WO2011119041A1 - Proton, or mixed proton and electronic conducting thin films - Google Patents

Proton, or mixed proton and electronic conducting thin films 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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Oestreng Erik
Ola Nilsen
Fjellvaag Helmer
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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
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    • 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

Process for preparing of a proton conducting ceramic thin film, where the process comprises utilizing atomic layer deposition technique and depositing atomic layers of oxides on a substrate by reaction with the top layer on said substrate thereby forming a proton conducting ceramic thin film. The invention also pertains to a fuel cell structure and to thin ceramic proton conducting oxide structures. The aim of the invention is to provide a method for producing thin proton conducting films of stable ceramic oxides, which method is improved in relation to previous methods, so that gas tight films can be produced. One film specifically mentioned is a thin film of Ca-substituted LaNbO4.

Description

Proton, or mixed proton and electronic conducting thin Alms
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 [
PCT Int. Appl. (2006), WO 2006066918 A2 20060629.
R. Haugsrud, T. Norby, Nature Materials 5 (2006) 193-196.
T. Norby, N. Christiansen, Solid State Ionics 77 (1995) 240-243.
N. Vajeeston; R. Haugsrud, T. Norby, Solid State Ionics 181 (2010) 510-516.
R. Haugsrud, Solid State Ionics 178 (2007) 555-560.].
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 M3+ of the lanthanide elements (No. 57-71 in the Periodic Table). Acidic cations comprise M3+, M4 , M5+ and M6+ cations of groups 4-7 and 13-16, and M4+ 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.
Some proton conducting oxides become selectively permeable to hydrogen by additional conduction by electrons. 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.
Many, but not all, of the 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 La26027(B03)8, TiP207, and La5.6W011 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.
ALD = atomic layer deposition (also known as ALCVD = atomic layer chemical vapour deposition, and ALE = atomic layer epitaxy) is a thin film technique that utilizes only gas to surface reactions, and the technique as such is described in the prior art, such as in [Puurunen, R. L. (2005). "Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process." J. Appl. Phys. 97(12): 121301/1- 121301/52.]. 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.
Until now research on fuel cells for high temperature applications has focused on depositing oxygen conducting materials for fuel cells, whereas deposition of stable proton conducting ceramic materials has not received similar attention.
There exist alternative deposition techniques for depositing these types of materials; however, 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.
Calcium substituted lanthanum phosphate has not been demonstrated deposited earlier by ALD.
Lanthanum tungstates have not been demonstrated deposited earlier by ALD.
Lanthanum borates have not been demonstrated deposited earlier by ALD.
Pure or substituted lanthanum molybdates have not been demonstrated deposited earlier by ALD.
Titanium phosphates have not been demonstrated deposited earlier by ALD.
Barium and strontium cerate, pure or substituted, have not been demonstrated deposited earlier by ALD.
Barium and strontium zirconate, pure or substituted, 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 C02 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 C02. For some film compositions 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.
In another aspect the present invention provides a method for producing a proton conducting calcium substituted lanthanum niobate thin film using ALD.
In yet another aspect the present invention provides a method for producing a proton conducting calcium substituted lanthanum phosphate thin film using ALD.
In yet another aspect 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 WF6, La(thd)3 or La(cp)3 or its derivatives, as metal containing precursors and H20, 03 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 H20, 03 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 TiP207, according to the present invention can be deposited using an ALD reactor and Me3(P04), T1CI4 or Ti (0'Pr)4 as metal containing precursors and H20, 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 YCp3, ZrCl4 or Zr(0'Bu)4, Ba(thd)2 or BaCp2 or its derivatives, as metal containing precursors and H20, 03 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 SrCp2 or its derivatives, BBr3 or B(OMe)3 or B2H6, La(thd)3 or La(cp)3 or its derivatives, as metal containing precursors and H20, 03 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 for lanthanum oxoborate borate according to the present invention can be deposited using an ALD reactor using BBr3 or B(OMe)3 or B2H6, La(thd)3 or La(cp)3 or its derivatives, as metal containing precursors and H20, 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.
