EP2839504A1 - Formulations comprising ammoniacal hydroxo-zinc compounds - Google Patents

Formulations comprising ammoniacal hydroxo-zinc compounds

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Publication number
EP2839504A1
EP2839504A1 EP13712255.2A EP13712255A EP2839504A1 EP 2839504 A1 EP2839504 A1 EP 2839504A1 EP 13712255 A EP13712255 A EP 13712255A EP 2839504 A1 EP2839504 A1 EP 2839504A1
Authority
EP
European Patent Office
Prior art keywords
hydroxo
compound
zinc
formulation according
zno
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13712255.2A
Other languages
German (de)
French (fr)
Inventor
Jürgen STEIGER
Duy Vu Pham
Dennis Weber
Silviu Botnaras
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Industries AG
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Filing date
Publication date
Application filed by Evonik Industries AG filed Critical Evonik Industries AG
Publication of EP2839504A1 publication Critical patent/EP2839504A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • 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
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • 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
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

Definitions

  • the present invention relates to ammoniacal formulations comprising hydroxo-zinc compounds, to processes for producing ZnO-containing layers, which use these formulations, to the ZnO-containing layers obtainable by this process, to the use of the formulations for producing electronic components, and to electronic components containing the ZnO-containing layers produced by the process. Because of its low production costs and its easy scalability, printed electronics is the focus of many current research and development projects, especially in the field of semiconductor technology. There is one
  • FETs field effect transistors
  • TFTs thin-film field effect transistors
  • each transistor An important component in each transistor is the semiconductor material, which has the switching parameters, e.g. the tension, influenced.
  • Important parameters for semiconductor materials are the respective field-effect mobilities, processabilities and processing temperatures during production.
  • zinc oxide is one of the most attractive inorganic oxide materials for transistor fabrication. Furthermore, because of its highly interesting piezoelectric and electromechanical properties, zinc oxide is also commonly used in semiconductor technology in general (Mater., Eng., B-Solid State Mater., Adv., Technol., 2001, 80, 383; IEEE Trans. Microw. Theory Tech , MT17, 957) and used in electronics and optoelectronics. Due to its band gap of 3.37 eV at room temperature (Klingshirn, Phys. Status Solidi B, 1975, 71, 547) and its high exciton-binding energy of 60 meV (Landolt's
  • the Hall mobility ⁇ ⁇ of the electrons in the ZnO single crystal is 400 cm 2 -V "1 -s " 1 , and these values have hitherto been obtained in practical layers were not reached.
  • Epitaxially, ie eg ZnO layers deposited or sputtered by means of chemical vapor deposition (CVD) show FET mobilities of 50 to 155 cm 2 -V 1 -s 1.
  • the prior art furthermore discloses layers based on mixed oxides containing ZnO
  • Hosono Journal of Non-Crystalline Solids, 2006, 352, 851-858 describes gas phase deposition field effect transistors with amorphous oxides of indium, gallium, and zinc, which allow not only pure ZnO layers, but also ZnO-containing layers, ie Layers comprising in addition to ZnO elementary or in combination (especially oxidic) present foreign metals, be suitable for use in field effect transistors.
  • Particle-based concepts are based primarily on the use of nanoparticulate systems, such. ZnO nanotubes (Nano Letters, 2005, 5, 12, 2408-2413).
  • the disadvantages of the particle concepts are, on the one hand, the colloidal instability of the particle dispersions used, which necessitates the use of dispersing additives, which in turn can adversely affect the resulting charge carrier mobility.
  • the particle-particle resistance is a problem because it reduces the mobility of charge carriers and generally increases the sheet resistance.
  • Keszler et al., J. Am. Chem. Soc. 2008, 130, 17603-17609 describe good processible ammoniacal solutions of zinc hydroxide compounds in which a Zn-amine-hydroxo complex of the generic formula
  • Schmechel et al. Thin Solid films 201 1, 519, 5623-5628, describe the use of zinc oxide hydrate in ammoniacal solution in the synthesis of ZnO-containing layers and at conversion temperatures of 125, 300 and 500 ° C produced field effect transistors. Also their electrical properties
  • turn-on voltage is meant the voltage between gate and source at which the transistor turns on, i. begins to conduct the electrical current between the source and drain. This value should be as close as possible to 0V
  • the present object is achieved by the novel ammoniacal formulation comprising a) at least one hydroxo-zinc compound, and b) at least one compound of an element of the third main group.
  • An ammoniacal formulation comprising at least one hydroxo-zinc compound is an aqueous, ammonia-containing composition in which a hydroxo-zinc compound is dissolved or in which non-hydroxo-zinc compounds form a hydroxo-zinc compound has been.
  • Corresponding hydroxo-zinc compounds may be one or more
  • the ammoniacal formulation has only a single hydroxo-zinc compound.
  • the hydroxo-zinc compound has only a single central ion, which is zinc.
  • Corresponding hydroxo-zinc compounds can furthermore attach to amine ligands (NH 3 ligands).
  • the hydroxo-zinc compound may have further ligands besides the Zn central ion (s) and the hydroxo and, if appropriate, ammin ligands.
  • the hydroxo-zinc compound exclusively hydroxo- and possibly amine ligands.
  • the at least one hydroxo-zinc compound can be dissociated in the ammoniacal formulation and optionally present solvated or dispersed. Particularly preferred because they are particularly suitable for the production of homogeneous layers with particularly good electrical properties, are
  • Corresponding formulations may be prepared from zinc nitrate solutions via basic precipitation with a hydroxide base such as NaOH and
  • the formulation of the invention comprises the at least one hydroxo-zinc compound, preferably in proportions of from 50 to 99.95 mol%, preferably from 85 to 99.95 mol%, particularly preferably from 95 to 99.95 mol%, based on the
  • the formulation of the invention further comprises at least one compound of an element of the 3rd main group.
  • the formulation comprises at least one compound of an element selected from the group consisting of boron (B), aluminum (AI), gallium (Ga), indium (In) and thallium (Tl).
  • B aluminum
  • AI aluminum
  • Ga gallium
  • In indium
  • Tl thallium
  • the at least one compound of an element of the 3rd main group is a compound of aluminum (AI), gallium (Ga) or indium (In).
  • the at least one compound of the element of the 3rd main group can be dissociated in the ammoniacal formulation and optionally present solvated or dispersed.
  • the ammoniacal formulation comprises at least two compounds of elements of the 3rd main group. These are more preferably compounds of different elements of the 3rd main group. Very good results are achieved when the formulation comprises at least one gallium compound and at least one indium compound.
  • the formulation according to the invention comprises the at least one compound of an element of the 3rd main group, preferably in proportions of from 0.05 to 50 mol%, preferably from 0.05 to 15 mol%, particularly preferably from 0.05 to 5 mol% on the total amount of zinc ions and atoms / ions of the element of the 3rd main group.
  • two or more compounds of elements of the 3rd main group are present in the formulation, their respective proportions are preferably 1 to 99 mol%, preferably 5 to 95 mol%, based on the total amount of the compounds of elements of the 3rd main group used.
  • ammoniacal formulations which, in addition to the hydroxo-zinc compound, also contain at least one compound of indium and at least one compound of gallium. More preferably, the ratio of the total amounts of the compounds used of
  • the formulation is particularly suitable for producing zinc oxide-containing layers having particularly good electrical properties if the hydroxo-zinc compound is present in proportions of 65-75 mol%.
  • the gallium compound is present in proportions of 25-34 mol% and the indium compound in proportions of 1-10 mol% based on the total amount of zinc ions and atoms / ions of the element of the 3rd main group.
  • Particularly useful compounds of elements of the 3rd main group are the corresponding nitrates, hydroxides, oxides, oxide hydroxides, halides and
  • Oxyhalides Very particular preference may be given to using the nitrates, hydroxides, oxides, oxide hydroxides, halides or oxyhalides of aluminum, indium or gallium. Best ZnO-containing layers result when formulations are used which a) by dissolving the nitrate salts of zinc and at least one element of the 3rd main group in trivalent oxidation state, b) precipitating a hydroxide-containing precipitate with a hydroxide base, c) separating the solvent, if necessary c) washing, and d) producing the precipitate in ammoniacal water.
