EP2467513B1 - Procédé de préparation des couches contenant de l'oxyde métallique - Google Patents

Procédé de préparation des couches contenant de l'oxyde métallique Download PDF

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Publication number
EP2467513B1
EP2467513B1 EP10744568.6A EP10744568A EP2467513B1 EP 2467513 B1 EP2467513 B1 EP 2467513B1 EP 10744568 A EP10744568 A EP 10744568A EP 2467513 B1 EP2467513 B1 EP 2467513B1
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Prior art keywords
process according
metal
metal oxide
och
coating
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Not-in-force
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EP10744568.6A
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German (de)
English (en)
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EP2467513A1 (fr
Inventor
Jürgen STEIGER
Duy Vu Pham
Heiko Thiem
Alexey Merkulov
Arne Hoppe
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Evonik Operations GmbH
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Evonik Degussa GmbH
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1258—Spray pyrolysis

Definitions

  • the invention relates to a method for producing metal-oxide-containing layers, to the method producible layers and their use.
  • Indium oxide indium (III) oxide, In 2 O 3
  • Indium (III) oxide, In 2 O 3 is due to the large band gap between 3.6 and 3.75 eV (measured for evaporated layers) [ HS Kim, PD Byrne, A. Facchetti, TJ Marks; J. Am. Chem. Soc. 2008, 130, 12580-12581 ] a promising semiconductor.
  • thin films of a few hundred nanometers in thickness can have a high transparency in the visible spectral range of greater than 90% at 550 nm.
  • charge carrier mobilities of up to 160 cm 2 / Vs.
  • ITO Indium oxide is often used together with tin (IV) oxide (SnO 2 ) as semiconducting mixed oxide ITO. Due to the relatively high conductivity of ITO layers with simultaneous transparency in the visible spectral range, it is used, inter alia, in the field of liquid crystal display (LCD), in particular as a "transparent electrode". These mostly doped metal oxide layers are industrially produced mainly by cost-intensive vapor deposition in a high vacuum.
  • metal oxide-containing layers are therefore in particular indium oxide-containing layers and their preparation, and among these, ITO layers and pure indium oxide layers, of great importance for the semiconductor and display industries.
  • metal alkoxides are discussed as possible starting materials or precursors for metal oxide synthesis.
  • metal alkoxides and metal oxo alkoxides are described independently of a possible use for the metal oxide.
  • metal oxo alkoxides also have at least one further oxygen radical (oxo radical) bonded directly to an indium atom or bridging at least two indium atoms.
  • Metal oxide layers can be prepared in principle by various methods.
  • metal oxide layers are based on sputtering techniques. However, these techniques have the disadvantage that they must be performed under high vacuum. Another disadvantage is that the films made with them have many oxygen defects that make it impossible to set a targeted and reproducible stoichiometry of the layers and thus lead to poor properties of the layers produced.
  • metal oxide layers are based on chemical vapor deposition.
  • indium, gallium or zinc oxide-containing layers of precursors such as metal alkoxides or metal oxoalkoxides can be prepared by vapor deposition.
  • metal oxide layers are advantageously produced by liquid-phase processes, ie by processes comprising at least one process step prior to conversion to the metal oxide, in which the substrate to be coated is coated with a liquid solution of at least one precursor of the metal oxide and optionally subsequently dried.
  • a metal oxide precursor in this case is a compound which can be decomposed thermally or with electromagnetic radiation and with which metal oxide-containing layers can be formed in the presence or absence of oxygen or other oxidizing substances.
  • Prominent examples of metal oxide precursors are, for example, metal alkoxides.
  • the layer production can be carried out i) by sol-gel processes, in which the metal alkoxides used are first converted into gels in the presence of water by hydrolysis and subsequent condensation and then converted into metal oxides, or ii) from non-aqueous solution.
  • WO 2008/083310 A1 describes methods for producing inorganic layers or organic / inorganic hybrid layers on a substrate, in which a metal alkoxide (for example one of the generic formula R 1 M- (OR 2 ) y x ) or a prepolymer thereof is applied to a substrate and then the resulting metal alkoxide Layer is cured in the presence of and reaction with water.
  • a metal alkoxide for example one of the generic formula R 1 M- (OR 2 ) y x
  • the usable metal alkoxides may be, inter alia, those of indium, gallium, tin or zinc.