Further 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.
Some results obtained by utilizing the present invention are illustrated in the enclosed figures. The figures are solely intended for illustration purposes and should not be construed in any manner limiting the invention:
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 H20, 03 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:
Nb-cycle:
Pulse of Nb(OEt)5, (Niobium ethoxide)
Purge
Pulse of H20
Purge
Ca-cycle
Pulse Ca(thd)2
Purge
Pulse of03
Purge
La-cycle
Pulse La(thd)3
Purge
Pulse of 03
Purge In general depositions can be performed within different deposition temperature intervals. To achieve an effective deposition process 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:
1) Nb-cycle - La-cycle
2) Nb-cycle - La-cycle - La-cycle
3) Nb-cycle - Nb-cycle - La-cycle - La-cycle
4) La-cycle - Nb-cycle - Nb-cycle
5) La-cycle - Nb-cycle- La-cycle - Nb-cycle - La-cycle
6) La-cycle - Nb-cycle- La-cycle - Nb-cycle - La-cycle- Nb-cycle - La-cycle
7) Etc.
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. For proton conducting LaNb04 films the 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 Me3(P04), La(thd)3, Ca(thd)2 as metal containing precursors and H20, 03 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:
P-cycle:
Pulse ofMe3(P04)
Purge
Pulse ofH20 + 03
Purge
Ca-cycle
Pulse Ca(thd)2
Purge
Pulse of 03
Purge
La-cycle
Pulse La(thd)3
Purge
Pulse of 03
Purge
Similar to the total scheme for deposition of lanthanum-niobat the sequence of the different sub-cycles can be freely selected.
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. For proton conducting LaPOy films the 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%. Examples
Example 1
Deposition of CaxL i-x b04
The invention has been exemplified by deposition of CaxLa1-xNb04. 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, SrTi03 and porous LaNb04 tablets, the selection of substrate did not influence the deposition process significantly.
The following precursors have been tested.
Figure imgf000012_0001
thd = 2,2,6,6-tetramethylheptane-3,5-dionate
Nb205 was selected as the niobium oxide and initial test was run to optimize the deposition thereof.
Figure imgf000012_0002
Table 1: Deposition of Nb205. Sample Pulse Nb Pulse La Nb Pulse Dep at% Dep at%
[number] [number] % Nb La
BA1010 1 4 20 38 62
BA1012 2 3 40 47 53
BA1014 1 1 50 59 41
BA1013 3 2 60 75 25
BA1011 4 1 80 82 18
Table 2: Deposition scheme for Nb and La and obtained composition.
The experiment BA1012 with 2 Nb sub-cycles and 3 La sub-cyclers per full deposition cycle results in deposition of 47 atom % Nb and 53 atom % La. This 3:2 relationship between La and Nb was shown to be a favourable combination. When performing the experiments the different cycles are distributed as equally as possible. In the case with the 3:2 distribution the following sub-cycle scheme was used: [La - Nb - La - Nb - La], where each sub-cycle comprises purging, ozone deposition and purging in addition to the La or Nb deposition.
For films grown on Si (111) tablets at a 3: 1 relationship between La and Nb the composition was measured using XPS.
Figure imgf000013_0001
Table 3: Composition of grown
Ca-doped films were obtained by introducing a Ca-deposition cycle at a regular interval but not necessarily within each full deposition cycle. For the BA1042 sample 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:LaNb04 with a layer of Ca:LaNb04 deposited on top. The sample with the deposited film was both gas tight and proton conductive. Example 2
Deposition of CaxLai-xPyOz
The invention has been exemplified by deposition of CaxLa1-xP04. 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.
The following deposition scheme was utilised for deposition of LaPyOz: La(thd)3 + 03 + Me3(P04) + (H20 + 03)
After introduction of each of the precursors and after each of the oxidation agents a purging step was performed. Different oxidation agents were tested initially and the use of a mixture of water and ozone after the phosphate precursor provide a good growth rate, stabile and consistent composition.
To measure the variation in growth rate and establish an operational growth window depositions where performed at temperatures from 225 - 325 °C, and at 400 °C. The growth rate is relatively constant at temperatures between 250 °C and 300 °C, which therefore may be considered an operational temperature window. At lower temperatures the growth rate is slow. At 400 °C film growth did not take place.
Variations in the repetition of the different sub-cycles where performed to try to change the phosphonlanthanum relationship. Pulse relationships with 1:1, 2:1, and 3:1 phosphor pulses to lanthanum pulses where performed, however the relationship in the deposited film stayed constant at 5:4 P:La. Films with a lower amount of phosphor could be obtained by introducing more lanthanum oxide pulses between the phosphor pulses.
Accordingly it is possible to deposit LaPyOz, with y<1.2, z is yet to be determined. The experiments show that lanthanum-phosphate films can be obtained using ALD technique.