  • hydroxide hydroxide preferably used are the bases NaOH and KOH. The separation can preferably be carried out by filtration or centrifugation.
  • the concentration of ammonia in the aqueous ammonia formulation which absorbs the precipitate is preferably from 20 to 33 wt .-%, preferably 25 to 30 wt .-%, based on the
  • steps c), c ') and d) can be repeated one or more times to achieve particularly good layers.
  • the total concentration of zinc ions and element atoms / ions of the 3rd main group to achieve particularly good results 0.05 to 2, preferably 0.1 to 1, particularly preferably 0.1 to 0.5 mol / l.
  • the formulation according to the invention is outstandingly suitable for the production of ZnO-containing layers without having to add further additives for this purpose. Nevertheless, the formulations according to the invention are compatible with various additives, such. B. substances that stabilize the same against reagglomeration and sedimentation. In general, this at least one additive, depending on the type, the concentration of hydroxo-zinc compound and the nature of the liquid phase of the dispersion in a proportion of 0.01 to 20 wt .-% based on the in the formulation Hydroxo Zinc compounds are present. As a rule, a low proportion of these substances will be sought, as this can have a positive effect on the performance of the electronic component. Particularly suitable additives are:
  • R 1 a straight-chain or branched or cycloaliphatic radical having 8 to 13 carbon atoms
  • R 2 hydrogen, an acyl radical, alkyl radical or carboxylic acid radical having in each case 1 to 8 C atoms,
  • SO styrene oxide
  • EO ethylene oxide
  • PO propylene oxide
  • n 2 to 18,
  • k 2 to 4, H or a linear or branched alkyl radical which may optionally be substituted by additional functional groups, and
  • Alkyl alkaryl, alkenyl or sulfopropyl.
  • Preferred compounds are, for example, in EP 940 406 A1
  • R 1 a straight-chain, branched or cycloaliphatic radical having 1 to 22
  • SO styrene oxide
  • EO ethylene oxide
  • BO butylene oxide
  • A is at least one divalent radical selected from the group of
  • Z is at least one radical selected from the group of sulfonic acids, sulfuric acids, phosphonic acids, phosphoric acids, carboxylic acids,
  • Isocyanates especially phosphoric acid and (meth) acrylic acid
  • a, b, c are independently values from 0 to 100, with the proviso that the sum of a + b + c> 0, preferably 5 to 35, especially 10 to 20, with the proviso that the sum of a + b + c + d> 0,
  • d 0, preferably 1 to 5
  • I, m, n independently of one another are> 2, preferably 2 to 4,
  • x, y are independently> 2.
  • R 1 are alkyl radicals having 1 to 4 carbon atoms or aryl radicals, but at least
  • radicals R 1 are methyl radicals
  • R 2 in the molecule are the same or different and may have the following meanings
  • R 3 is a hydrogen or alkyl radical
  • R 4 is a hydrogen, alkyl or carboxyl radical
  • c is a number from 1 to 20,
  • d is a number from 0 to 50
  • e is a number from 0 to 50
  • R 5 is a hydrogen, alkyl, carboxyl or an optionally
  • Ether groups containing Dimethylolpropanrest, f is a number from 2 to 20
  • R 6 is a hydrogen, alkyl or carboxyl radical
  • g is a number from 2 to 6
  • h is a number from 0 to 20
  • i is a number from 1 to 50
  • j is a number from 0 to 10
  • k is a number from 0 to 10
  • radical R 1 with the proviso that in the average molecule at least one radical R 2 has the meaning (a), where a is a number from 1 to 500, preferably 1 to 200 and especially 1 to 50 and b is a number from 0 to 10, preferably ⁇ 5 and especially 0.
  • copolymers based on styrene-based oxyalkylene glycol or polyalkylene oxide alkenyl ethers and unsaturated carboxylic acid derivatives, preferably dicarboxylic acid derivatives can be used, with a) from 1 to 80 mol% of at least one of the structural groups of the formula (8a), (8b ), (8c) and / or (8d)
  • (SO), and the alkylene oxide derivatives may be randomly or blockily distributed in the polyether, but preferably the groups are block-like and in the order
  • R 2 H, an aliphatic, optionally branched hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon having 5 to 8 C atoms, an aryl radical having 6 to 14 C atoms, which is optionally substituted or a Phosphorklar- ( preferably monoester), sulphate or sulphonate derivative. From 1 to 90 mol% of the formula (9)
  • R 3 an aliphatic, optionally branched
  • Hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic
  • Hydrocarbon having 5 to 8 carbon atoms, an aryl radical having 6 to 14 carbon atoms
  • T -U 1 -R 4 or -U 1 - (C m H, m O) n - (C m H
  • R 4 H, M a , R 3 or -Q 1 -NQ 2 Q 3 ,
  • Q 1 is a divalent alkylene radical having 2 to 24 carbon atoms
  • Q 2 and Q 3 are aliphatic and / or alicyclic alkyl radicals having 1 to 12 carbon atoms, optionally oxidized to
  • T 1 -U 1 - (C m H, m O) n - (C m H
  • polyacrylic acids having a weight-average molecular weight M w of preferably 200 to 2,000,000 g / mol, particularly preferably an M w of 1,000 to 50,000 g / mol, and their salts can be used.
  • the formulation according to the invention can furthermore not only be used directly with or without the addition of additives for producing ZnO-containing layers, but the formulation can also be embedded in matrix formers, such as e.g. PMMA, polystyrene, PP, PE, PC or PVC can be used for the production of ZnO-containing layers.
  • matrix formers such as e.g. PMMA, polystyrene, PP, PE, PC or PVC can be used for the production of ZnO-containing layers.
  • the formulation according to the invention is an aqueous formulation.
  • one or more other solvents may be present in the formulation in typical amounts for solvents or for additives.
  • organic solvents in particular alcohols, ethers and ethoxy alcohols.
  • ethers Especially preferred are secondary and tertiary alcohols.
  • secondary and tertiary alcohols are particularly well suited as additives for obtaining formulations which are easy to print.
  • the invention further provides a process for producing a ZnO-containing layer, in which a formulation of the invention is applied to a substrate and subsequently thermally converted, and the ZnO-containing layers obtainable by this process.
  • Corresponding layers are preferably semiconducting. How one skilled in the art can control the formation of semiconducting layers is known.
  • the substrate may be an Si or Si / SiO 2 wafer, a glass substrate or a polymer substrate (in particular a polymer film), the latter in particular based on PET, PE, PEN, PEI, PEEK, PI, PC, PEA , PA or PP, act.
  • a polymer substrate in particular a polymer film
  • the application of the formulation of the invention on the substrate can by dip coating, slot-the coating, spin coating, spraying or various Printing process (flexographic printing, gravure printing, ink-jet printing, screen printing, tampon printing or offset printing).
  • the thermal conversion is preferably carried out at temperatures of 120 to 450 ° C, more preferably 125 to 400 ° C. Most preferably, the thermal conversion takes place at temperatures of 125 to 300 ° C.
  • the thermal conversion can be done by the use of hot plates, ovens, laser and UV and / or microwave radiation. The big advantage of the present
  • Invention is that the choice of a low processing temperature of up to 300 ° C allows the use of polymer substrates, in particular polymer films.
  • the ZnO-containing layer produced from the formulation according to the invention can be aftertreated.
  • the properties of the produced ZnO-containing layer can be further improved by post-treatment with reducing or oxidizing atmospheres, by moisture, plasma treatment, laser treatment, UV irradiation.
  • the formulations according to the invention can preferably be used for the production of electronic components.
  • the formulations according to the invention are suitable for the production of transistors - in particular TFTs -, optoelectronic components and sensors.
  • TFTs prepared using the formulations of the invention are particularly suitable for use in LCDs or in circuits for RFI D tags.
