EP2588407A1 - Selenide powders and manufacturing process - Google Patents

Selenide powders and manufacturing process

Info

Publication number
EP2588407A1
EP2588407A1 EP11733611.5A EP11733611A EP2588407A1 EP 2588407 A1 EP2588407 A1 EP 2588407A1 EP 11733611 A EP11733611 A EP 11733611A EP 2588407 A1 EP2588407 A1 EP 2588407A1
Authority
EP
European Patent Office
Prior art keywords
oxygen
metal
mixture
precursor
selenides
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.)
Withdrawn
Application number
EP11733611.5A
Other languages
German (de)
French (fr)
Inventor
Hossein Aminian
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.)
Umicore NV SA
Original Assignee
Umicore NV SA
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 Umicore NV SA filed Critical Umicore NV SA
Priority to EP11733611.5A priority Critical patent/EP2588407A1/en
Publication of EP2588407A1 publication Critical patent/EP2588407A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • C—CHEMISTRY; METALLURGY
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)

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.
EP11733611.5A 2010-07-02 2011-06-30 Selenide powders and manufacturing process Withdrawn EP2588407A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11733611.5A EP2588407A1 (en) 2010-07-02 2011-06-30 Selenide powders and manufacturing process

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10006875 2010-07-02
US34437410P 2010-07-08 2010-07-08
EP11733611.5A EP2588407A1 (en) 2010-07-02 2011-06-30 Selenide powders and manufacturing process
PCT/EP2011/060996 WO2012001094A1 (en) 2010-07-02 2011-06-30 Selenide powders and manufacturing process

Publications (1)

Publication Number Publication Date
EP2588407A1 true EP2588407A1 (en) 2013-05-08

Family

ID=42985440

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11733611.5A Withdrawn EP2588407A1 (en) 2010-07-02 2011-06-30 Selenide powders and manufacturing process

Country Status (6)

Country Link
EP (1) EP2588407A1 (en)
JP (1) JP2013533841A (en)
KR (1) KR20130098272A (en)
CN (1) CN102971254A (en)
CA (1) CA2803044A1 (en)
WO (1) WO2012001094A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111320144A (en) * 2020-03-30 2020-06-23 中北大学 Melanin-nano selenium and preparation method thereof

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 A kind of transition metal dichalcogenide compound with striped structure and preparation method thereof
CN113874547B (en) * 2019-11-12 2024-06-18 株式会社力森诺科 Deposit removal method and film forming method
CN111807333B (en) * 2020-07-28 2023-06-23 安徽大学 Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice
KR20240109987A (en) * 2021-11-22 2024-07-12 미쓰이금속광업주식회사 Lithium sulfide and its production method and method of producing sulfide solid electrolyte
CN114671414B (en) * 2022-03-25 2023-05-16 浙江大学 Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method
CN116332137B (en) * 2023-01-05 2024-05-24 南京信息工程大学 A multi-element metal selenide absorbing material and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
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
US6127202A (en) 1998-07-02 2000-10-03 International Solar Electronic Technology, Inc. Oxide-based method of making compound semiconductor films and making related electronic devices
CN101219779B (en) * 2008-01-14 2010-07-28 重庆大学 Method for preparing selenide or telluride nanomaterials from composite alkali metal hydroxide solvent
KR100989077B1 (en) * 2008-02-27 2010-10-25 한국과학기술연구원 Manufacturing method of thin film for solar cell using paste and thin film for solar cell obtained by
TWI421214B (en) * 2008-12-03 2014-01-01 財團法人工業技術研究院 IBIIIAVIA family amorphous phase compound and method for producing IBIIIAVIA family amorphous phase precursor applied to thin film solar cell
CN101613091B (en) * 2009-07-27 2011-04-06 中南大学 CIGS powder, CIGS target, CIGS film and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012001094A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111320144A (en) * 2020-03-30 2020-06-23 中北大学 Melanin-nano selenium and preparation method thereof

Also Published As

Publication number Publication date
CN102971254A (en) 2013-03-13
WO2012001094A1 (en) 2012-01-05
JP2013533841A (en) 2013-08-29
KR20130098272A (en) 2013-09-04
CA2803044A1 (en) 2012-01-05

Similar Documents

Publication Publication Date Title
CA2706380C (en) Preparation of nanoparticle material
WO2012001094A1 (en) Selenide powders and manufacturing process
JP6688832B2 (en) Antimony-doped nanoparticles
TWI552373B (en) CIGS nanoparticle ink formulation with high crack-free limit
JP2017206431A (en) Cu2ZnSnS4 nanoparticles
US20180248057A1 (en) Preparation of Copper-Rich Copper Indium (Gallium) Diselenide/Disulphide Nanoparticles
TWI675890B (en) Cigs nanoparticle ink formulation with a high crack-free limit

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130204

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20131206

RIC1 Information provided on ipc code assigned before grant

Ipc: B82Y 30/00 20110101AFI20131122BHEP

Ipc: C01B 19/00 20060101ALI20131122BHEP

Ipc: H01L 31/032 20060101ALI20131122BHEP

RIN1 Information on inventor provided before grant (corrected)

Inventor name: AMINIAN, HOSSEIN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140417