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WO2011119041A1 - Minces films conducteurs protoniques ou mixtes protoniques et électroniques - Google Patents

Minces films conducteurs protoniques ou mixtes protoniques et électroniques Download PDF

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WO2011119041A1
WO2011119041A1 PCT/NO2011/000098 NO2011000098W WO2011119041A1 WO 2011119041 A1 WO2011119041 A1 WO 2011119041A1 NO 2011000098 W NO2011000098 W NO 2011000098W WO 2011119041 A1 WO2011119041 A1 WO 2011119041A1
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thin film
proton conducting
ceramic
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Erik ØSTRENG
Ola Nilsen
Helmer FJELLVÅG
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical 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
    • C23C16/455—Chemical 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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical 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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel 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

  • the present invention relates to a process for preparing ceramic proton conducting oxide thin films and mixed ceramic proton and electronic conducting oxide thin films.
  • Oxide based proton conducting ceramic films and coatings are of special interest in connection with proton conducting solid oxide fuel cells, steam electrolysers, electrochemical hydrogen pumps and hydrogenation/dehydrogenation reactors, sensors, catalytic membranes, and within hydrogen permeable membranes for production and purification of hydrogen as well as hydrogenation and dehydrogenation reactors, as described in prior art [
  • Proton conducting ceramic materials are mostly based on doped or undoped binary or ternary oxides such as oxides with perovskite or fluorite related structures or related ceramic materials.
  • the oxides consists of different classes of cations which are described as basic, amphoteric (intermediate basic-acidic properties) or acidic according to their chemical properties which relates to the ionic size, formal oxidation state, and chemical bonding of the cation in a given chemical compound. Acidity increases while basicity decreases as the cation's size decreases and formal oxidation state increases.
  • Basic cations comprise M of group 2 and 12 of the Periodic Table; and M of group 3 and 13; and M 3+ of the lanthanide elements (No. 57-71 in the Periodic Table).
  • Acidic cations comprise M 3+ , M 4 , M 5+ and M 6+ cations of groups 4-7 and 13-16, and M 4+ of the lanthanide elements Ce and Pr.
  • Amphoteric cations comprise M of group 2, 11 and 12 of the Periodic Table; M of group 7, 8 and 13.
  • Binary oxides are compounds between oxide ions and one type of cations from either of the classes of cations.
  • Ternary oxides are compounds between oxide ions and two different cations (A and B) from one or two classes of cations.
  • the first type of cations (“A") may be basic or amphoteric and the second type (“B") may be amphoteric or acidic.
  • Such ternary oxides of certain group 14, 15, 16 elements may be named as oxoacid salt (e.g. silicate, phosphate, sulfate).
  • a ceramic proton conducting oxide is an undoped or acceptor-doped oxide in which water vapour dissolves and by which the oxide becomes hydrated and thereby contains hydroxide ions.
  • the material becomes proton conducting as the protons on hydroxide ions jump between oxide ions.
  • Ceramic proton conductors which also show electronic conductivities are a subgroup of ceramic proton conductive materials and is also known under the term mixed conductor.
  • Ceramic materials have to be cation acceptor doped in order to achieve a suitable proton conductivity.
  • To acceptor dope cations in the structure means to substitute a constituent cation of the binary or ternary oxide with another cation which has a lower formal oxidation number than the constituent cation.
  • the terms substituted and doped implies the same effect in this respect and the terms are therefore used interchangeably in this text.
  • Non-limiting examples of ceramic proton conducting oxide materials, which do not need to be acceptor doped are La 26 0 27 (B0 3 ) 8 , TiP 2 0 7 , and La5 .6 W0 11 4 .
  • Ceramic proton conducting oxide materials may also be formed as solid solutions between two or more compounds.
  • Solid solution means a binary or ternary oxide where one or two constituent cations are substituted by a basic, amphoteric or acidic cation with the same formal oxidation state as the constituent cation.
  • the object of the present invention is to provide an improved method for producing a proton conducting thin film of a stable ceramic oxide.
  • Another object is to provide a gas tight film on a dense or porous hydrogen permeable electron conducting substrate so as to act as an electrolyte in an electrochemical device such as fuel cell, steam electrolyser, hydrogen pump, or sensor.
  • Another object is to provide a gas tight film of a mixed proton electron conducting oxide on a dense or porous hydrogen permeable substrate so as to act as a selective hydrogen permeable membrane in an application for separation or purification of hydrogen or a hydrogenation or dehydrogenation reactor.
  • Another object is to provide a gas tight thin, proton conducting, stable ceramic film on a substrate structure so as to close pinholes or other defects in the substrate.
  • a thin film is produced by the ALD technique by using different types of precursors.
  • the precursors are pulsed sequentially into the reaction chamber where they react with a surface; each pulse is followed by a purging time with an inert gas or an evacuation of the reactor. In this way gas phase reactions are eliminated and film is constructed by precursor units in the order that they are pulsed.