  • the subject matter of the present invention is thus likewise an electronic component, in particular a transistor, an optoelectronic component and a sensor, each of which contains at least one, preferably semiconductive, ZnO-containing layer which has been produced by the methods described above. Examples:
  • Inventive Example 1 From nitrate salts of zinc, gallium, and indium in a molar ratio of 66.5: 28.5: 5, 15 ml of a solution of the total concentration 0.5 mol / l are prepared with completely demineralized water. This is followed by precipitation with 10 ml of 2.5 mol / L NaOH. The precipitate is separated by centrifugation (4,500 rpm, 10 minutes) and the liquid phase discarded. The precipitate is dispersed in completely demineralized water, stirred and centrifuged again,
  • nitrate salts of zinc and gallium in a molar ratio of 70:30 15 ml of a solution of the total concentration of 0.5 mol / l are used with completely demineralized water. This is followed by precipitation with 10 ml of 2.5 mol / L NaOH. The precipitate is separated by centrifugation (4,500 rpm, 10 minutes) and the liquid phase discarded. The precipitate is dispersed in completely demineralized water, stirred and centrifuged again. Subsequently, the liquid phase is discarded. This step is repeated four more times. Finally, the remaining precipitate is stirred in 28% aqueous ammonia solution for at least 1 h to give a saturated solution.
  • Silicon wafers with a 230 nm thick Si0 2 layer and prestructured source and drain contacts made of ITO are coated by spin coating (100 ⁇ , 3,000 rpm, 30 s) with the solutions according to Example 1, 2 or 3. Subsequently, the respective layer is annealed at 160 ° C. Bottom gate and bottom contact TFTS fabricated using the resulting layers have the electrical data listed in Table 1:

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Abstract

The invention relates to ammoniacal formulations comprising a) at least one hydroxo-zinc compound and b) at least one compound of an element of the 3rd primary group, to the use thereof, to a method using said formulations to produce layers comprising ZnO and to electronic components produced using same.

Description

Formulierungen enthaltend ammoniakalische Hydroxo-Zink-Verbindungen  Formulations containing ammoniacal hydroxo-zinc compounds
Die vorliegende Erfindung betrifft ammoniakalische Formulierungen enthaltend Hydroxo-Zink-Verbindungen, Verfahren zur Herstellung ZnO-haltiger Schichten, bei denen diese Formulierungen eingesetzt werden, die nach diesem Verfahren erhältlichen ZnO-haltigen Schichten, die Verwendung der Formulierungen zur Herstellung elektronischer Bauteile, sowie elektronische Bauteile enthaltend die nach dem Verfahren hergestellten ZnO-haltigen Schichten. Wegen der niedrigen Produktionskosten und der leichten Skalierbarkeit steht gedruckte Elektronik im Fokus vieler aktueller Forschungs- und Entwicklungsprojekte, insbesondere im Bereich der Halbleitertechnologie. Dabei ist ein The present invention relates to ammoniacal formulations comprising hydroxo-zinc compounds, to processes for producing ZnO-containing layers, which use these formulations, to the ZnO-containing layers obtainable by this process, to the use of the formulations for producing electronic components, and to electronic components containing the ZnO-containing layers produced by the process. Because of its low production costs and its easy scalability, printed electronics is the focus of many current research and development projects, especially in the field of semiconductor technology. There is one
elektronischer Schaltkreis undenkbar ohne Feldeffekttransistoren (FETs), die im Fall gedruckter Elektronik als Dünnschichtfeldeffekttransistoren (TFTs; thin-film field effect transistors) klassifiziert werden können. electronic circuit inconceivable without field effect transistors (FETs), which in the case of printed electronics can be classified as thin-film field effect transistors (TFTs).
Eine wichtige Komponente in jedem Transistor ist das Halbleitermaterial, welches die Schaltparameter, wie z.B. die Spannung, beeinflusst. Wichtige Parameter für Halbleitermaterialien sind die jeweiligen Feldeffektbeweglichkeiten, Verarbeitbarkeiten und Verarbeitungstemperaturen bei der Herstellung. An important component in each transistor is the semiconductor material, which has the switching parameters, e.g. the tension, influenced. Important parameters for semiconductor materials are the respective field-effect mobilities, processabilities and processing temperatures during production.
Wegen seiner Eigenschaften, die denen des Galliumnitrids ähneln, und wegen seiner einfachen und preisgünstigen Herstellung gehört Zinkoxid zu den attraktivsten anorganischen Oxidmaterialien für die Transistorherstellung. Weiterhin wird Zinkoxid wegen seiner hochinteressanten piezoelektrischen und elektromechanischen Eigenschaften auch oft in der Halbleiter-Technologie allgemein (Mater. Sei. Eng. B-Solid State Mater. Adv. Technol. 2001 , 80, 383; IEEE Trans. Microw. Theory Tech. 1969, MT17, 957) und in der Elektronik und Optoelektronik eingesetzt. Aufgrund seiner Bandlücke von 3.37 eV bei Raumtemperatur (Klingshirn, Phys. Status Solidi B, 1975, 71 , 547) und seiner hohen Excitonenbindungsenergie von 60 meV (Landolt-Because of its properties similar to those of gallium nitride, and because of its simple and inexpensive production, zinc oxide is one of the most attractive inorganic oxide materials for transistor fabrication. Furthermore, because of its highly interesting piezoelectric and electromechanical properties, zinc oxide is also commonly used in semiconductor technology in general (Mater., Eng., B-Solid State Mater., Adv., Technol., 2001, 80, 383; IEEE Trans. Microw. Theory Tech , MT17, 957) and used in electronics and optoelectronics. Due to its band gap of 3.37 eV at room temperature (Klingshirn, Phys. Status Solidi B, 1975, 71, 547) and its high exciton-binding energy of 60 meV (Landolt's
Börnstein New Series, Group III Vol. 41 B) hat Zinkoxid auch andere weit verbreitete Anwendungen, wie in der Laser-Technologie bei Raumtemperatur. Börnstein New Series, Group III Vol. 41 B), zinc oxide also has other widespread applications, as in laser technology at room temperature.
Die Hall-Beweglichkeit μΗ der Elektronen im ZnO-Einkristall beträgt 400 cm2-V"1-s"1, wobei diese Werte bei in praktischen Versuchen hergestellten Schichten bislang nicht erreicht wurden. Epitaktisch, d.h. z. B. mittels Chemical Vapour Deposition (CVD) abgeschiedene oder gesputterte ZnO-Schichten zeigen FET-Beweglichkeiten von 50 bis 155 cm2-V1-s"1. Im Stand der Technik sind weiterhin Schichten auf Basis von Mischoxiden enthaltend ZnO bekannt. So beschreibt Hosono, Journal of Non-Crystalline Solids, 2006, 352, 851 -858 über Gasphasendeposition erhaltene Feldeffekttransistoren mit amorphen Oxiden von Indium, Gallium und Zink. Somit können nicht nur reine ZnO-Schichten, sondern auch ZnO-haltige Schichten, d.h. Schichten aufweisend neben ZnO elementar oder in Verbindung (insbesondere oxidisch) vorliegende Fremdmetalle, für den Einsatz in Feldeffekttransistoren geeignet sein. The Hall mobility μ Η of the electrons in the ZnO single crystal is 400 cm 2 -V "1 -s " 1 , and these values have hitherto been obtained in practical layers were not reached. Epitaxially, ie eg ZnO layers deposited or sputtered by means of chemical vapor deposition (CVD) show FET mobilities of 50 to 155 cm 2 -V 1 -s 1. The prior art furthermore discloses layers based on mixed oxides containing ZnO For example, Hosono, Journal of Non-Crystalline Solids, 2006, 352, 851-858 describes gas phase deposition field effect transistors with amorphous oxides of indium, gallium, and zinc, which allow not only pure ZnO layers, but also ZnO-containing layers, ie Layers comprising in addition to ZnO elementary or in combination (especially oxidic) present foreign metals, be suitable for use in field effect transistors.
