EP2670877A1 - Dispositif de séparation et procédé de fabrication d'un creuset associé - Google Patents

Dispositif de séparation et procédé de fabrication d'un creuset associé

Info

Publication number
EP2670877A1
EP2670877A1 EP12713863.4A EP12713863A EP2670877A1 EP 2670877 A1 EP2670877 A1 EP 2670877A1 EP 12713863 A EP12713863 A EP 12713863A EP 2670877 A1 EP2670877 A1 EP 2670877A1
Authority
EP
European Patent Office
Prior art keywords
crucible
protective layer
separating device
titanium
titanium oxide
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Withdrawn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
EP12713863.4A
Other languages
German (de)
English (en)
Inventor
Johan MATHIASSON
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.)
Beijing Apollo Ding Rong Solar Technology Co Ltd
Original Assignee
Solibro GmbH
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 Solibro GmbH filed Critical Solibro GmbH
Publication of EP2670877A1 publication Critical patent/EP2670877A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10Oxidising
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623Sulfides, selenides or tellurides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • C23C14/243Crucibles for source material
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • H01L31/182Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/546Polycrystalline silicon PV cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/4998Combined manufacture including applying or shaping of fluent material
    • Y10T29/49982Coating
    • Y10T29/49986Subsequent to metal working

Definitions

  • the invention relates to a deposition device for depositing thin layers and to a method for producing a crucible for such a deposition device.
  • Such deposition devices can be used, for example, for depositing some or all layers of a thin-film solar cell onto a substrate.
  • a thin-film solar cell onto a substrate.
  • Selenium films are deposited on a substrate to produce so-called CIGS solar cells.
  • the material to be deposited is placed in a crucible of the separators and heated while the substrate is disposed opposite an opening of the crucible.
  • Heating the material in the crucible causes the material to evaporate and exit the crucible through the opening to cover the substrate.
  • the material in the crucible As the material in the crucible is heated, it may react with the material of the crucible itself, which may then over time lead to corrosion of the crucible surface and deterioration of the crucible.
  • crucibles formed of titanium which are used to vaporize
  • Such crucibles are for example in
  • crucibles formed from titanium oxide have been prepared in
  • Lithium ion batteries Lithium ion batteries.
  • the use of such inert materials for the whole crucible reduces the problem of reaction with the
  • the object is according to the invention by a separating device with the features of claim 1 and by a method for producing a crucible for such a separating device with the features of
  • the invention is based on the combined advantage of a crucible body formed of metal and a protective layer which separates this metal material from the deposition material and thus protects the crucible from corrosion. Having a metal body, the crucible has the advantage of being less sensitive to temperature changes. Further, the metal body of the crucible may be cheaper to manufacture than a crucible formed entirely of a ceramic material. Since only the interior of the crucible can come into contact with the deposition material, it may be sufficient to only part or all of it
  • the separation device requires heating means for heating the deposition material, for example selenium, which is arranged in the crucible, to the temperature necessary for separation.
  • the heating means may thus comprise one or more resistive heaters disposed in contact with or near the crucible.
  • Other heating means for direct or indirect heating of the deposition / evaporation material may include inductive heating means, laser heating means, ionizing heating means or other suitable means.
  • the step of covering the crucible body with the protective layer may take place immediately before putting a new crucible into operation
  • the protective layer may be formed on the surface of the crucible body by a deposition method such as physical or chemical deposition, for example, by electroplating the titanium oxide on the
  • the titanium oxide (Ti x O y ) of the protective layer is an induced oxide layer.
  • the titanium oxide protective layer is formed by oxidizing said part of the inner surface of the crucible body.
  • this surface part must be made of a titanium-based alloy with a
  • the crucible body may be formed of a layered metal structure in which the uppermost layer or a part of the uppermost layer comprises a titanium-based alloy. If the titanium oxide of the protective layer is an induced oxide layer, it can by means of heating the crucible body in a
  • Oxygen atmosphere or in an oxygen-rich atmosphere can be generated, for example in an oven.
  • the body of the crucible is formed of a titanium-based alloy. It may even be formed entirely of a titanium-based alloy, which is later either covered with titanium oxide or whose surface may be oxidized, in order to protect it
  • a titanium-based alloy in the present sense may be any metallic alloy whose principal constituent element is titanium.
  • titanium is the element with the highest content in a titanium-based alloy.
  • the material should contain enough titanium to get a
  • the titanium content of such a titanium-based alloy is at least 50 weight percent (wt%).
  • the titanium content is much higher, for example above 60 wt%, above 70 wt%, above 80 wt%, above 90 wt%, or above 95 wt%.
  • a titanium-based alloy according to the invention may also be a pure one
  • Titanium metal or a titanium metal containing contaminants or impurities of another material.
  • the body of the crucible is formed of sheet metal.
  • the metal sheet may be formed by a rolling process.
  • the Crucible body may be formed of two or more interconnected parts.
  • the protective layer should preferably have a thickness of at least 50 nm, at least 100 nm, at least 150 nm, at least 200 nm, at least 300 nm or at least 500 nm. It is advantageous for the protective layer to have a certain minimum thickness in order to protect the metal of the crucible body. A thickness of a few nanometers or less might be too low for this purpose. On the other hand, if the protective layer is too thick, it may peel off due to the brittle structure of the titanium oxide. The surface of the crucible would then be exposed and vulnerable to the
  • means are provided for holding a solar cell substrate in order to evaporate material disposed in the crucible on a surface of the
  • Such a deposition device can be designed, for example, to deposit one or several layers for the production of thin-film solar cells, for example CIGS solar cells.
  • the deposition device can be designed to coat a substrate with selenium.
  • the retaining means would advantageously allow the arrangement of a substantially rectangular glass plate adjacent to the crucible opening.
  • the crucible body may be made by any suitable method before it is completely or partially covered with the protective layer.
  • a preferred method which can be used to produce the metallic material for the body of the crucible is a rolling process, in particular hot rolling or cold rolling of the metal.
  • the metal sheet produced in this way can then be formed into the crucible body.
  • one or all parts of the crucible body by casting be obtained from a molten metal or by metal machining of a metal piece.
  • FIG. 1 shows an arrangement for depositing a material from a crucible on a substrate.
  • Embodiment of the invention. 1 shows a schematic representation of a deposition arrangement with a substrate 4, which is held by means of a substrate holder 5.
  • a surface 41 of the substrate faces a crucible 1 filled with a deposition material 3.
  • Heating means 2 are arranged around the crucible 1, which can heat the crucible 1 and consequently the deposition material 3, which therefore evaporates and on with the
  • the remainder of the separation device comprising the crucible 1 and the substrate 5 is not shown in FIG. 1, for example a vacuum chamber in which the crucible 1 is arranged.
  • the crucible 1 is formed entirely of metal, there is a possibility that the deposition material (evaporation material) 3 with the
  • Inner surface 12 of crucible 1 reacts when heated to a sufficient temperature.
  • the inner surface 12 is at least partially covered with a protective layer 13.
  • Preferred embodiments of such a crucible 1 are shown in FIGS. 2 and 3. While the crucible 1 shown in Fig. 2 has cylindrical side walls and has a square, a rectangular, a circular or any other suitable shape, the crucible 1 shown in Fig. 3 has a conical shape. In both cases, the crucible 1 has a crucible body 11 and a protective layer 13 which covers at least part of the inner surface 12. In the embodiments shown in FIGS. 2 and 3, the entire inner surface 12 of the crucible 1 is covered with the protective layer 13. In other preferred
  • the crucible body 11 may be completely covered with the protective layer 13.
  • Both crucibles 1 shown in FIGS. 2 and 3 have heating means 2 for
  • Heating the evaporation material (not shown in FIGS. 2 and 3) to allow its evaporation on the substrate 4.
  • the heating means 2 may include any type of heater for transferring energy to the heater
  • Devices include inductive heating means, laser heating means, ion heating means and the like.
  • FIG. 4a), 4b), and 4c) illustrate schematically methods for the production of a crucible 1 with a protective layer 12 according to a preferred embodiment.
  • the crucible body 11 can be formed, for example, from sheet metal, which was obtained by means of a rolling process.
  • the crucible body 11 used for this process is preferably formed from a titanium-based alloy.
  • the crucible body 11 is placed in an oven 6 to be heated.
  • an oxygen atmosphere By heating the Crucible 1 in an oxygen atmosphere is oxidized the entire surface or, in the case of limited oxygen exposure, part of the surface of the crucible 1 to form the protective layer 13, as shown schematically in Fig. 4c).
  • the protective layer 13 may additionally be reinforced by a deposition method such as physical or chemical deposition. Alternatively, such methods may be used to create the entire protective layer 13.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physical Vapour Deposition (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
EP12713863.4A 2011-02-04 2012-01-31 Dispositif de séparation et procédé de fabrication d'un creuset associé Withdrawn EP2670877A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011000502A DE102011000502A1 (de) 2011-02-04 2011-02-04 Abscheidevorrichtung und Verfahren zur Herstellung eines Tiegels hierfür
PCT/DE2012/100020 WO2012103885A1 (fr) 2011-02-04 2012-01-31 Dispositif de séparation et procédé de fabrication d'un creuset associé