  • This technique makes it possible to change building units at the resolution of one monolayer, and therefore enables production of artificial structures of films with different types of inorganic or organic building units or combinations thereof.
  • the ALD technique is superior with respect to formation of pin-hole free films on substrates with complex geometries such as cathodes or anodes in fuel cell applications.
  • a number of ceramic proton conducting materials have previously been described in connection with the production of fuel cells. Similarly, a number of ceramic proton conducting materials with additional conduction by electrons have been described in connection with production of dense, ceramic hydrogen permeable membranes. Calcium substituted lanthanum niobate has not been demonstrated deposited earlier by ALD.
  • Titanium phosphates have not been demonstrated deposited earlier by ALD.
  • Proton conducting barium or strontium cerate and zirconate has previously been suggested deposited by, among other, ALD in US 7691523 by the formulation solid perovskite electrolyte membrane.
  • the patent US 7691523 does not exemplify deposition by ALD, but rather PLD.
  • the mentioned barium or strontium cerate and zirconate are based on rather basic earth alkaline materials which make them prone to degradation under exposure to organic compounds or C0 2 due to formation of carbonate.
  • the present invention has main focus on utilization of proton conducting ceramics based on less basic elements than Sr and Ba, amongst others phosphates, niobates and tungstenates
  • the present invention provides a method for producing proton conducting thin films using ALD.
  • the method according to the present invention results in stable films, most types being less prone to degradation by C0 2 .
  • the problem with high grain boundary resistance is also avoided by formation of textured materials by ALD.
  • the present invention thus provides a process for fabricating a ceramic proton conducting oxide thin film, where the process comprises utilizing atomic layer deposition technique and depositing atomic layers, building a ceramic oxide on a substrate by reaction with the top layer on said substrate, thereby forming a stable ceramic proton conducting oxide thin film.
  • the present invention provides a method for producing a proton conducting calcium substituted lanthanum niobate thin film using ALD.
  • the present invention provides a method for producing a proton conducting calcium substituted lanthanum phosphate thin film using ALD.
  • the present invention provides a method for producing a proton conducting, pure or substituted, lanthanum tungstate thin film using ALD.
  • a thin film for lanthanum tungstanate according to the present invention can be deposited using an ALD reactor using WF 6 , La(thd) 3 or La(cp) 3 or its derivatives, as metal containing precursors and H 2 0, 0 3 or a mixture thereof as oxygen containing precursor, wherein thd stands for 2,2,6,6-tetramethylheptane-3,5-dionate and cp stands for cyclopentadienyl.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors..
  • the films are deposited through alternating pulses of these precursors separated by purging by inert gas or evacuation. The process is repeated until the desired film thickness is achieved.
  • a thin film of lanthanum molybdate according to the present invention can be deposited using an ALD reactor using Mo(CO) 6 , La(cp) 3 or its derivatives, as metal containing precursors and H 2 0, 0 3 or a mixture thereof as oxygen containing precursor, wherein cp stands for cyclopentadienyl.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors..
  • the films are deposited through alternating pulses of these precursors separated by purging by inert gas or evacuation. The process is repeated until the desired film thickness is achieved.
  • a thin film of titanium phosphate such as but not limited to TiP 2 0 7 , according to the present invention can be deposited using an ALD reactor and Me 3 (P0 4 ), T1CI4 or Ti (0'Pr) 4 as metal containing precursors and H 2 0, O3 or a mixture thereof as oxygen containing precursor, wherein Pr stands for propyl.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors.
  • the films are deposited through alternating pulses of these precursors separated by purging by inert gas or evacuation. The process is repeated until the desired film thickness is achieved.
  • a thin film of yttrium doped barium zirconate according to the present invention can be deposited using an ALD reactor and Y(thd) 3 or YCp 3 , ZrCl 4 or Zr(0'Bu) 4 , Ba(thd) 2 or BaCp 2 or its derivatives, as metal containing precursors and H 2 0, 0 3 or a mixture thereof as oxygen containing precursor, wherein thd stands for 2,2,6,6- tetramethylheptane-3,5-dionate and Bu stands for butyl.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors..
  • the films are deposited through alternating pulses of these precursors separated by purging by inert gas or evacuation. The process is repeated until the desired film thickness is achieved.
  • a thin film for strontium doped lanthanum borate according to the present invention can be deposited using an ALD reactor using Sr(thd) 2 or SrCp 2 or its derivatives, BBr 3 or B(OMe) 3 or B 2 H 6 , La(thd) 3 or La(cp) 3 or its derivatives, as metal containing precursors and H 2 0, 0 3 or a mixture thereof as oxygen containing precursor, wherein thd stands for 2,2,6,6-tetramethylheptane-3,5-dionate and cp stands for cyclopentadienyl.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors.
  • a thin film for lanthanum oxoborate borate according to the present invention can be deposited using an ALD reactor using BBr 3 or B(OMe) 3 or B 2 H 6 , La(thd) 3 or La(cp) 3 or its derivatives, as metal containing precursors and H 2 0, O3 or a mixture thereof as oxygen containing precursor, wherein thd stands for 2,2,6,6-tetramethylheptane-3,5- dionate and cp stands for cyclopentadienyl.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors.
