Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02612—Formation types
  • H01L21/02617—Deposition types
  • H01L21/02623—Liquid deposition
  • H01L21/02628—Liquid deposition using solutions
• • 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
  • C23C18/16—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 reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
  • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
  • H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
  • H10D62/86—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group II-VI materials, e.g. ZnO
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D64/00—Electrodes of devices having potential barriers
  • H10D64/60—Electrodes characterised by their materials

Definitions

• the present invention relates to a process for the preparation of indium oxide-containing layers, the indium oxide-containing layers which can be prepared by the process according to the invention and to the use thereof.
• Semiconducting electronic component layers via pressure and other liquid deposition processes, in comparison to many other processes, such as Chemical Vapor Deposition (CVD), allows a process engineering simplification and much lower production costs, since the deposition of the semiconductor can take place here in a continuous process.
• CVD Chemical Vapor Deposition
• Semiconducting layers are to be understood here and below as layers which have charge carrier mobilities of 1 to 50 cm 2 / Vs for a component with a channel length of 20 ⁇ m at 50 V gate-source voltage and 50 V source-drain voltage.
• Indium oxide indium (III) oxide, ln 2 O 3
• eV measured for vapor deposited layers
• Facchetti, TJ Marks, J. Am. Chem. 2008, 130, 12580-12581) is a promising and therefore popular semiconductor.
• thin films of a few hundred nanometers in thickness can provide one have high transparency in the visible spectral range of greater than 90% at 550 nm.
• charge carrier mobilities of up to 160 cm 2 / Vs. So far, however, such values can not yet be achieved by solution processing (H. Nakazawa, Y. Ito, E. Matsumoto, K. Adachi, N. Aoki, Y. Ochiai, J. Appl. Phys., 2006, 100, 093706. and A. Gupta, H. Cao, Parekh, KKV Rao, AR Raju, UV Waghmare, J. Appl. Phys., 2007, 101, 09N513).
• 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 displays (LCDs), in particular as “transparent electrodes.” These mostly doped metal oxide layers are industrially predominantly through Due to the great economic interest in ITO-coated substrates, there are now a number of coating methods based on sol-gel techniques for indium oxide-containing layers.
• indium oxide semiconductors via printing processes: 1) particle concepts in which (nano) particles are present in printable dispersion and are converted by sintering processes into the desired semiconductor layer after the printing process, and 2) precursor concepts in which at least one soluble or dispersible precursor is converted to an indium oxide-containing layer after printing a corresponding composition.
• particle concepts in which (nano) particles are present in printable dispersion and are converted by sintering processes into the desired semiconductor layer after the printing process
• precursor concepts in which at least one soluble or dispersible precursor is converted to an indium oxide-containing layer after printing a corresponding composition.
• a precursor is a thermally decomposable or with electromagnetic radiation compound, with the metal oxide-containing layers can be formed in the presence or absence of oxygen or other oxidizing agents to understand.
• the particle concept has two significant disadvantages compared to the use of precursors: Firstly, the particle dispersions have a colloidal instability, which makes the application of (in relation to the later layer properties disadvantageous) dispersing additives required, on the other hand form many of the usable particles (eg due to passivation layers) only incomplete layers due to sintering, so that in the layers partially particulate structures occur. At the particle boundary there is a considerable particle-particle Resistance, which reduces the mobility of the charge carriers and increases the general sheet resistance.
• Marks et al. Components in whose preparation a precursor-containing composition comprising the salt lnCl 3 and the base monoethanolamine (MEA) dissolved in methoxyethanol is used. After spin-coating the composition, the corresponding indium oxide layer is formed by thermal treatment at 400 ° C. (Kim HS, PD Byrne, A. Facchetti, TJ Marks, J. Am. Chem. Soc., 2008, 130, 12580-12581 and supplemental informations).
• indium alkoxide or indium-halogen-alkoxide-containing compositions offer the advantage that they can be converted at lower temperatures to coatings containing indium oxide. Furthermore, it has hitherto been assumed that halogen-containing precursors potentially have the disadvantage of leading to halogen-containing layers of reduced quality. For this reason, attempts have been made in the past to stratify with indium alkoxides.
• Bradley et al. report a similar reaction as Chatterjee et al. and, with approximately identical starting materials (lnCl 3 , isopropyl sodium) and reaction conditions, an indium oxoalkoxide cluster with oxygen as the central atom (DC Bradley, H. Chudzynska, DM Frigo, ME Hammond, MB Hursthouse, MA Mazid, Polyhedron 1990 , 9, 719).
