 55 °C, by slowly adding a solution of NaOH over the course of about 2 hours. The pH varies from an initial value of 1.7 to about 12, whereby the recovery of the metals as hydroxides is nearly quantitative.
The precipitated hydroxide is then washed and dried in a conventional oven at 90 °C. The dried powder is calcined in air at 550 °C for 2 hours. It is mixed with a stoichiometric amount of Se powder, and this mixture is reduced with ¾ in an oven at about 300 °C. The resulting powder is CIGS (CuIno.65Ga0.35Se2), which can be dispersed for further use. A shows the corresponding crystallo graphic analysis, demonstrating the single-phase nature of the product.
The H2 can successfully be substituted by forming gas. The reduction temperature should be 300 °C or more to make a CIGS with only one phase present. Tests at 250 °C indeed result in the formation of multiple phases, which is undesirable as multiple phases may persist after annealing.

Claims

Claims
1. Process for the synthesis of a submicron or nanoparticulate powder comprising selenides of a metal or a metal mixture, comprising the steps of:
- selecting an oxygen-bearing precursor of said metal or metal mixture;
- mixing said oxygen-bearing precursor with an at least stoichiometric amount of selenium; and,
- reducing the mixture with ¾ at a temperature sufficient to ensure the reaction with the oxygen of the precursor, and the formation of selenides.
2. Process according to claim 1, where the oxygen-bearing precursor is an oxide or hydroxide.
3. Process according to claim 2, where the oxygen-bearing precursor is an oxide prepared by:
- precipitating a salt of one or more of said metals; and,
- calcining the precipitate.
4. Process according to any one of claims 1 or 3, where the metal or metal mixture comprises one or more metals from the list consisting of Cu, In, and Ga.
5. Process according to any one of claims 1 to 4, where the powder is CIGS.
6. Process according to any one of claims 1 to 6, where the powder has a
stoichiometric excess of Se.
7. Use of the powder prepared according to any one of claims 1 to 6 for the manufacture of a dispersion, paste or ink. photovoltaic cell.
PCT/EP2011/060996 2010-07-02 2011-06-30 Selenide powders and manufacturing process WO2012001094A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA2803044A CA2803044A1 (en) 2010-07-02 2011-06-30 Selenide powders, and manufacturing process
KR1020137000588A KR20130098272A (en) 2010-07-02 2011-06-30 Selenide powders and manufacturing process
EP11733611.5A EP2588407A1 (en) 2010-07-02 2011-06-30 Selenide powders and manufacturing process
CN201180031937XA CN102971254A (en) 2010-07-02 2011-06-30 Selenide powders and manufacturing process
JP2013517292A JP2013533841A (en) 2010-07-02 2011-06-30 Selenide powder and production method

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10006875 2010-07-02
EP10006875.8 2010-07-02
US34437410P 2010-07-08 2010-07-08
US61/344,374 2010-07-08

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JP (1) JP2013533841A (en)
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CN114671414A (en) * 2022-03-25 2022-06-28 浙江大学 Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method thereof

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CN103601169A (en) * 2013-06-13 2014-02-26 南昌大学 Preparation method of carbon-hybrid nano belt
CN111517291B (en) * 2019-02-01 2021-08-20 中国科学院物理研究所 Transition metal dichalcogenide with stripe structure and preparation method thereof
CN111320144B (en) * 2020-03-30 2022-02-22 中北大学 Melanin-nano selenium and preparation method thereof
CN111807333B (en) * 2020-07-28 2023-06-23 安徽大学 Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice

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EP0978882A2 (en) 1998-07-02 2000-02-09 International Solar Electric Technology, Inc. An oxide-based method of making compound semiconductor films and making related electronic devices
US6268014B1 (en) * 1997-10-02 2001-07-31 Chris Eberspacher Method for forming solar cell materials from particulars
US20090214763A1 (en) 2008-02-27 2009-08-27 Korea Institute Of Science And Technology Preparation of thin film for solar cell using paste
US20100133479A1 (en) * 2008-12-03 2010-06-03 Industrial Technology Research Institute Fabrication method for ibiiiavia-group amorphous compound and ibiiiavia-group amorphous precursor for thin-film solar cells

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CN101219779B (en) * 2008-01-14 2010-07-28 重庆大学 Method for producing selenide and telluride nano-material with composite base metal hydroxide solvent
CN101613091B (en) * 2009-07-27 2011-04-06 中南大学 CIGS powder, CIGS target, CIGS film and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US6268014B1 (en) * 1997-10-02 2001-07-31 Chris Eberspacher Method for forming solar cell materials from particulars
EP0978882A2 (en) 1998-07-02 2000-02-09 International Solar Electric Technology, Inc. An oxide-based method of making compound semiconductor films and making related electronic devices
US20090214763A1 (en) 2008-02-27 2009-08-27 Korea Institute Of Science And Technology Preparation of thin film for solar cell using paste
US20100133479A1 (en) * 2008-12-03 2010-06-03 Industrial Technology Research Institute Fabrication method for ibiiiavia-group amorphous compound and ibiiiavia-group amorphous precursor for thin-film solar cells

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114671414A (en) * 2022-03-25 2022-06-28 浙江大学 Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method thereof

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CA2803044A1 (en) 2012-01-05
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KR20130098272A (en) 2013-09-04
EP2588407A1 (en) 2013-05-08

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