  • the films are deposited through alternating pulses of these precursors separated by purging by inert gas or evacuation. The process is repeated until the desired film thickness is achieved.
  • the present invention also provides a ceramic proton conducting oxide thin film, prepared by the above process, wherein the film is pin-hole free.
  • the invention provides a ceramic mixed proton and electronic conducting oxide structure comprising a porous oxide substrate provided with a gas tight ceramic proton conducting oxide thin film, which is selectively permeable to hydrogen.
  • the invention also provides a fuel cell structure consisting of ceramic proton conducting oxide thin film as described above, deposited on a porous or dense hydrogen-permeable electron-conducting substrate acting as one half electrode.
  • the invention further provides a ceramic proton conducting thin film on a porous or dense substrate, codeposited with reducible oxides that upon activation in reducing atmosphere convert to catalytically active centers on the said proton conducting thin film, and thereby constitute a catalytic proton conducting ceramic membrane.
  • Fig. 1 is a scanning electron microscope (SEM) picture of a calcium doped lanthanum niobate film obtained utilizing the present invention
  • Fig. 2 is a scanning electron microscope (SEM) picture of a calcium doped lanthanum niobate film obtained utilizing the present invention
  • Figure 3 shows an impedance plot for a proton conducting solid oxide fuel cell (PC- SOFC) wherein the proton conducting electrolyte is obtain according to the present invention.
  • the thin films according to the present invention can be deposited using an ALD reactor and Nb(EtO) 5 , La(thd) 3 , Ca(thd) 2 as metal containing precursors and H 2 0, 0 3 or a mixture thereof as oxygen containing precursor, wherein thd stands for 2,2,6,6- tetramethylheptane-3,5-dionate.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors..
  • the films are deposited through alternating pulses of these precursors separated by purging by inert gas or evacuation. The process is repeated until the desired film thickness is achieved.
  • Films can be deposited using an optimised pulsing scheme of the individual deposition sub-cycles comprising:
  • a temperature window should be established. The window defines a temperature interval where all sub-cycles can successfully take place. If a temperature window can not be found for the selected precursors, the precursors must be exchanged and new tests performed to evaluate if there exist a temperature window for the new precursor selection.
  • the sequence and the number of repetitions of the different sub-cycles can be varied to obtain films with different compositions.
  • Examples of possible deposition schemes for deposition of lanthanum-niobate films comprise:
  • the total deposition scheme can comprise any repetition of these deposition schemes either separately or any combination thereof.
  • the sub-cycle for the dopant Ca will only be included a limited number of times in the total deposition scheme. This can be done either by exchanging one La- or Nb-cycle with a Ca-cycle or by introducing an extra sub-cycle.
  • the amount of dopant can vary depending on the desired properties of the resulting film.
  • concentration of the dopant Ca will normally be between 0.1% and 5%, based on the total number of La and Ca atoms. In one embodiment the concentration of Ca is approximately 0.5%.
  • Other thin films according to the present invention can be deposited using an ALD reactor and Me 3 (P0 4 ), La(thd) 3 , Ca(thd) 2 as metal containing precursors and H 2 0, 0 3 or a mixture thereof as oxygen containing precursor, wherein thd stands for 2,2,6,6- tetramethylheptane-3,5-dionate.
  • the suggested precursors are only examples of suitable precursors for deposition of these materials and do not limit this invention to these said precursors.
  • the films are deposited through alternating pulses of these precursors separated by purging by inert gas or evacuation. The process is repeated until the desired film thickness is achieved.
  • Films can be deposited using a pulsing scheme of the individual deposition sub-cycles comprising:
  • the sub-cycle for the dopant Ca will only be included a limited number of times in the total deposition scheme. This can be done either by exchanging one La- or Nb-cycle with a Ca-cycle or by introducing an extra sub-cycle.
  • the amount of dopant can vary depending on the desired properties of the resulting film.
  • concentration of the dopant Ca will normally be between 0.1% and 5%, based on the total number of La and Ca atoms. In one embodiment the concentration of Ca is between 0.2 and 0.6%.
  • the invention has been exemplified by deposition of Ca x La 1-x Nb0 4 .
  • the procedure works well and its proton conducting properties has been characterised.
  • the thin films have been deposited using an ASM F-120 Sat reactor. Films were deposited on a substrate selected from Si(l 11), MgO, SrTi0 3 and porous LaNb0 4 tablets, the selection of substrate did not influence the deposition process significantly.
  • Nb 2 0 5 was selected as the niobium oxide and initial test was run to optimize the deposition thereof.
  • Table 2 Deposition scheme for Nb and La and obtained composition.
  • Ca-doped films were obtained by introducing a Ca-deposition cycle at a regular interval but not necessarily within each full deposition cycle.
  • the ratio between La and Ca cycles was 49: 1
  • Figure 1 and 2 respectively shows the SEM picture of a porous tablet of Ca:LaNb0 4 with a layer of Ca:LaNb0 4 deposited on top.
  • the sample with the deposited film was both gas tight and proton conductive.
  • Example 2
  • the invention has been exemplified by deposition of Ca x La 1-x P0 4 .
  • the thin films have been deposited using an ASM F-120 Sat reactor.
  • the films were deposited on substrates selected from Si(l 11) and Si(001), the selection of substrate did not influence the deposition process significantly.

