EP2134883A1 - Oxynitrid-sputtering-target - Google Patents

Oxynitrid-sputtering-target

Info

Publication number
EP2134883A1
EP2134883A1 EP08788046A EP08788046A EP2134883A1 EP 2134883 A1 EP2134883 A1 EP 2134883A1 EP 08788046 A EP08788046 A EP 08788046A EP 08788046 A EP08788046 A EP 08788046A EP 2134883 A1 EP2134883 A1 EP 2134883A1
Authority
EP
European Patent Office
Prior art keywords
target
atomic
nitrogen
lithium
target according
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Withdrawn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
EP08788046A
Other languages
English (en)
French (fr)
Inventor
Michel Martin
Olivier Blandenet
Philippe Maurin-Perrier
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.)
Hydromecanique et Frottement SAS
Original Assignee
HEF SAS
Hydromecanique et Frottement SAS
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 HEF SAS, Hydromecanique et Frottement SAS filed Critical HEF SAS
Publication of EP2134883A1 publication Critical patent/EP2134883A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/3426—Material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/40—Printed batteries, e.g. thin film batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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

  • the subject of the invention is an ionic sputtering target of lithium oxynitride. It also relates to a method of manufacturing an electrolyte in the form of a thin layer of lithium oxynitride from said target. Finally, it relates to an electrochemical device comprising a substrate provided with said electrolyte.
  • the electrochemical devices of the all-solid microbattery type with an electrochromic system or else a micro or super capacitance system, comprise an electrolyte membrane in the form of a mineral thin film with a thickness of between 1 and 2 ⁇ , the layer being deposited under vacuum by sputtering from a target.
  • the targets currently used are of the oxide type such as, for example, lithium phosphate (Li 3 PO 4 ), lithium silicate (SiO 4 ) lithium borate (LiBO 2 ), lithium sulphate (Li 2 SO 4 ) and are generally sprayed. under pure nitrogen which improves the electrochemical performance.
  • oxide type such as, for example, lithium phosphate (Li 3 PO 4 ), lithium silicate (SiO 4 ) lithium borate (LiBO 2 ), lithium sulphate (Li 2 SO 4 ) and are generally sprayed. under pure nitrogen which improves the electrochemical performance.
  • the document Scripta materials 42 (2000) 43-49 describes the implementation of a molar composition target Li 3 PO 4 + Li 3 N to obtain a thin layer of lithium oxynitride.
  • the target is sprayed under nitrogen at high power densities of between 2 and 5 watts per cm 2 . Under these conditions, the deposition rate remains low, less than 5 nm per minute at 5 watts per cm 2 .
  • the HAMON thesis finally puts the accent on the lack of consistency of the mechanical properties of the thin layers obtained from one sample to another.
  • the problem to be solved by the invention is therefore to develop a target which makes it possible to industrialize the process for depositing metal oxynitride thin films by ion sputtering at a deposition rate greater than 30 nm / min while obtaining a maximum conductivity for a given material and improved mechanical properties of the thin layer.
  • the Applicant has developed a novel metal sputtering oxynitride target comprising: between 30% and 40% by weight of a metal, in particular lithium; - between 2% and 10% atomic nitrogen; between 35% and 50% atomic oxygen, the 100% complement consisting of at least one element selected from the group consisting of phosphorus (P), boron (B), silicon (Si), germanium (Ge), gallium (Ga), sulfur (S) and aluminum (Al).
  • the ionic conductivity of the thin layers is too low.
  • the thin layers obtained frequently have growth defects which renders them unsuitable for use as electrolytes, in particular at deposition rates higher than 1 ⁇ m / hour.
  • the total atomic concentration in the target of the element (s) chosen from the group comprising phosphorus (P), boron (B), silicon (Si), germanium (Ge), gallium ( Ga), the sulfur (S) and the aluminum (Al) is between 10% and 25%, advantageously between 12% and 20%.
  • the target further contains phosphorus and / or boron and / or silicon.
  • the atomic concentration of lithium is between 33% and 38%
  • the atomic concentration of nitrogen is between 4% and 8%
  • the atomic concentration of oxygen is between 40 and 45%.
  • the target may contain impurities that can come either from the starting components used in its manufacture, or be incorporated at the time of manufacture.
  • the impurities represent less than 2 mol% of the target. At this rate, no substantial change in the properties of the materials obtained is observed.
  • the target may be in the form of a homogeneous glass or be formed of homogeneous grains or grains of different types distributed regularly. in the target.
  • Preferred targets of the invention have the following crude formulas: Li 3 P 1 O 311 No 10 ; Li 2 , 5Po, 5Si, 5O 2, 6 No, 6; (Li 3 PO 4 ) o, 6 (B2 ⁇ 3 ) o, 2 (Li 3 N) o, 3
  • the invention also relates to a method of manufacturing a thin film based on metal oxynitride by magnetic field assisted sputtering in an oxidizing reactive atmosphere of a target, as previously described.
  • the reactive atmosphere may consist of a gas such as pure nitrogen or a mixture of gases, in particular a nitrogen / argon mixture.
  • the spraying is carried out at a power density of between 0.5 W / cm 2 and 5 W / cm 2 .
  • the invention also relates to an electrochemical device such as for example a microbattery, an electrochromic system or a micro super capacitor comprising an electrolyte in the form of a thin layer obtained according to the method described above.
  • an electrochemical device such as for example a microbattery, an electrochromic system or a micro super capacitor comprising an electrolyte in the form of a thin layer obtained according to the method described above.