  • a disadvantage of the use of sol-gel method is that the hydrolysis-condensation reaction is started automatically by addition of water and is difficult to control after their start. If the hydrolysis-condensation process is already started prior to application to the substrate, the gels produced in the meantime, because of their increased viscosity, are often unsuitable for processes for producing fine oxide layers. On the other hand, if the hydrolysis-condensation process is started only after application to the substrate by supplying water in liquid form or as a vapor, the resulting poorly mixed and inhomogeneous gels often lead to correspondingly inhomogeneous layers having disadvantageous properties.
  • JP 2007-042689 A describes metal alkoxide solutions which may contain indium alkoxides, as well as methods of making semiconductor devices using these metal alkoxide solutions.
  • the metal alkoxide films are thermally treated and converted to the oxide layer, but these systems do not provide sufficiently homogeneous films.
  • pure indium oxide layers can not be produced by the process described therein.
  • a method is to be provided which avoids the use of high vacuum, in which the energy required for the decomposition or conversion of precursors or educts can be easily introduced in a targeted and uniform manner, which avoids the mentioned disadvantages of sol-gel techniques resulting in metal oxide layers with targeted, uniform and reproducible stoichiometry, high homogeneity and good electrical performance.
  • a liquid-phase process for producing non-aqueous solution containing metal oxide layers comprising an anhydrous composition containing i) at least one metal oxoalkoxide of the generic formula M x O y (OR) z [O (R'O) c H ] a X b [R "OH] d
  • M In, Ga, Sn and / or Zn
  • z 3 - 50
  • R, R ', R " organic radical
  • X F, Cl, Br, I and ii) at least one solvent applied to a substrate, optionally dried, and converted to a metal oxide-containing layer.
  • the liquid phase process according to the invention for producing metal oxide-containing layers from nonaqueous solution is a process comprising at least one process step in which the substrate to be coated is coated with a liquid nonaqueous solution containing at least one metal oxide precursor and optionally subsequently dried , In particular, this is not a sputtering, CVD or sol-gel process.
  • a metal oxide precursor is a thermally or decomposable with electromagnetic radiation compound to understand with the presence or absence of oxygen or other oxidizing agents metal oxide-containing layers can be formed.
  • a non-aqueous solution or an anhydrous composition is meant here and below a solution or formulation which has not more than 200 ppm H 2 O.
  • the process product of the process according to the invention, the metal oxide-containing layer is to be understood as meaning a metal- or semimetallin-containing layer which has indium, gallium, tin and / or zinc atoms or ions which are substantially oxidic.
  • the metal oxide-containing layer may also contain carbene, halogen or alkoxide fractions from incomplete conversion or incomplete removal of by-products formed.
  • the metal oxide-containing layer may be a pure indium, gallium, tin and / or zinc oxide layer, i.
  • alkoxide or halogen fractions consisting essentially of oxidic indium, gallium, tin and / or zinc atoms or ions, or proportionately even more metals, which may be present even in elemental or oxidic form , exhibit.
  • alkoxide or halogen fractions consisting essentially of oxidic indium, gallium, tin and / or zinc atoms or ions, or proportionately even more metals, which may be present even in elemental or oxidic form , exhibit.
  • To produce pure indium, gallium, tin and / or zinc oxide layers only indium, gallium, tin and / or zinc-containing precursors, preferably only oxoalkoxides and alkoxides, should be used in the process according to the invention.
  • metals containing layers in addition to the metal-containing precursors are also precursors of metals in the oxidation state 0 (for producing layers containing other metals in neutral form) or metal oxide precursors (such as other metal alkoxides or oxoalkoxide ).
  • the present inventive method is particularly well suited for the production of metal oxide layers, when the Metalloxoalkoxid is used as the sole metal oxide precursor.
  • Very good layers result when the only metal oxide precursor [In 5 ( ⁇ 5 -O) ( ⁇ 3 -O i Pr) 4 ( ⁇ 2 -O i Pr) 4 (O i Pr) 5 ], [Sn 3 O (O i Bu) 10 ( i BuOH) 2 ] or [Sn 6 O 4 (OR) 4 ].
  • layers are used in their preparation as the only metal oxide precursor [In 5 ( ⁇ 5 -O) ( ⁇ 3 -O i Pr) 4 ( ⁇ 2 -O i Pr) 4 (O i Pr) 5 ] was, even more preferred.
  • the at least one metal oxoalkoxide is preferably present in proportions of from 0.1 to 15% by weight, more preferably from 1 to 10% by weight, very preferably from 2 to 5% by weight, based on the total mass of the anhydrous composition.
  • the anhydrous composition further contains at least one solvent, ie the composition may contain both a solvent or a mixture of different solvents.
  • Aprotic and weakly protic solvents ie those selected from the group of aprotic nonpolar solvents, ie alkanes, substituted alkanes, alkenes, alkynes, aromatics with or without aliphatic or aromatic substituents, halogenated hydrocarbons, are preferably usable for the process according to the invention in the formulation.