Mischoxidtransistoren werden auch an anderer Stelle beschrieben: Jeong et al., Adv. Mater. 2009, 21 , 329-333 beschreibt zum Beispiel über Cosputtering hergestellte ZrlnZnO-Dünnschicht-Transistoren. Park et al., Electrochemical and Solid-State Letters, 13 (9) H295-H297 (2010) beschreiben über Magnetron-Sputtering hergestellte Hf-ZnO-Dünnschicht-Transistoren. Lee et al. beschreiben über PECVD hergestellte In-Ga-ZnO-Dünnschicht-Transistoren. Den in diesen Publikationen beschriebenen Verfahren zur Herstellung von Dünnschicht-Transistoren ist jedoch gemein, dass sie einen hohen apparativen Aufwand erfordern und, u. a. aufgrund des Herstellungsprozesses, noch nicht zu Transistoren mit ausreichend guten elektrischen Eigenschaften führen. Mixed oxide transistors are also described elsewhere: Jeong et al., Adv. Mater. 2009, 21, 329-333, for example, describes cosputtering ZrInZnO thin film transistors. Park et al., Electrochemical and Solid State Letters, 13 (9) H295-H297 (2010) describe magnetron sputtered Hf-ZnO thin film transistors. Lee et al. describe PECVD fabricated In-Ga-ZnO thin film transistors. However, the process described in these publications for the production of thin-film transistors has in common that they require a high expenditure on equipment and, u. a. due to the manufacturing process, not yet lead to transistors with sufficiently good electrical properties.
Aufgrund der bereits erwähnten Vorteile von Druckprozessen wäre es somit wünschenswert, ZnO-haltige Schichten mit möglichst hohen, für den Einsatz in Schaltkreisen geeigneten Ladungsträgerbeweglichkeiten über Druckverfahren herstellen zu können. Because of the already mentioned advantages of printing processes, it would thus be desirable to be able to produce ZnO-containing layers with the highest possible charge carrier mobilities suitable for use in circuits via printing processes.
Eine Anforderung an Systeme für gedruckte Elektronik, an der die meisten heut- zutage bekannten Herstellungstechnologien für ZnO-haltige Schichten scheitern, ist die gewünschte niedrige Prozessierungstemperatur. Diese sollte signifikant unterhalb von 300 °C, noch besser unterhalb von 200 °C liegen, um für flexible polymerbasierte Substrate geeignet zu sein. Prinzipiell gibt es zwei Möglichkeiten zur Realisierung gedruckter Elektronik: Partikel- Konzepte und Precursor-Konzepte. One requirement for printed electronics systems, where most of today's known ZnO-containing film fabrication technologies fail, is the desired low processing temperature. This should be significantly below 300 ° C, more preferably below 200 ° C, to be suitable for flexible polymer-based substrates. In principle, there are two possibilities for the realization of printed electronics: particle concepts and precursor concepts.
Partikel-basierte Konzepte setzen dabei vor allem auf den Einsatz nanopartikulärer Systeme, wie z. B. ZnO-Nanoröhren (Nano Letters, 2005, 5, 12, 2408-2413). Die Nachteile der Partikel-Konzepte liegen zum einen in der kolloidalen Instabilität der eingesetzten Partikel-Dispersionen, die die Verwendung von Dispergieradditiven erforderlich macht, welche wiederum die resultierende Ladungsträgerbeweglichkeit negativ beeinflussen können. Zum anderen stellt der Partikel-Partikel-Widerstand ein Problem dar, da dieser die Beweglichkeit von Ladungsträgern verringert und allgemein den Schichtwiderstand erhöht. Particle-based concepts are based primarily on the use of nanoparticulate systems, such. ZnO nanotubes (Nano Letters, 2005, 5, 12, 2408-2413). The disadvantages of the particle concepts are, on the one hand, the colloidal instability of the particle dispersions used, which necessitates the use of dispersing additives, which in turn can adversely affect the resulting charge carrier mobility. On the other hand, the particle-particle resistance is a problem because it reduces the mobility of charge carriers and generally increases the sheet resistance.
Für den Precursor-Ansatz können prinzipiell verschiede Zn2+-Salze zur ZnO- Synthese verwendet werden, z. B. ZnCI2, ZnBr2, Zn(OAc)2, andere Zn-Salze von Carbonsäuren, Zn(N03)2 und Zn(S04)2. Trotz der resultierenden guten Beweglichkeitswerte sind solche Precursoren jedoch für die druckbare Elektronik nicht geeignet, weil die Prozessierungstemperatur immer weit über 350°C liegt (siehe z. B. J. Am. Chem. Soc. 2007, 129, 2750 - 2751 für die Zersetzung von Zn(OAc)2 bzw. IEEE Trans., 54, 6, 2007, 1301 -1307 für die Zersetzung von ZnCI2). Durch Einsatz von z. B. Chelatliganden kann die Prozessierungstemperatur zwar verringert werden, ihre Verwendung erweist sich jedoch als nachteilig für die resultierenden Schichten (DE 20 2005 010 697 U1 ). Im Gegensatz zu den aufgeführten Zinksalzen sind die einfach industriell verfügbaren Dialkylzinkverbindungen, wie z. B. Me2Zn und Et2Zn, sehr reaktiv. Gerade aus diesem Grund ist die Prozessierung mit ihnen jedoch sehr aufwendig, und so besteht ein Bedarf an anderen ZnO-Precursoren, die für die druckbare Elektronik gut geeignet sind. In principle, different Zn 2+ salts can be used for the ZnO synthesis for the precursor approach, eg. ZnCl 2 , ZnBr 2 , Zn (OAc) 2 , other Zn salts of carboxylic acids, Zn (NO 3 ) 2 and Zn (SO 4 ) 2 . However, despite the resulting good mobility values, such precursors are not suitable for printable electronics because the processing temperature is always well above 350 ° C. (see, for example, J. Am. Chem. Soc., 2007, 129, 2750-2751 for the decomposition of Zn (FIG. OAc) 2 and IEEE Trans., 54, 6, 2007, 1301-1307 for the decomposition of ZnCl 2 ). By using z. B. Chelatliganden Although the processing temperature can be reduced, but their use proves to be detrimental to the resulting layers (DE 20 2005 010 697 U1). In contrast to the listed zinc salts are the industrially available dialkylzinc compounds such. Me 2 Zn and Et 2 Zn, very reactive. However, for this reason, the processing with them is very expensive, and so there is a need for other ZnO precursors that are well suited for printable electronics.
Keszler et al., J. Am. Chem. Soc. 2008, 130, 17603-17609 beschreiben gut prozessierbare ammoniakalische Lösungen von Zink-Hydroxid-Verbindungen, in denen sich ein Zn-Ammin-Hydroxo-Komplex der generischen Formel Keszler et al., J. Am. Chem. Soc. 2008, 130, 17603-17609 describe good processible ammoniacal solutions of zinc hydroxide compounds in which a Zn-amine-hydroxo complex of the generic formula
Zn(OH)x(NH3)y (2"x)+ bildet, die über eine basische Fällung aus Zinknitratlösungen und anschließendes Auflösen des resultierenden Niederschlages in ammoniakalischem Wasser hergestellt werden können. Mit diesen können bei Temperaturen ab ca. 150 °C ZnO-haltige Schichten hergestellt werden. Gute Feldeffektmobilitäten, Einschaltspannungen und ein gutes Hystereseverhalten, die diese Schichten für den Einsatz in Feldeffekttransistoren geeignet machen, resultieren jedoch nur bei einer Konvertierungstemperatur von mindestens 300 °C. Diese hohen Konvertierungstemperaturen sind jedoch nachteilig, wenn flexible Substrate als Träger eingesetzt werden sollen. Flexible Substrate wie z. B. Polymerfolien sind jedoch für die Zn (OH) x (NH 3 ) y (2 "x) + , which can be prepared by a basic precipitation from zinc nitrate solutions and subsequent dissolution of the resulting precipitate in ammoniacal water with ZnO Good field effect mobilities, turn-on voltages and a good hysteresis behavior, these layers for the Use in field effect transistors make suitable, but only result in a conversion temperature of at least 300 ° C. However, these high conversion temperatures are disadvantageous when flexible substrates are to be used as carriers. Flexible substrates such. B. polymer films are, however, for the
Erzeugung flexibler Bauelemente aufweisend ZnO-haltige Schichten von essentieller Bedeutung. Generation of flexible components comprising ZnO-containing layers of essential importance.