  • the x, y and z values correspond to the atomic concentrations of Li, O and N.
  • the targets of Examples 1a, 2a and 3a are in accordance with the targets of the invention.
  • the targets of Examples Ib, 2b and 3b, and 6 are examples illustrating targets of the prior art and targets 4 and 5 of nonconforming targets. The formulas of the different targets tested are reproduced in the table below.
  • PiO 3 No 10 whose ionic conductivity of lithium at ambient temperature is 2.5 E-6 Scm -1 is obtained.
  • a layer of this electrolyte with a thickness of 1.5 ⁇ m is perfectly satisfactory for insertion into a lithium microbattery.
  • Example Ib A homogeneous Li 3 PO 4 spray and composition target not according to the invention is pulverized by high frequency magnetron sputtering under a pure nitrogen pressure of 0.8 Pa at a power density of 4 W / cm. 2 and at a target distance / substrates of 10 cm.
  • a deposition rate of 3 ⁇ m / h of a vitreous thin layer is obtained on a part of its surface and of dull appearance in places.
  • the thin layer has a composition Li 2 6 P 1 O 3> 6 No , 1 and its lithium ionic conductivity at ambient is 0.3 E-6 Scm -1 .
  • the conductivity obtained at this power density from such a target is about three to four times lower than expected from this material and secondly the growth of the thin layer formed under these conditions does not make reliable industrial production since significant areas of the thin layer show a columnar growth unsuitable for use as an electrolyte in a microbattery, an electrochromic system or super capacity.
  • the deposition rate obtained is 3 ⁇ m / h and a thin glassy film with a homogeneous appearance of composition Li 2 , 4Po, 5SiO, 5 ⁇ 2j 2 No, 8 and an ionic conductivity of lithium at room temperature of 12 E is obtained. 6 Scm "1.
  • a layer of this electrolyte with a thickness of 1.5 microns is perfectly satisfactory for insertion into a microbattery.
  • a composition of Li 2 S Po 1S sputtering target If O1S O 31S homogeneous non-compliant to the invention is sprayed by spraying high frequency magnetron under a pressure of 0.6 Pa with a 50/50 mixture of argon / nitrogen a power of 3.5 W / cm 2 at a target distance / substrates of 10 cm.
  • the deposition rate obtained is 2.5 ⁇ m / h and a thin vitreous matrix layer having small grains included in the layer is obtained.
  • the average composition of the thin layer is Li 24 Po 1S Si O1S O 313 No. 11 and its lithium ionic conductivity at room temperature is 2 E-7 Scm -1 .
  • This thin layer can be used as an electrolyte for microbatteries, but its conductivity is low for this type of material and the growth of the layer shows what could be a phase separation which risks compromising its industrialization.
  • the raw composition of the target is in accordance with the invention.
  • the target is sputtered by high frequency magnetron sputtering at 0.8Pa nitrogen at a power density of 2W / cm 2 and at a target distance / substrate of 10cm.
  • a deposition rate of 2 ⁇ m / h of a vitreous thin layer having the composition Li 21S Po 10 Bo 13 O 21S No 1S is obtained, the ionic conductivity of lithium at ambient temperature being 1.2 E-6 Scm -1 .
  • a layer of this electrolyte with a thickness of 1.5 ⁇ m is perfectly satisfactory for insertion into a microbattery.
  • Example 3b A molar composition target (Li 3 P ⁇ 4 ) o , 6 (LiB0 2 ) o , 4 not according to the invention obtained by homogeneous agglomeration of the two powders: Li 3 PO 4 ; LiBO 2 is pulverized by high frequency magnetron sputtering at 0.8Pa nitrogen at a power density of 2W / cm and at a target distance / substrate of 10cm. A deposition rate of 1.6 ⁇ m / h of a vitreous thin layer having the composition Li 2 2 Po 10 Bo 13 O 2 C No 11 having a lithium ion conductivity at ambient temperature of 4 E-7 is obtained. Scm "1. As seen in the examples and 3a, one can expect to obtain with this type of material, the thin film having an ionic conductivity at room temperature approximately four times better.
  • a target composition Li 2 2 P 1 O 214 No ⁇ not according to the invention is sprayed by high frequency magnetron sputtering at 0.8Pa nitrogen at a power density of 2W / cm 2 and a target distance / substrates of 10 cm.
  • the thin layer obtained has a high state of tensile stresses when it is deposited on a white soda-lime glass substrate and it can even be noted local delamination of the thin layer whose observation under a microscope confirms its voltage state.
  • the electrochemical stability of the thin layer indicates that it begins to deteriorate when applied to it with a polarization greater than 4 V.
  • a good material of the same family of composition Li 2 8 P 1 O 3 No 1O supports more than 5 V and does not have a high state of stress, a high deposition rate is obtained with this target, but the properties compatible with industrialization of the thin films produced are not obtained.
  • a sputtering target of a non-conforming homogeneous Li 1 P 1 O 214 No 14 composition is pulverized by high frequency magnetron sputtering at a pressure of 0.8 Pa of a 50/50 Argon / Nitrogen gas mixture at a power density of 2 W. / cm and at a target distance / substrates of 10 cm.
  • Li 1 P 1 O 23 No 14 the ionic conductivity of lithium at room temperature is 1E-8 Scm -1 .
  • a layer of this electrolyte with a thickness of 1.5 ⁇ m can be used for its insertion in a microbattery, for example, but its conductivity is too far from the current standards obtained in example la to claim its industrialization.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Analytical Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Physical Vapour Deposition (AREA)
  • Conductive Materials (AREA)
EP08788046A 2007-04-06 2008-03-26 Oxynitrid-sputtering-target Withdrawn EP2134883A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0754340A FR2914653B1 (fr) 2007-04-06 2007-04-06 Cible de pulverisation cathodique d'oxynitrure
PCT/FR2008/050520 WO2008132409A1 (fr) 2007-04-06 2008-03-26 Cible de pulverisation cathodique d'oxynitrure