  • Tetramethylsilane the group of aprotic polar solvents, ie the ethers, aromatic ethers, substituted ethers, esters or acid anhydrides, ketones, tertiary amines, nitromethane, DMF (dimethylformamide), DMSO (dimethylsulfoxide) or propylene carbonate and the weak protic solvents, ie the alcohols , the primary and secondary amines and formamide.
  • aprotic polar solvents ie the ethers, aromatic ethers, substituted ethers, esters or acid anhydrides, ketones, tertiary amines, nitromethane, DMF (dimethylformamide), DMSO (dimethylsulfoxide) or propylene carbonate
  • the weak protic solvents ie the alcohols , the primary and secondary amines and formamide.
  • Solvents include alcohols such as toluene, xylene, anisole, mesitylene, n-hexane, n-heptane, tris- (3,6-dioxaheptyl) -amine (TDA), 2-aminomethyltetrahydrofuran, phenetole, 4-methylanisole, 3-methylanisole, methylbenzoate , N-methyl-2-pyrrolidone (NMP), tetralin, ethyl benzoate and diethyl ether.
  • Very particularly preferred solvents are methanol, ethanol, isopropanol, tetrahydrofurfuryl alcohol, tert-butanol and toluene, and mixtures thereof.
  • the composition used in the process according to the invention preferably has a viscosity of from 1 mPa ⁇ s to 10 Pa ⁇ s, in particular from 1 mPa ⁇ s to 100 mPa ⁇ s, according to DIN 53019 Parts 1 to 2 and measured at 20 ° C on.
  • Corresponding viscosities can be set by addition of polymers, cellulose derivatives, or, for example, SiO 2 obtainable under the trade name Aerosil, and in particular by PMMA, polyvinyl alcohol, urethane thickener or polyacrylate thickener.
  • the substrate used in the method according to the invention is preferably a substrate consisting of glass, silicon, silicon dioxide, a metal or transition metal oxide, a metal or a polymeric material, in particular PI or PET.
  • the process according to the invention is particularly advantageously a coating process selected from printing processes (in particular flexographic / gravure printing, inkjet printing, offset printing, digital offset printing and screen printing), spraying processes, spin-coating processes, dip processes (dip -coating ”) and methods selected from Meniscus Coating, Slit Coating, Slot Die Coating, and Curtain Coating.
  • printing processes in particular flexographic / gravure printing, inkjet printing, offset printing, digital offset printing and screen printing
  • spraying processes spin-coating processes
  • dip processes dip -coating
  • methods selected from Meniscus Coating, Slit Coating, Slot Die Coating, and Curtain Coating are preferred.
  • the coated substrate After coating and before conversion, the coated substrate can continue to be dried. Corresponding measures and conditions for this are known to the person skilled in the art.
  • the conversion to a metal oxide-containing layer can take place by thermal means and / or by irradiation with electromagnetic, in particular actinic radiation.
  • the conversion takes place on the thermal paths through temperatures of greater than 150 ° C. Particularly good results can be achieved, however, if temperatures of 250 ° C to 360 ° C are used for the conversion.
  • the thermal conversion can furthermore be assisted by irradiating UV, IR or VIS radiation before or during the thermal treatment or by treating the coated substrate with air or oxygen.
  • the quality of the layer produced by the process according to the invention can furthermore be determined by a combined temperature and gas treatment (with H 2 or O 2 ) following the conversion step, plasma treatment (Ar, N 2 , O 2 or H 2 plasma), laser Treatment (with wavelengths in the UV, VIS or IR range) or an ozone treatment can be further improved.
  • a combined temperature and gas treatment with H 2 or O 2
  • plasma treatment Ar, N 2 , O 2 or H 2 plasma
  • laser Treatment with wavelengths in the UV, VIS or IR range
  • an ozone treatment can be further improved.
  • the subject matter furthermore relates to metal oxide-containing layers which can be prepared by the process according to the invention.
  • metal oxide-containing layers which can be prepared by the process according to the invention.
  • Even better properties are produced by the novel process producible pure indium oxide.
  • the metal oxide-containing layers which can be produced by the process according to the invention are advantageously suitable for the production of electronic components, in particular the production of transistors (in particular thin-film transistors), diodes, sensors or solar cells.
  • a doped silicon substrate having an edge length of about 15 mm and having an approximately 200 nm thick silicon oxide coating and ITO / gold finger structures was coated with 100 ⁇ l of a 5% by weight solution of [In 5 ( ⁇ 5 -O) ( ⁇ 3 -O i Pr) 4 ( ⁇ 2 -O i Pr) 4 (O i Pr) 5 ] in alcohol (methanol, ethanol or isopropanol) or toluene by spin coating (2000 rpm). To exclude water, dry solvents (less than 200 ppm water) were used and the coating was still carried out in a glove box (less than 10 ppm H 2 O). After the coating operation, the coated substrate was annealed in the air at a temperature of 260 ° C or 350 ° C for one hour.
  • the inventive coating exhibits a charge carrier mobility of up to 6 cm 2 / Vs (at 30 V gate-source voltage, 30 V source-drain voltage, 1 cm channel width and 20 ⁇ m channel length).
  • Table 1 Carrier mobilities