Claims

C l a i m s
1.
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.
2.
Process according to claim 1 , wherein said ceramic oxide thin film comprises at least two different classes of cations forming ternary or substituted binary ceramic proton conducting oxide thin film.
3.
Process according to claim 1, wherein said ceramic oxide thin film comprises at least three different cations from at least two different classes of cations forming solid solutions or substituted ternary ceramic proton conducting oxide thin film.
4.
Process according to claim 2, wherein said cation classes are A3+ from group 3 and the lanthanide elements; and B cations from group 5; and acceptor dopants C from group 2 and 12 are substituted for some of the A cations.
5.
Process according to claim 2, wherein said cation classes are A3+ from group 3 and the lanthanide elements, and B5+ cations from group 15 and acceptor dopants C2+ from group 2 and 12 are substituted for some of the A cations.
6.
Process according to claim 4 or 5, with a substitution level of C from group 2 and 12 in the range 0.1 % to 30%.
7.
Process according to claim 4, wherein said cations are La and Nb and an acceptor dopant element..
8:
Process according to claim 4, wherein said cations are La and cations of tungsten.
9.
Process according to claim 5, wherein said cations are La3+, P5+, and Ca2+. 10.
Process according to claim 5, wherein said cations are La , Nb , and Ca .
11
Process according to claim 10, wherein the process comprises alternately pulsing cation containing precursor and oxygen containing precursor separated by purging, wherein, a La-containing precursor, a Nb-containing precursor, and a Ca-containing precursor suitable for ALD-growth are pulsed as cation containing precursors and H20, 03 or a mixture thereof are pulsed as oxygen containing precursor..
12.
Process according to claim 9, wherein the process comprises alternately pulsing cation containing precursors and oxygen containing precursors separated by purging, wherein a La-containing precursor, a P-containing precursor, and a Ca-containing precursor suitable for ALD-growth are pulsed as cation containing precursors and H20, 03 or a mixture thereof is pulsed as oxygen containing precursor.
13.
Ceramic proton conducting oxide thin film, prepared by the process of claims 1, wherein the thin film is pin-hole free. 14
• Ceramic proton conducting oxide thin film according to claim 13, wherein the thin film is gas tight.
15Ceramic proton conducting oxide thin film according to any of claims 13 or 14, with thickness 0.5 nm to 500 nm.
16.
Ceramic proton conducting thin film according to any of claims 13-15, deposited 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.
17
Ceramic proton 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 provided there is additional conduction by electrons in the film.
18.
Ceramic proton conducting oxide structure, comprising a porous oxide substrate structure provided with a gas tight ceramic proton conducting oxide thin film.
19.
Ceramic proton conductor structure according to claim 18 with the said oxide substrate being proton conducting.
20.
Proton conductor according to claim 18, wherein said thin film comprises Ca substituted LaNbQ4.
21. Fuel cell structure consisting of ceramic proton conducting oxide thin film according to any of claims 13-15 deposited on a porous or dense hydrogen-permeable electron- conducting substrate acting as one half electrode.
22.
Fuel cell structure according to claim 21, wherein the ceramic proton conducting oxide is Ca-substituted LaNb04.
23.
Process according to claim 2, wherein said cation A4+ are from group 4 and B5+ cations from group 15; and acceptor atoms C and C from group 2, 3, 12 and 13 are substituted for some of the A4+ cations.
24.
Process according to claim 23, wherein said cations are Ti3+ and P5+. 25.
Process according to claim 2, wherein said cation A3+ are from group 3 and the lanthanide elements, and B6+ cations from group 6.
26.
Process according to claim 25, wherein said cations are La3+ and W6+ 27.
Process according to claim 2, wherein said cation A2+ are from group 2 and 12, and B4_t cations from group 4, 5 and the lanthanide elements.
28.
Process according to claim 27, wherein said cations A are Ca2+, Sr2*, Ba2+, Zn2+ and the B4+ cations are Ce4+, Pr4+,Tii4+, Zr4+, Hf4*, Nb4+.
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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 (en) * 2004-12-23 2006-06-29 Universitetet I Oslo Proton conductors
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 (en) * 2004-12-23 2006-06-29 Universitetet I Oslo Proton conductors
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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