Publications (1)

Publication Number Publication Date
EP2134883A1 true EP2134883A1 (de) 2009-12-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP08788046A Withdrawn EP2134883A1 (de) 2007-04-06 2008-03-26 Oxynitrid-sputtering-target

Country Status (7)

Country Link
US (1) US8728287B2 (de)
EP (1) EP2134883A1 (de)
JP (1) JP5599703B2 (de)
KR (3) KR20150023850A (de)
CN (1) CN101652496B (de)
FR (1) FR2914653B1 (de)
WO (1) WO2008132409A1 (de)

Families Citing this family (7)

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CN101872855B (zh) * 2010-06-17 2012-10-17 复旦大学 一种用于锂离子电池的负极材料v2on及其制备方法
FR2964963A1 (fr) * 2010-09-21 2012-03-23 St Microelectronics Tours Sas Electrolyte solide vitreux pour cellule electrochimique
US8894825B2 (en) 2010-12-17 2014-11-25 Semiconductor Energy Laboratory Co., Ltd. Sputtering target, method for manufacturing the same, manufacturing semiconductor device
US9566618B2 (en) 2011-11-08 2017-02-14 Tosoh Smd, Inc. Silicon sputtering target with special surface treatment and good particle performance and methods of making the same
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FR2914653A1 (fr) 2008-10-10
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FR2914653B1 (fr) 2009-05-22
KR20160087396A (ko) 2016-07-21
KR20150023850A (ko) 2015-03-05
US8728287B2 (en) 2014-05-20
CN101652496A (zh) 2010-02-17
KR20090127906A (ko) 2009-12-14
CN101652496B (zh) 2012-10-03
JP2010523815A (ja) 2010-07-15

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