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Formation Of Insulating Films (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Thin Film Transistor (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (12)

  1. Procédé en phase liquide pour la fabrication de couches contenant un oxyde métallique à partir d'une solution non aqueuse, caractérisé en ce qu'une composition anhydre contenant :
    i) au moins un oxoalcoxyde métallique de formule générique

            MxOy(OR)z[O(R'O)cH]aXb[R''OH]d

    avec
    x = 3 à 25,
    y = 1 à 10,
    z = 3 à 50,
    a = 0 à 25,
    b = 0 à 20,
    c = 0 à 1,
    d = 0 à 25,
    M = In, Ga, Sn et/ou Zn,
    R, R', R" = radical organique,
    X = F, Cl, Br, I et
    ii) au moins un solvant
    est appliquée sur un substrat, éventuellement séchée et transformée en une couche contenant un oxyde métallique.
  2. Procédé selon la revendication 1, caractérisé en ce qu'en tant qu'au moins un oxoalcoxyde métallique, un oxoalcoxyde de formule MxOy(OR)z avec x = 3 à 20, y = 1 à 8, z = 3 à 25, OR = groupe alcoxy, oxyalkylalcoxy, aryloxy ou oxyarylalcoxy en C1-C15 ;
    de manière particulièrement préférée un tel oxoalcoxyde de formule générique MxOy(OR)z avec x = 3 à 15, y = 1 à 5, z = 10 à 20, OR = -OCH3, -OCH2CH3, -OCH2CH2OCH3, -OCH(CH3)2 ou -OC(CH3)3.
  3. Procédé selon la revendication 2, caractérisé en ce que ledit au moins un oxoalcoxyde métallique est [In5(µ5-O)(µ3-OiPr)4(µ2-OiPr)4(OiPr)5], [Sn3O(OiBu)10BuOH)2] et/ou [Sn6O4(OR)4].
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit au moins un oxoalcoxyde métallique est le seul précurseur d'oxyde métallique utilisé dans le procédé.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit au moins un oxoalcoxyde métallique est présent en proportions de 0,1 à 15 % en poids, par rapport à la masse totale de la composition anhydre.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit au moins un solvant est un solvant aprotique ou faiblement protique.
  7. Procédé selon la revendication 6, caractérisé en ce que ledit au moins un solvant est choisi dans le groupe constitué par le méthanol, l'éthanol, l'isopropanol, l'alcool tétrahydrofurfurylique, le tert-butanol et le toluène.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la composition présente une viscosité de 1 mPas·s à 10 Pa·s.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le substrat est constitué de verre, de silicium, de dioxyde de silicium, d'un oxyde d'un métal ou d'un métal de transition, d'un métal ou d'un matériau polymère.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'application de la composition anhydre sur le substrat a lieu par un procédé d'impression, un procédé de pulvérisation, un procédé de revêtement par rotation, un procédé d'immersion ou un procédé choisi dans le groupe constitué par le couchage à ménisque, le couchage à fente, le couchage à filière droite et le couchage au rideau.
  11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la transformation a lieu thermiquement par des températures supérieures à 150 °C.
  12. Procédé selon la revendication 11, caractérisé en ce qu'une exposition à un rayonnement UV, IR ou VIS a lieu avant, pendant ou après le traitement thermique.
EP10744568.6A 2009-08-21 2010-08-13 Procédé de préparation des couches contenant de l'oxyde métallique Not-in-force EP2467513B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009028802A DE102009028802B3 (de) 2009-08-21 2009-08-21 Verfahren zur Herstellung Metalloxid-haltiger Schichten, nach dem Verfahren herstellbare Metalloxid-haltige Schicht und deren Verwendung
PCT/EP2010/061836 WO2011020792A1 (fr) 2009-08-21 2010-08-13 Procédé de production de couches contenant de l'oxyde métallique