Publications (1)

Publication Number Publication Date
EP2670877A1 true EP2670877A1 (fr) 2013-12-11

Family

ID=45952809

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12713863.4A Withdrawn EP2670877A1 (fr) 2011-02-04 2012-01-31 Dispositif de séparation et procédé de fabrication d'un creuset associé

Country Status (8)

Country Link
US (1) US20140026815A1 (fr)
EP (1) EP2670877A1 (fr)
JP (1) JP6050255B2 (fr)
KR (1) KR20130110211A (fr)
CN (1) CN103459650A (fr)
DE (1) DE102011000502A1 (fr)
TW (1) TWI576447B (fr)
WO (1) WO2012103885A1 (fr)

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KUMAR S ET AL: "Thermal oxidation of CP-Ti: Evaluation of characteristics and corrosion resistance as a function of treatment time", MATERIALS SCIENCE AND ENGINEERING C, ELSEVIER SCIENCE S.A, CH, vol. 29, no. 6, 1 August 2009 (2009-08-01), pages 1942 - 1949, XP026322583, ISSN: 0928-4931, [retrieved on 20090313], DOI: 10.1016/J.MSEC.2009.03.007 *
See also references of WO2012103885A1 *

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JP6050255B2 (ja) 2016-12-21
US20140026815A1 (en) 2014-01-30
TW201233831A (en) 2012-08-16
WO2012103885A4 (fr) 2012-10-18
TWI576447B (zh) 2017-04-01
WO2012103885A1 (fr) 2012-08-09
KR20130110211A (ko) 2013-10-08
CN103459650A (zh) 2013-12-18
JP2014508860A (ja) 2014-04-10

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