Fleischhaker et al., J. Mater. Chem., 2010, 20, 6622-6625, beschreiben einen alternativen Ansatz zur Herstellung von ammoniakalischen Lösungen von Zink- Hydroxid-Verbindungen. Dabei wird kommerziell erhältliches ZnO in wässrigerFleischhaker et al., J. Mater. Chem., 2010, 20, 6622-6625, describe an alternative approach to the preparation of ammoniacal solutions of zinc hydroxide compounds. In this case, commercially available ZnO in aqueous
Ammmoniaklösung aufgelöst. Daraus bei Konvertierungstemperaturen von 150 °C erhältliche ZnO-haltige Schichten weisen jedoch keine ausreichend guten elektrischen Eigenschaften (insbesondere Feldeffektmobilitäten, Ammonia solution dissolved. However, ZnO-containing layers obtainable at conversion temperatures of 150 ° C. do not have sufficiently good electrical properties (in particular field effect mobilities,
Einschaltspannungen und Hystereseverhalten) auf. Switch-on voltages and hysteresis behavior).
Schmechel et al., Thin Solid films 201 1 , 519, 5623-5628, beschreiben den Einsatz von Zinkoxidhydrat in ammoniakalischer Lösung bei der Synthese ZnO-haltiger Schichten sowie bei Konvertierungstemperaturen von 125, 300 bzw. 500 °C hergestellte Feldeffekttransistoren. Auch deren elektrische Eigenschaften Schmechel et al., Thin Solid films 201 1, 519, 5623-5628, describe the use of zinc oxide hydrate in ammoniacal solution in the synthesis of ZnO-containing layers and at conversion temperatures of 125, 300 and 500 ° C produced field effect transistors. Also their electrical properties
(insbesondere Feldeffektmobilitäten, Einschaltspannungen und Hystereseverhalten) sind jedoch noch nicht zufriedenstellend. (especially field effect mobilities, turn-on voltages and hysteresis behavior) are still unsatisfactory.
Moon et al., J. Mater. Chem., 201 1 , 21 , 13524, beschreiben Yttrium-dotierte ZnO- Transistoren, die aus ammoniakalischen Formulierungen umfassend Hydroxo-Zink- Verbindungen und Y(OH)3 hergestellt werden. Die beschriebenen Y-dotiertenMoon et al., J. Mater. Chem., 201 1, 21, 13524, describe yttrium-doped ZnO transistors prepared from ammoniacal formulations comprising hydroxo-zinc compounds and Y (OH) 3 . The described Y-doped
Schichten zeigen jedoch bei den elektrischen Eigenschaften, insbesondere bei den Feldeffektbeweglichkeiten, schlechtere Werte als nicht Y-dotierte Schichten. However, layers show in the electrical properties, especially in the Feldeffektbeweglichkeiten, worse values than non-Y-doped layers.
Weiterhin sind die erforderlichen Konvertierungstemperaturen für die gewünschten Zwecke nicht einsetzbar. Furthermore, the required conversion temperatures for the desired purposes can not be used.
Es ist somit Aufgabe der vorliegenden Erfindung, gegenüber dem bekannten Stand der Technik Systeme bereitzustellen, mit denen die bestehenden Ansätze zur Herstellung ZnO-haltiger Schichten aus Precursor-basierenden Systemen dahingehend verbessert werden können, dass auch bei niedrigen Verarbeitungs- temperaturen ZnO-haltige Schichten mit guten elektrischen Eigenschaften, insbesondere mit hohen Elektronenbeweglichkeiten μΡΕτ, einer günstigen Hysterese und einer günstigen Einschaltspannung resultieren. Unter einer günstigen Hysterese ist dabei ein Wert für die Quantifizierung der Pfadabhängigkeit einer Messung, d.h. die Differenz zwischen gemessener Spannung zwischen„Hin-" und„Rückweg" zu verstehen, die möglichst klein sein soll. Dabei lässt sich die Hysterese bei einem bestimmten Drainstrom (hier: 1 ■ 10"8 A) als Unterschied der Gatespannung zwischen der Hin- und der Rückkurve als waagerechte Linie zwischen den beiden It is therefore an object of the present invention to provide over the known prior art systems with which the existing approaches for producing ZnO-containing layers of precursor-based systems can be improved to the effect that even at low processing temperatures ZnO-containing layers good electrical properties, especially with high electron mobilities μ Ρ Ετ, a favorable hysteresis and a favorable turn-on voltage result. Under a favorable hysteresis is a value for the quantification of the path dependence of a measurement, ie to understand the difference between measured voltage between "back" and "return", which should be as small as possible. In this case, the hysteresis at a certain drain current (here: 1 ■ 10 "8 A) as a difference of the gate voltage between the outward and the return curve can be a horizontal line between the two
Schnittpunkten mit der Transferkennlinie bestimmen. Unter Einschaltspannung ist die Spannung zwischen Gate und Source zu verstehen, bei der der Transistor einschaltet, d.h. anfängt, den elektrischen Strom zwischen Source und Drain zu leiten. Dieser Wert sollte möglichst nahe bei 0 V liegen Determine points of intersection with the transfer characteristic. By turn-on voltage is meant the voltage between gate and source at which the transistor turns on, i. begins to conduct the electrical current between the source and drain. This value should be as close as possible to 0V
Die vorliegende Aufgabe wird gelöst durch die erfindungsgemäße ammoniakalische Formulierung umfassend a) mindestens eine Hydroxo-Zink-Verbindung, und b) mindestens eine Verbindung eines Elements der 3. Hauptgruppe. The present object is achieved by the novel ammoniacal formulation comprising a) at least one hydroxo-zinc compound, and b) at least one compound of an element of the third main group.
Unter einer ammoniakalischen Formulierung umfassend mindestens eine Hydroxo- Zink-Verbindung ist dabei eine wässrige, ammoniakhaltige Zusammensetzung zu verstehen, in der eine Hydroxo-Zink-Verbindung gelöst bzw. in der aus nicht- Hydroxo-Zink-Verbindungen eine Hydroxo-Zink-Verbindung gebildet wurde. An ammoniacal formulation comprising at least one hydroxo-zinc compound is an aqueous, ammonia-containing composition in which a hydroxo-zinc compound is dissolved or in which non-hydroxo-zinc compounds form a hydroxo-zinc compound has been.
Entsprechende Hydroxo-Zink-Verbindungen können ein oder mehrere Corresponding hydroxo-zinc compounds may be one or more
Komplexatome aufweisen, bei denen es sich im Wesentlichen um Zink handelt. Bevorzugt weist die ammoniakalische Formulierung nur eine einzige Hydroxo-Zink- Verbindung auf. Bevorzugt, da dies zu besonders guten und homogenen Schichten führt, weist die Hydroxo-Zink-Verbindung nur ein einziges Zentralion auf, bei dem es sich um Zink handelt. Weiterhin weist die Hydroxo-Zink-Verbindung Hydroxo- Gruppen (= -OH-Gruppen) als Liganden auf. Entsprechende Hydroxo-Zink- Verbindungen können weiterhin Ammin-Liganden (NH3-Liganden) anlagern. Die Hydroxo-Zink-Verbindung kann neben dem/den Zn-Zentralion(en) und den Hydroxo- und ggf. Ammin-Liganden weitere Liganden aufweisen. Bevorzugt, weil dies zuHave complex atoms, which is essentially zinc. Preferably, the ammoniacal formulation has only a single hydroxo-zinc compound. Preferably, since this leads to particularly good and homogeneous layers, the hydroxo-zinc compound has only a single central ion, which is zinc. Furthermore, the hydroxo-zinc compound Hydroxo- groups (= -OH groups) as ligands. Corresponding hydroxo-zinc compounds can furthermore attach to amine ligands (NH 3 ligands). The hydroxo-zinc compound may have further ligands besides the Zn central ion (s) and the hydroxo and, if appropriate, ammin ligands. Preferably, because this too
Schichten mit besonders guten elektrischen Eigenschaften führt, weist die Hydroxo- Zink-Verbindung ausschließlich Hydroxo- und ggf. Ammin-Liganden auf. Layers with particularly good electrical properties leads, the hydroxo-zinc compound exclusively hydroxo- and possibly amine ligands.