• a general method for the preparation of halogen-alkoxy-metal compounds is described in US 4,681, 959 A: There is generally described a two-step process for the preparation of metal alkoxides (especially of tetraalkoxy compounds such as tetramethyltitanate) in which a halide of at least divalent metal with an alcohol - optionally in the presence of an aromatic solvent - first to an intermediate product (a Halogen-alkoxy compound of the metal) is reacted. Preference is given to expelled hydrogen halide produced with an inert gas such as nitrogen.
• JP 02-113033 A and JP 02-145459 A discloses that chlorine-containing alkoxides of indium can be prepared after dissolution of indium chloride in an alcohol corresponding to the alkoxide residue to be incorporated by subsequent addition of a certain proportion of an alkali metal or an alkali metal alkoxide.
• a corresponding method also describes JP 02-145459 A.
• indium oxide-containing layers of indium alkoxides and indium-halogen alkoxides can in principle i) by sol-gel processes in which the precursors used in the presence of water by hydrolysis and subsequent condensation first react to gels and then converted into metal oxides , or ii) take place from non-aqueous solution.
• the conversion to indium oxide-containing layers can be carried out thermally and / or by electromagnetic radiation.
• 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 of the generic formula R 1 M (OR 2 ) y x ) or a prepolymer thereof is applied to a Substrate is applied and then the resulting metal alkoxide layer is cured in the presence of and reaction with water with the addition of heat.
• a metal alkoxide for example of the generic formula R 1 M (OR 2 ) y x
• the usable metal alkoxides may be, inter alia, an indium alkoxide.
• JP 01-115010 A also deals with a thermal conversion in a sol-gel process.
• This document describes compositions for transparent, conductive thin layers which have a long pot life, do not hydrolyze as a composition, and the chlorine-containing indium alkoxides of the formula ln (OR) xCl 3 . x have. These compositions, after application to a substrate, can gel the alkoxide on the substrate by the water content in air, subsequent drying at up to 200 ° C at temperatures of 400 - 600 ° C to be converted.
• JP 02-1 13033 A describes methods for applying an antistatic coating to a non-metallic material, in which the non-metallic material is coated with a composition comprising a chlorine-containing indium alkoxide, the composition is gelled in air and subsequently calcined.
• JP 2007-042689 A describes metal alkoxide solutions which may contain indium alkoxides, as well as processes for the production of semiconductor components which use these metal alkoxide solutions.
• the metal alkoxide solutions can be converted to the oxide layer via a thermal treatment.
• JP 02-145459 A describes indium-halogen-alkoxide-containing coating compositions which do not hydrolyze on storage and which can be converted into an indium oxide-containing layer by calcination.
• JP 59-198607 A describes methods for producing transparent conductive layers which may have a protective film of various resins.
• the transparent conductive layer may be an indium oxide-containing layer, and may be prepared by a liquid phase method in which a corresponding composition is applied to a substrate, dried, and thermally converted.
• an InCI (OC 3 H 7 ) 2 -containing composition can be used.
• JP 59-198606 A describes compositions for forming transparent electrically conductive layers, the lnCl x (OR) 3 . Have x and an organic solvent and have a water content of 0, 1 - 10% based on the organic solvent. Thus, this composition is a sol of an indium halide alkoxide.
• the composition is fired after application to a substrate and drying at typically 150 ° C at temperatures of preferably 300 ° C.
• a purely thermally carried out conversion has the disadvantage that no fine structures can be produced with it and furthermore that no precise control of the resulting layer properties is possible.
• methods have been developed for conversion to indium oxide-containing layers, which are based on the use of electromagnetic radiation (in particular UV radiation).
• JP 09-157855 A describes a sol-gel process for producing a metal oxide layer in which a metal oxide sol prepared by hydrolysis from a metal alkoxide or a metal salt (eg, an indium alkoxide or salt) is applied to the surface of a substrate , optionally at a temperature at which the gel is not yet crystallized, is dried and irradiated with UV radiation of less than 360 nm.
• a metal oxide sol prepared by hydrolysis from a metal alkoxide or a metal salt eg, an indium alkoxide or salt
• JP 2000-016812 A describes a process for producing a metal oxide layer via a sol-gel process.
• the substrate is coated with a coating composition of a metal oxide sol of a metal salt or metal alkoxide, in particular an In 2 0 3 -SnO 2 composition, and irradiated with ultraviolet radiation of a wavelength smaller than 360 nm and heat treated.
• JP 11-106935 A describes a method for producing an oxide-based transparent conductive film in which, inter alia, an anhydrous composition comprising an alkoxide of a metal (eg indium) is applied to a substrate and heated. The film can be further subsequently converted with UV or VIS radiation into a metal oxide-based thin film.