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Abstract

La présente invention se rapporte à un procédé de préparation d'un mince film céramique conducteur protonique, le procédé consistant à utiliser une technique de dépôt de couche atomique et à déposer des couches atomiques d'oxydes sur un substrat par réaction avec la couche supérieure sur ledit substrat, ce qui permet de former un mince film céramique conducteur protonique. L'invention se rapporte également à une structure de pile à combustible et à de minces structures d'oxydes conducteurs protoniques céramiques. L'invention a pour objet de proposer un procédé de fabrication de minces films conducteurs protoniques d'oxydes céramiques stables, lequel procédé est amélioré par rapport aux précédents procédés de telle sorte que des films étanches au gaz puissent être produits. Un film mentionné de façon précise est un mince film de LaNbO4 substitué au calcium (Ca).
PCT/NO2011/000098 2010-03-22 2011-03-22 Minces films conducteurs protoniques ou mixtes protoniques et électroniques Ceased WO2011119041A1 (fr)

Applications Claiming Priority (2)

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US31604310P 2010-03-22 2010-03-22
US61/316,043 2010-03-22

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WO2011119041A1 true WO2011119041A1 (fr) 2011-09-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6727995B1 (en) * 2001-07-12 2004-04-27 Advanced Micro Devices, Inc. Gate oxide thickness measurement and control using scatterometry
US20040202918A1 (en) * 2003-04-10 2004-10-14 Peter Mardilovich Fuel cell or electrodes with passive support
US20060008696A1 (en) * 2004-06-30 2006-01-12 Suk-Won Cha Nanotubular solid oxide fuel cell
WO2006066918A2 (fr) * 2004-12-23 2006-06-29 Universitetet I Oslo Conducteurs de protons
US20090110996A1 (en) * 2007-10-31 2009-04-30 Samsung Electronics Co., Ltd. Method of preparing fuel cell comprising proton conducting solid perovskite electrolyte membrane with improved low temperature ion conductivity, and membrane electrode assembly of fuel cell prepared by the method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6727995B1 (en) * 2001-07-12 2004-04-27 Advanced Micro Devices, Inc. Gate oxide thickness measurement and control using scatterometry
US20040202918A1 (en) * 2003-04-10 2004-10-14 Peter Mardilovich Fuel cell or electrodes with passive support
US20060008696A1 (en) * 2004-06-30 2006-01-12 Suk-Won Cha Nanotubular solid oxide fuel cell
WO2006066918A2 (fr) * 2004-12-23 2006-06-29 Universitetet I Oslo Conducteurs de protons
US20090110996A1 (en) * 2007-10-31 2009-04-30 Samsung Electronics Co., Ltd. Method of preparing fuel cell comprising proton conducting solid perovskite electrolyte membrane with improved low temperature ion conductivity, and membrane electrode assembly of fuel cell prepared by the method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAGRASO A. ET AL: "Development of proton conducting SOFCs based on LaNbO4 electrolyte - Status in Norway", FUEL CELLS, February 2011 (2011-02-01), pages 17 - 25 *

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