Die mindestens eine Hydroxo-Zink-Verbindung kann dabei in der ammoniakalischen Formulierung dissoziiert und ggf. solvatisiert oder dispergiert vorliegen. Besonders bevorzugt, weil diese sich besonders gut zur Herstellung von homogenen Schichten mit besonders guten elektrischen Eigenschaften eignen, sind The at least one hydroxo-zinc compound can be dissociated in the ammoniacal formulation and optionally present solvated or dispersed. Particularly preferred because they are particularly suitable for the production of homogeneous layers with particularly good electrical properties, are
ammoniakalische Lösungen von Zink-Hydroxid-Verbindungen, die einen Zn-Ammin- Hydroxo-Komplex der generischen Formel Zn(OH)x(NH3)y (2"x)+ mit 1 < x < 2 und 1 < y < 6 enthalten. Entsprechende Formulierungen können aus Zinknitratlösungen über eine basische Fällung mit einer Hydroxidbase wie z. B. NaOH und Ammoniacal solutions of zinc hydroxide compounds containing a Zn-ammine hydroxo complex of the generic formula Zn (OH) x (NH 3 ) y (2 "x) + with 1 <x <2 and 1 <y <6 Corresponding formulations may be prepared from zinc nitrate solutions via basic precipitation with a hydroxide base such as NaOH and
anschließendes Auflösen des resultierenden Niederschlages in ammoniakalischem Wasser hergestellt werden. Die erfindungsgemäße Formulierung weist die mindestens eine Hydroxo-Zink- Verbindung bevorzugt in Anteilen von 50 bis 99,95 Mol-%, bevorzugt von 85 bis 99,95 Mol-%, besonders bevorzugt von 95 bis 99,95 Mol-% bezogen auf die then dissolving the resulting precipitate in ammoniacal water. The formulation of the invention comprises the at least one hydroxo-zinc compound, preferably in proportions of from 50 to 99.95 mol%, preferably from 85 to 99.95 mol%, particularly preferably from 95 to 99.95 mol%, based on the
Gesamtstoffmenge von Zinkionen und Atomen/Ionen des Elements der 3. Total amount of zinc ions and atoms / ions of the element of FIG.
Hauptgruppe auf. Main group on.
Die erfindungsgemäße Formulierung weist weiterhin mindestens eine Verbindung eines Elements der 3. Hauptgruppe auf. Somit weist die Formulierung mindestens eine Verbindung eines Elements ausgewählt aus der Gruppe bestehend aus Bor (B), Aluminium (AI), Gallium (Ga), Indium (In) und Thallium (Tl) auf. Dabei resultieren besonders gute Ergebnisse, wenn das Element der 3. Hauptgruppe dreiwertig vorliegt. Besonders gute Ergebnisse werden erzielt, wenn die mindestens eine Verbindung eines Elements der 3. Hauptgruppe eine Verbindung von Aluminium (AI), Gallium (Ga) oder Indium (In) ist. Die mindestens eine Verbindung des Elements der 3. Hauptgruppe kann dabei in der ammoniakalischen Formulierung dissoziiert und ggf. solvatisiert oder dispergiert vorliegen. The formulation of the invention further comprises at least one compound of an element of the 3rd main group. Thus, the formulation comprises at least one compound of an element selected from the group consisting of boron (B), aluminum (AI), gallium (Ga), indium (In) and thallium (Tl). This results in particularly good results when the element of the 3rd main group is trivalent. Particularly good results are achieved if the at least one compound of an element of the 3rd main group is a compound of aluminum (AI), gallium (Ga) or indium (In). The at least one compound of the element of the 3rd main group can be dissociated in the ammoniacal formulation and optionally present solvated or dispersed.
Bevorzugt, weil dies zu besonders guten elektrischen Eigenschaften der mit Hilfe entsprechender Zusammensetzungen herstellbaren ZnO-haltigen Schichten führt, umfasst die ammoniakalische Formulierung mindestens zwei Verbindungen von Elementen der 3. Hauptgruppe. Dabei sind diese weiter bevorzugt Verbindungen unterschiedlicher Elemente der 3. Hauptgruppe. Ganz besonders gute Ergebnisse werden erzielt, wenn die Formulierung mindestens eine Gallium-Verbindung und mindestens eine Indium-Verbindung aufweist. Die erfindungsgemäße Formulierung weist die mindestens eine Verbindung eines Elements der 3. Hauptgruppe bevorzugt in Anteilen von 0,05 bis 50 Mol-%, bevorzugt von 0,05 bis 15 Mol-%, besonders bevorzugt von 0,05 bis 5 Mol-% bezogen auf die Gesamtstoffmenge von Zinkionen und Atomen/Ionen des Elements der 3. Hauptgruppe auf. Preferably, because this leads to particularly good electrical properties of the ZnO-containing layers which can be produced with the aid of corresponding compositions, the ammoniacal formulation comprises at least two compounds of elements of the 3rd main group. These are more preferably compounds of different elements of the 3rd main group. Very good results are achieved when the formulation comprises at least one gallium compound and at least one indium compound. The formulation according to the invention comprises the at least one compound of an element of the 3rd main group, preferably in proportions of from 0.05 to 50 mol%, preferably from 0.05 to 15 mol%, particularly preferably from 0.05 to 5 mol% on the total amount of zinc ions and atoms / ions of the element of the 3rd main group.
Liegen zwei oder mehr Verbindungen von Elementen der 3. Hauptgruppe in der Formulierung vor, betragen deren jeweiligen Anteile bevorzugt 1 bis 99 Mol-%, bevorzugt 5 bis 95 Mol-% bezogen auf die Gesamtstoffmenge der eingesetzten Verbindungen von Elementen der 3. Hauptgruppe. If two or more compounds of elements of the 3rd main group are present in the formulation, their respective proportions are preferably 1 to 99 mol%, preferably 5 to 95 mol%, based on the total amount of the compounds of elements of the 3rd main group used.
Besonders bevorzugt sind ammoniakalische Formulierungen, die neben der Hydroxo-Zink-Verbindung noch mindestens eine Verbindung von Indium und mindestens eine Verbindung von Gallium aufweisen. Weiter bevorzugt beträgt dabei das Verhältnis der Gesamtstoffmengen der eingesetzten Verbindungen von Particular preference is given to ammoniacal formulations which, in addition to the hydroxo-zinc compound, also contain at least one compound of indium and at least one compound of gallium. More preferably, the ratio of the total amounts of the compounds used of
Elementen der 3. Hauptgruppe bezogen auf die Stoffmenge der darin vorhandenen Ga- bzw. In-Atome 50 bis 99 Mol-%, bevorzugt 66 bis 95 Mol-%, und besonders bevorzugt 75 bis 90 Mol-% für die Ga-Verbindungen und 1 bis 50 Mol-%, bevorzugt 5 bis 33 Mol-% und besonders bevorzugt 10 bis 25 Mol-% für die In-Verbindungen.  Elements of the 3rd main group based on the molar amount of the Ga or In atoms present therein 50 to 99 mol%, preferably 66 to 95 mol%, and particularly preferably 75 to 90 mol% for the Ga compounds and 1 to 50 mol%, preferably 5 to 33 mol% and particularly preferably 10 to 25 mol% of the In compounds.