Publications (2)

Publication Number Publication Date
EP2467513A1 EP2467513A1 (fr) 2012-06-27
EP2467513B1 true EP2467513B1 (fr) 2017-11-15

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EP10744568.6A Not-in-force EP2467513B1 (fr) 2009-08-21 2010-08-13 Procédé de préparation des couches contenant de l'oxyde métallique

Country Status (9)

Country Link
US (1) US9309595B2 (fr)
EP (1) EP2467513B1 (fr)
JP (1) JP5766191B2 (fr)
KR (1) KR101725573B1 (fr)
CN (1) CN102575350B (fr)
DE (1) DE102009028802B3 (fr)
RU (1) RU2553151C2 (fr)
TW (1) TWI485284B (fr)
WO (1) WO2011020792A1 (fr)

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DE102008058040A1 (de) * 2008-11-18 2010-05-27 Evonik Degussa Gmbh Formulierungen enthaltend ein Gemisch von ZnO-Cubanen und sie einsetzendes Verfahren zur Herstellung halbleitender ZnO-Schichten
DE102009009337A1 (de) 2009-02-17 2010-08-19 Evonik Degussa Gmbh Verfahren zur Herstellung halbleitender Indiumoxid-Schichten, nach dem Verfahren hergestellte Indiumoxid-Schichten und deren Verwendung
DE102010031895A1 (de) 2010-07-21 2012-01-26 Evonik Degussa Gmbh Indiumoxoalkoxide für die Herstellung Indiumoxid-haltiger Schichten
DE102010031592A1 (de) 2010-07-21 2012-01-26 Evonik Degussa Gmbh Indiumoxoalkoxide für die Herstellung Indiumoxid-haltiger Schichten
DE102010043668B4 (de) * 2010-11-10 2012-06-21 Evonik Degussa Gmbh Verfahren zur Herstellung von Indiumoxid-haltigen Schichten, nach dem Verfahren hergestellte Indiumoxid-haltige Schichten und ihre Verwendung
DE102011084145A1 (de) 2011-10-07 2013-04-11 Evonik Degussa Gmbh Verfahren zur Herstellung von hochperformanten und elektrisch stabilen, halbleitenden Metalloxidschichten, nach dem Verfahren hergestellte Schichten und deren Verwendung
DE102012209918A1 (de) * 2012-06-13 2013-12-19 Evonik Industries Ag Verfahren zur Herstellung Indiumoxid-haltiger Schichten
EP2954114B1 (fr) 2013-02-06 2019-03-13 Koninklijke Philips N.V. Plaque de traitement pour appareil de traitement de vêtements
DE102013212018A1 (de) * 2013-06-25 2015-01-08 Evonik Industries Ag Metalloxid-Prekursoren, sie enthaltende Beschichtungszusammensetzungen, und ihre Verwendung
EP2874187B1 (fr) 2013-11-15 2020-01-01 Evonik Operations GmbH Transistor à film mince et résistance de contact faible
DE102014202718A1 (de) 2014-02-14 2015-08-20 Evonik Degussa Gmbh Beschichtungszusammensetzung, Verfahren zu ihrer Herstellung und ihre Verwendung
EP3360933A1 (fr) * 2017-02-08 2018-08-15 Evonik Degussa GmbH Formulations à structures directes à base de précurseurs d'oxyde métallique destinées à fabriquer des couches d'oxyde
EP3409813A1 (fr) * 2017-06-01 2018-12-05 Evonik Degussa GmbH Dispositif contenant des couches contenant de l'oxyde de métal
CN111254423B (zh) * 2020-03-26 2021-12-07 上海大学 一种芳香族聚酰胺纤维电镀银的方法及应用

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KR20120043770A (ko) 2012-05-04
JP5766191B2 (ja) 2015-08-19
CN102575350A (zh) 2012-07-11
RU2012110476A (ru) 2013-09-27
DE102009028802B3 (de) 2011-03-24
JP2013502364A (ja) 2013-01-24
TW201120242A (en) 2011-06-16
CN102575350B (zh) 2014-12-17
US9309595B2 (en) 2016-04-12
RU2553151C2 (ru) 2015-06-10
TWI485284B (zh) 2015-05-21
US20120181488A1 (en) 2012-07-19
KR101725573B1 (ko) 2017-04-10
WO2011020792A1 (fr) 2011-02-24
EP2467513A1 (fr) 2012-06-27

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