• DE 10 2009 054 997 describes liquid-phase processes for the production of indium oxide-containing layers from nonaqueous solution in which an anhydrous composition containing at least one solvent or dispersion medium and at least one precursor of the formula lnX (OR) 2 is applied to a substrate in an anhydrous atmosphere electromagnetic radiation ⁇ 360 nm irradiated and thermally converted.
• liquid-phase method for producing indium oxide-containing layers according to claim 1, wherein a coating composition preparable from a mixture containing at least one indium oxide precursor and at least one solvent or dispersion medium in the order of points a) to d )
• this process is not a sputtering or CVD process.
• SATP Standard Ambient Temperature and Pressure
• a coating composition which can be prepared from a mixture containing the at least one indium oxide precursor of the generic formula lnX (OR) 2 comprises both coating compositions containing the precursor lnX (OR) 2 and coating compositions (if appropriate in addition to lnX (OR) 2 ) Indium-oxo-alkoxides or indium-halogen-oxo-alkoxides (especially those of the generic formulas ln 7 O 2 (OH) (OR) i 2 X 4 which can be prepared from InX (OR) 2 in admixture with the at least one solvent or dispersion medium (ROH) x or ln 6 O 2 X 6 (OR) 6 (R'CH (O) COOR ") 2 (HOR) x (HNR '" 2 ) y ).
• the process according to the invention is preferably carried out with coating compositions comprising lnX (OR) 2 .
• the indium oxide-containing layer is to be understood as meaning a metal-containing or semimetallin-containing layer which has indium atoms or ions which are substantially oxidic.
• the indium oxide-containing layer may also contain nitrogen (from the reaction), carbon (in particular carbene), halogen and / or alkoxide fractions from an incomplete conversion or incomplete removal of byproducts.
• the indium oxide-containing layer can be a pure indium oxide layer, ie, if any nitrogen, carbon (in particular carbene), alkoxide or halogen fractions are not taken into consideration, it consists essentially of oxidic indium atoms or ions, or even proportionally other metals, semimetals or non-metals, which may be present even in elemental or oxidic form have.
• To produce pure indium oxide layers should be in the inventive method only indium-halogen alkoxides, preferably only an indium-halogen alkoxide can be used.
• Irradiation with electromagnetic radiation takes place according to the invention with electromagnetic radiation having significant proportions of radiation in the range of 170-210 nm and of 250-258 nm.
• the absolute values can be measured directly and with the aid of various commercially available apparatuses, for example the "UV Power Meter C9536" from Hamamatsu.
• the irradiation with electromagnetic radiation with significant proportions of radiation in the range of 183-187 nm and 250-258 nm in turn, a corresponding understanding of the term "with significant proportions "(the summarily determined intensity for these two wavelength ranges with respect to the sample to be irradiated is at least 5 mW / cm 2 , with the proviso that on the lower intensity of the two areas always an intensity of at least 0 relative to the substrate , 5 mW / cm 2 is omitted.
• the radiation having significant levels of radiation is in the range 170-210 nm and 250-258 nm, even more preferably corresponding radiation has significant proportions in the range 183-187 nm and 250-258 nm in an intensity-wavelength spectrum which is linearly scaled with respect to both axes over the entire emission of the lamp, at least 85% of its intensity (determined via the percentage of the sum of the integrals of the partial regions at the total intensity of the radiation determined as integral over all wavelengths of the spectrum ) within the two respective areas.
• Corresponding radiation with significant amounts of radiation in the range of 170-210 nm and 250-258 nm can preferably be generated by using low-pressure mercury vapor lamps, in particular quartz glass low-pressure mercury vapor lamps.
• a quartz glass low-pressure mercury vapor lamp which can be used with particular preference is a lamp of the company Jelight Company, Inc, which is available under the trade name Model 144AX-220 and whose spectrum is shown in FIG.
• the indium oxide precursors InX (OR) 2 to be used according to the invention preferably have alkyl or alkyloxyalkyl radicals R selected from the group of the C1- to C15-alkyl or alkyloxyalkyl groups, ie alkyl or alkyloxyalkyl groups having a total of 1-15 carbon atoms. They are preferably alkyl or alkoxyalkyl radicals R selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 OCH 3, -CH (CH 3 ) 2 or -C (CH 3 ) 3 .
• An indium-halogen alkoxide may have identical or different radicals R.
• indium-halogen alkoxides which have the same alkyl or alkoxyalkyl radical R for the process according to the invention.
• all halogens can be used in the indium-halogenated alkoxide.