Liegt in der Formulierung mindestens eine Gallium- und mindestens eine Indium- Verbindung vor, ist die Formulierung besonders gut zur Herstellung Zinkoxid-haltiger Schichten mit besonders guten elektrischen Eigenschaften geeignet, wenn die Hydroxo-Zink-Verbindung in Anteilen von 65 - 75 Mol-%, die Galliumverbindung in Anteilen von 25 - 34 Mol-% und die Indiumverbindung in Anteilen von 1 - 10 Mol-% bezogen auf die Gesamtstoffmenge von Zinkionen und Atomen/Ionen des Elements der 3. Hauptgruppe vorliegt. If at least one gallium compound and at least one indium compound is present in the formulation, the formulation is particularly suitable for producing zinc oxide-containing layers having particularly good electrical properties if the hydroxo-zinc compound is present in proportions of 65-75 mol%. , the gallium compound is present in proportions of 25-34 mol% and the indium compound in proportions of 1-10 mol% based on the total amount of zinc ions and atoms / ions of the element of the 3rd main group.
Besonders gut einsetzbare Verbindungen von Elementen der 3. Hauptgruppe sind die entsprechende Nitrate, Hydroxide, Oxide, Oxidhydroxide, Halogenide undParticularly useful compounds of elements of the 3rd main group are the corresponding nitrates, hydroxides, oxides, oxide hydroxides, halides and
Oxidhalogenide. Ganz besonders bevorzugt können die Nitrate, Hydroxide, Oxide, Oxidhydroxide, Halogenide oder Oxidhalogenide von Aluminium, Indium oder Gallium eingesetzt werden. Beste ZnO-haltige Schichten resultieren, wenn Formulierungen eingesetzt werden, die a) durch Auflösen der Nitratsalze von Zink und mindestens einem Element der 3. Hauptgruppe in dreiwertiger Oxidationsstufe, b) Ausfällen eines hydroxidhaltigen Niederschlages mit einer Hydroxidbase, c) Abtrennen des Lösemittels, ggf. c') Waschen, und d) Aufnahme des Niederschlages in ammoniakalischem Wasser herstellbar ist. Als Hydroxidbase bevorzugt einsetzbar sind die Basen NaOH und KOH. Das Abtrennen kann bevorzugt über Filtration oder Zentrifugation erfolgen. Bei der Aufnahme des Niederschlages in ammoniakalischem Wasser kann dieser vollständig oder zum Teil in Lösung gehen. Die Konzentration des Ammoniaks in der wässrigen Ammoniakformulierung, die den Niederschlag aufnimmt, beträgt dabei bevorzugt 20 bis 33 Gew.-%, bevorzugt 25 bis 30 Gew.-%, bezogen auf die Oxyhalides. Very particular preference may be given to using the nitrates, hydroxides, oxides, oxide hydroxides, halides or oxyhalides of aluminum, indium or gallium. Best ZnO-containing layers result when formulations are used which a) by dissolving the nitrate salts of zinc and at least one element of the 3rd main group in trivalent oxidation state, b) precipitating a hydroxide-containing precipitate with a hydroxide base, c) separating the solvent, if necessary c) washing, and d) producing the precipitate in ammoniacal water. As hydroxide hydroxide preferably used are the bases NaOH and KOH. The separation can preferably be carried out by filtration or centrifugation. When taking up the precipitate in ammoniacal water, it can go completely or partially into solution. The concentration of ammonia in the aqueous ammonia formulation which absorbs the precipitate is preferably from 20 to 33 wt .-%, preferably 25 to 30 wt .-%, based on the
Gesamtmasse an Ammoniak und Wasser. Ein vollständiges Auflösen ist jedoch nicht erforderlich für die Ausführbarkeit der vorliegenden Erfindung. Weiterhin können die Schritte c), c') und d) zur Erzielung besonders guter Schichten ein- oder mehrfach wiederholt werden. Total mass of ammonia and water. However, complete dissolution is not required for the practicability of the present invention. Furthermore, steps c), c ') and d) can be repeated one or more times to achieve particularly good layers.
Bevorzugt beträgt die Gesamtkonzentration an Zinkionen und Elementatomen/-ionen der 3. Hauptgruppe zur Erzielung besonders guter Ergebnisse 0,05 bis 2, bevorzugt 0,1 bis 1 , besonders bevorzugt 0,1 bis 0,5 mol/l. Preferably, the total concentration of zinc ions and element atoms / ions of the 3rd main group to achieve particularly good results 0.05 to 2, preferably 0.1 to 1, particularly preferably 0.1 to 0.5 mol / l.
Die erfindungsgemäße Formulierung eignet sich hervorragend zu Herstellung ZnO- haltiger Schichten, ohne dass ihr dafür weitere Additive zugesetzt werden müssen. Nichtsdestotrotz sind die erfindungsgemäßen Formulierungen kompatibel mit verschiedenen Additiven, wie z. B. Substanzen, die selbige gegen Reagglomeration und Sedimentation stabilisieren. In der Regel kann dieses mindestens eine Additiv, abhängig vom Typ, der Konzentration an Hydroxo-Zink-Verbindung und der Art der flüssigen Phase der Dispersion in einem Anteil von 0,01 bis 20 Gew.-% bezogen auf die in der Formulierung befindlichen Hydroxo-Zink-Verbindungen vorliegen. In der Regel wird man einen niedrigen Anteil dieser Stoffe anstreben, da dies positive Auswirkungen auf die Leistungsfähigkeit des elektronischen Bauteiles haben kann. Besonders geeignete Additive sind: The formulation according to the invention is outstandingly suitable for the production of ZnO-containing layers without having to add further additives for this purpose. Nevertheless, the formulations according to the invention are compatible with various additives, such. B. substances that stabilize the same against reagglomeration and sedimentation. In general, this at least one additive, depending on the type, the concentration of hydroxo-zinc compound and the nature of the liquid phase of the dispersion in a proportion of 0.01 to 20 wt .-% based on the in the formulation Hydroxo Zinc compounds are present. As a rule, a low proportion of these substances will be sought, as this can have a positive effect on the performance of the electronic component. Particularly suitable additives are:
I) Styrenoxidbasiertes Polyalkylenoxid mit statistischer Verteilung oder als Block- copolymer der allgemeinen Formel (1 ), R10(SO)a(EO)b(PO)c(BO)dR2 wobei I) styrene-based polyalkylene oxide with random distribution or as a block copolymer of the general formula (1), R 1 0 (SO) a (EO) b (PO) c (BO) d R 2 wherein
R1 = ein geradkettiger oder verzweigter oder cycloaliphatischer Rest mit 8 bis 13 Kohlenstoffatomen, R 1 = a straight-chain or branched or cycloaliphatic radical having 8 to 13 carbon atoms,
R2 = Wasserstoff, ein Acylrest, Alkylrest oder Carbonsäurerest mit jeweils 1 bis 8 C-Atomen, R 2 = hydrogen, an acyl radical, alkyl radical or carboxylic acid radical having in each case 1 to 8 C atoms,
SO = Styrenoxid, EO = Ethylenoxid, PO = Propylenoxid,  SO = styrene oxide, EO = ethylene oxide, PO = propylene oxide,
BO = Butylenoxid und BO = butylene oxide and
a = 1 bis 5, a = 1 to 5,
b = 3 bis 50, b = 3 to 50,
c = 0 bis 3, c = 0 to 3,
d = 0 bis 3 sind, wobei b > a + c + d ist. d = 0 to 3, where b> a + c + d.
Verbindungen mit a=1 bis 1 ,9 sind beispielsweise in EP 1 078 946 A1 beschrieben. Compounds with a = 1 to 1, 9 are described for example in EP 1 078 946 A1.
II) Ein Phosphorsäureester der allgemeinen Formel (2), II) A phosphoric acid ester of the general formula (2),
mit R = with R =
wobei in which
x = 1 oder 2, x = 1 or 2,
n = 2 bis 18, n = 2 to 18,
m, o = 2 bis 100, m, o = 2 to 100,
k = 2 bis 4, H oder ein linearer oder verzweigter Alkylrest, der gegebenenfalls mit zusätzlichen funktionellen Gruppen substituiert sein kann, und k = 2 to 4, H or a linear or branched alkyl radical which may optionally be substituted by additional functional groups, and
Alkyl-, Alkaryl-, Alkenyl- oder Sulfopropylrest.  Alkyl, alkaryl, alkenyl or sulfopropyl.