• the indium-halogen alkoxide lnX (OR) 2 is preferably used in proportions of 0, 1 to 10 wt .-%, particularly preferably 0.5 to 6 wt .-%, most preferably 1 to 5 wt .-% based on the total mass of the composition used.
• the composition comprising the indium-halogen-alkoxide may have this dissolved, ie dissociated or complexed at the molecular level with solvent molecules, or dispersed in the liquid phase.
• the inventive method is suitable - in the case that only indium-containing precursors are used, particularly well for the production of ln 2 0 3 layers with high quality and good properties. Particularly good layers result when the only precursor used is an indium-halogen alkoxide.
• the composition may also have other precursors, preferably alkoxides and halogen alkoxides of other elements, dissolved or dispersed.
• alkoxides and halogeno-alkoxides of B, Al, Ga, Ge, Sn, Pb, P, Hf, Zn and Sb are the compounds Ga (OiPr) 3 , Ga (OtBu ) 3 , Zn (OMe) 2 , Sn (OtBu) 4 . Accordingly, by using these compounds, indium oxide-containing layers which moreover have the elements B, Al, Ga, Ge, Sn, Pb, P, Zn and Sb or their oxides can be prepared.
• the composition further comprises at least one solvent or dispersion medium.
• the composition may also comprise two or more solvents or dispersion media. However, to obtain particularly good indium oxide-containing layers, only one solvent or dispersion medium should be present in the composition.
• Preferably usable solvents or dispersion media are aprotic and weakly protic solvents or dispersion media, i. those selected from the group of aprotic nonpolar solvents / dispersion media, i. the alkanes, substituted alkanes, alkenes, alkynes, aromatics with or without aliphatic or aromatic substituents, halogenated hydrocarbons, tetramethylsilane, the group of aprotic polar solvents / dispersion media, i.
• Particularly preferably usable solvents or dispersion media are alcohols and toluene, xylene, anisole, mesitylene, n-hexane, n-heptane, tris (3,6-dioxaheptyl) -amine (TDA), 2-aminomethyltetrahydrofuran, phenetole, 4-methylanisole , 3-methylanisole, methyl benzoate, butyl acetate, ethyl lactate, methoxyethanol, butoxyethanol, 1-methoxy-2-propanol, N-methyl-2-pyrrolidone (NMP), tetralin, ethyl benzoate and diethyl ether.
• TDA 3-,6-dioxaheptyl) -amine
• 2-aminomethyltetrahydrofuran 2-aminomethyltetrahydrofuran
• phenetole 4-methylanisole , 3-methylanisole, methyl benzoate, but
• Very particularly preferred solvents or dispersion media are methanol, ethanol, isopropanol, tetrahydrofurfuryl alcohol, tert-butanol, butyl acetate, ethyl lactate, methoxyethanol, 1-methoxy-2-propanol, and toluene and mixtures thereof. Because of their low toxicity, the solvents ethanol, isopropanol, tetrahydrofurfuryl alcohol, tert-butanol, butyl acetate, ethyl lactate, 1-methoxy-2-propanol and toluene are even more preferred.
• the solvent or dispersion medium is preferably used in proportions of 99.9 to 90 wt .-% based on the total mass of the composition.
• 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 determined in accordance with DIN 53019 Parts 1 to 2 and measured at 20, in order to achieve particularly good printability ° C on.
• Corresponding viscosities can be achieved by addition of polymers, cellulose derivatives or, for example, under the trade name Aerosil available Si0 2 , and in particular preferably be adjusted by PMMA, polyvinyl alcohol, urethane thickener or Polyacrylatverdicker.
• 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, PEN, PEEK, PC 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 - very particularly preferably continuous, thermal or piezo inkjet printing, offset printing, digital offset printing and screen printing), spraying methods , Spin-coating, dip-coating and methods selected from meniscus coating, slit coating, slot die coating, and curtain coating.
• the process according to the invention is very particularly preferably a printing process.
• inkjet and liquid toner techniques are particularly suitable as printing methods, since these methods are particularly well suited for structured application of the printing material.
• the radiation is irradiated with significant amounts of radiation in the range of 170-210 nm and 250-258 nm. This results in particularly good results when the irradiation is carried out in the presence of oxygen (0 2 ). Very good results result when the irradiation is carried out in an atmosphere containing 15-25% by volume of oxygen.
• oxygen in the inventive method has the advantage that is selectively generated by the selected wavelengths of 0 2 atomic oxygen (O) or ozone (0 3 ), which react with the organic radicals of the precursor and thus the required temperature for lower the thermal conversion to an indium oxide-containing layer of a certain quality.
• structured semiconductor surfaces can be produced particularly well with the method according to the invention if the irradiation in step b) is effected by a mask which predetermines the corresponding structure.
• the resulting atomic oxygen reacts with or removes organic precursor components at the sites accessible through the mask.
• the thus selectively irradiated areas are therefore after annealing more resistant to workup than unirradiated areas.
• the unirradiated areas can be removed after tempering already by the use of especially weak acids (particularly preferably 0.1 M oxalic acid).
• the invention thus also relates to a corresponding method in which the irradiation in step b) is effected by a mask which predetermines the corresponding structure and, after the temperature control in a step e), unirradiated areas are removed by the use of aqueous acids.
• Particularly preferred mask types are contact masks and shadow masks.
• a contact mask is a mask resting on the sample, which has recesses or areas of thinner material (in particular holes) at the locations where the structuring is to take place.
• a particularly preferred type of contact mask is an etched or laser cut sheet with recesses giving the final layout.
• a shadow mask is used in structuring at some distance from the sample.
• Preferred shadow masks are made of quartz glass, since quartz glass has the advantage of being transparent to UV light.
• the shaded areas are preferably chrome plated and prevent UV light from passing through.
• Corresponding shadow masks are often referred to as chrome-glass masks. Shadow masks and not contact masks are preferably used, since they have the advantage of not being used in direct contact with the sample surface.
• the process according to the invention for the production of layers containing indium oxide is, in principle, equally suitable for carrying out in the presence or absence of water.
• sol-gel processes in which the indium oxide precursor is converted to a gel before irradiation in the presence of water, which is then irradiated, preferably because this simplifies the process
• inventive method is not carried out as a sol-gel method.
• the process according to the invention can furthermore be carried out in completely anhydrous atmosphere (ie less than 500 ppm of water is present) and with anhydrous compositions (ie also containing less than 500 ppm of water) or in / with corresponding aqueous atmospheres and compositions.
• the relative humidity is not more than 70%.
• the coated substrate is further preferably dried. Corresponding measures and conditions for this are known to the person skilled in the art. Drying differs from conversion in that it removes the solvent or dispersion medium at temperatures which essentially do not yet effect any conversion of the material. If the drying takes place thermally, the temperature is not more than 120 ° C.
• the final conversion to an indium oxide-containing layer takes place by thermal means.
• the final conversion is carried out by temperatures of less than 500 ° C and greater than 120 ° C.
• temperatures of 150 ° C. to 400 ° C. are used for the conversion.
• Methods for achieving these temperatures are preferably based on the use of ovens, hot air, hot plates, IR lamps and electron guns.
• 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 film produced according to the inventive method may further by subsequent to the conversion step combined temperature and gas treatment (with H 2 or 0 2), plasma treatment (Ar, N 2 - 0 2 - or H 2 plasma), Laser treatment (with wavelengths in the UV, VIS or IR range) or an ozone treatment can be further improved.
• temperature and gas treatment with H 2 or 0 2
• plasma treatment Ar, N 2 - 0 2 - or H 2 plasma
• Laser treatment with wavelengths in the UV, VIS or IR range
• an ozone treatment can be further improved.
• the coating process can be repeated to increase the thickness.
• the coating process can take place in such a way that after each individual application irradiated with electromagnetic radiation and then converted, or there are several applications, each followed by an electromagnetic irradiation, with a single thermal conversion step after the last order.
• the invention furthermore relates to the indium oxide-containing layers which can be prepared by the process according to the invention.
• Particularly good properties have indium oxide-containing layers, which are pure indium oxide layers, which can be prepared by the process according to the invention.
• only indium-containing precursors preferably only indium-halogen alkoxides, more preferably only one indium-halogen alkoxide, are used in their preparation.
• the indium oxide-containing layers which can be produced by the process according to the invention are advantageously suitable for the production of conductive or semiconducting layers for electronic components, in particular for the production of transistors (in particular thin-film transistors), diodes, sensors or solar cells.
• EXAMPLE Indium Chloroalkoxide Precursor
• a doped silicon substrate with an edge length of about 15 mm and with an approximately 200 nm thick silicon oxide coating and ITO / gold finger structures, 100 ⁇ l of a 1.0% by weight solution of lnCl (OMe ) 2 in ethanol.
• spin coating takes place at 2000 rpm (5 seconds).
• the coated substrate is irradiated directly after this coating process for 5 minutes with UV radiation originating from a mercury-vapor lamp (illuminant GLF-100, Jelight 144AX-220, quartz glass, Jelight) in the wavelength range of 150-300 nm.
• Comparative Example indium alkoxide as precursor

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• Oxygen, Ozone, And Oxides In General (AREA)
• Thin Film Transistor (AREA)

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• 2010
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• 2016
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