Bevorzugt eingesetzte Verbindungen sind beispielsweise in EP 940 406 A1 Preferred compounds are, for example, in EP 940 406 A1
beschrieben. described.
III) Weiterhin können Blockcopolymere und deren Salze der allgemeinen Formel (3), [R10(SO)a(EO)b(CH2CHCH30)c(BO)d]xP(=0)(OH)3-x (3), eingesetzt werden, III) Furthermore, block copolymers and their salts of general formula (3), [R 1 0 (SO) a (EO) b (CH 2 CHCH 3 0) c (BO) d ] x P (= 0) (OH) 3 -x (3), to be used,
wobei in which
R1 = ein geradkettiger, verzweigter oder cycloaliphatischer Rest mit 1 bis 22 R 1 = a straight-chain, branched or cycloaliphatic radical having 1 to 22
Kohlenstoffatomen,  Carbon atoms,
SO = Styrenoxid, EO = Ethylenoxid, BO = Butylenoxid und  SO = styrene oxide, EO = ethylene oxide, BO = butylene oxide and
a = 1 bis < 2, a = 1 to <2,
b = 0 bis 100, b = 0 to 100,
c = 0 bis 10, c = 0 to 10,
d = 0 bis 3 sind, wobei b > a + c + d ist. d = 0 to 3, where b> a + c + d.
IV) Weiterhin können Verbindungen eingesetzt werden, die erhältlich sind durch die teilweise oder vollständige Umsetzung von: IV) Furthermore, compounds can be used which are obtainable by the partial or complete conversion of:
A) einem oder mehreren aminofunktionellen Polymeren mit  A) one or more amino-functional polymers with
B) einem oder mehreren Polyestern der allgemeinen Formeln (4)/(4a) B) one or more polyesters of the general formulas (4) / (4a)
T-C(0)-[0-A-C(0)]x-OH (4), T-0-[C(0)-A-0-]y-Z (4a) und TC (0) - [0-AC (0)] x -OH (4), T-0- [C (O) -A-O-] y -Z (4a) and
C) einem oder mehreren Polyethern der allgemeinen Formel (5)/(5a) C) one or more polyethers of the general formula (5) / (5a)
T-C(0)-B-Z (5), T-O-B-Z (5a), worin T ein Wasserstoffrest und/oder ein gegebenenfalls substituierter, linearer oder  T-C (O) -B-Z (5), T-O-B-Z (5a), wherein T is a hydrogen radical and / or an optionally substituted, linear or
verzweigter Aryl-, Arylalkyl-, Alkyl- oder Alkenylrest mit 1 bis 24  branched aryl, arylalkyl, alkyl or alkenyl radical having 1 to 24
Kohlenstoffatomen ist,  Carbon atoms,
A mindestens ein zweiwertiger Rest ist, ausgesucht aus der Gruppe der A is at least one divalent radical selected from the group of
linearen, verzweigten, cyclischen und aromatischen Kohlenwasserstoffe, Z mindestens ein Rest ist, ausgesucht aus der Gruppe der Sulfonsäuren, Schwefelsäuren, Phosphonsäuren, Phosphorsäuren, Carbonsäuren, linear, branched, cyclic and aromatic hydrocarbons, Z is at least one radical selected from the group of sulfonic acids, sulfuric acids, phosphonic acids, phosphoric acids, carboxylic acids,
Isocyanate, Epoxide, insbesondere der Phosphorsäure und (Meth)acrylsäure, Isocyanates, epoxides, especially phosphoric acid and (meth) acrylic acid,
B ein Rest der allgemeinen Formel (6) ist B is a radical of general formula (6)
-(C,H2|0)a -(CmH2mO)b -(C H2 0)c-(SO)d- (6) - (C, H 2 | O) a - (C m H 2m O) b - (CH 2 O) c - (SO) d - (6)
a, b, c unabhängig voneinander Werte von 0 bis 100 sind, mit der Maßgabe, dass die Summe aus a + b + c > 0, vorzugsweise 5 bis 35, insbesondere 10 bis 20 ist, mit der Maßgabe, dass die Summe aus a + b + c + d > 0, a, b, c are independently values from 0 to 100, with the proviso that the sum of a + b + c> 0, preferably 5 to 35, especially 10 to 20, with the proviso that the sum of a + b + c + d> 0,
d > 0, vorzugsweise 1 bis 5 ist, d> 0, preferably 1 to 5,
I, m, n unabhängig voneinander > 2, vorzugsweise 2 bis 4 ist,  I, m, n independently of one another are> 2, preferably 2 to 4,
x, y unabhängig voneinander > 2 sind. x, y are independently> 2.
V) Weiterhin können Organopolysiloxane der allgemeinen Formel (7) eingesetzt werden, V) Furthermore, it is possible to use organopolysiloxanes of the general formula (7)
- -
wobei die Reste where the radicals
R1 Alkylreste mit 1 bis 4 Kohlenstoffatomen oder Arylreste sind, jedoch mindestensR 1 are alkyl radicals having 1 to 4 carbon atoms or aryl radicals, but at least
80 % der Reste R1 Methylreste sind, 80% of the radicals R 1 are methyl radicals,
R2 im Molekül gleich oder verschieden sind und nachfolgende Bedeutungen haben können R 2 in the molecule are the same or different and may have the following meanings
a)  a)
R3 ein Wasserstoff- oder Alkylrest, R4 ein Wasserstoff-, Alkyl- oder Carboxylrest, R 3 is a hydrogen or alkyl radical, R 4 is a hydrogen, alkyl or carboxyl radical,
c eine Zahl von 1 bis 20,  c is a number from 1 to 20,
d eine Zahl von 0 bis 50,  d is a number from 0 to 50,
e eine Zahl von 0 bis 50 ist,  e is a number from 0 to 50,
oder  or
b) -(CH2-)fOR5, worin, b) - (CH 2 -) f OR 5 , in which
R5 ein Wasserstoff-, Alkyl-, Carboxyl- oder ein gegebenenfallsR 5 is a hydrogen, alkyl, carboxyl or an optionally
Ethergruppen enthaltender Dimethylolpropanrest, f eine Zahl von 2 bis 20 ist Ether groups containing Dimethylolpropanrest, f is a number from 2 to 20
oder  or
c) -(CH2-)g(OC2H4-)h(OC3H6-)i(OC4H8)j(OCH2 CH(C6H5))kOR6 c) - (CH 2 -) g (OC 2 H 4) h (OC 3 H 6 -) i (OC 4 H 8 ) j (OCH 2 CH (C 6 H 5 )) k OR 6
worin  wherein
R6 ein Wasserstoff-, Alkyl- oder Carboxylrest, R 6 is a hydrogen, alkyl or carboxyl radical,
g eine Zahl von 2 bis 6,  g is a number from 2 to 6,
h eine Zahl von 0 bis 20,  h is a number from 0 to 20,
i eine Zahl von 1 bis 50,  i is a number from 1 to 50,
j eine Zahl von 0 bis 10,  j is a number from 0 to 10,
k eine Zahl von 0 bis 10 ist  k is a number from 0 to 10
oder  or
d) dem Rest R1 entspricht, mit der Maßgabe, dass im durchschnittlichen Molekül mindestens ein Rest R2 die Bedeutung (a) hat, wobei a eine Zahl von 1 bis 500, vorzugsweise 1 bis 200 und insbesondere 1 bis 50 und b eine Zahl von 0 bis 10, vorzugsweise < 5 und insbesondere 0 ist. d) the radical R 1 , with the proviso that in the average molecule at least one radical R 2 has the meaning (a), where a is a number from 1 to 500, preferably 1 to 200 and especially 1 to 50 and b is a number from 0 to 10, preferably <5 and especially 0.
Solche Verbindungen sind beispielsweise in EP 1 382 632 A1 beschrieben. Such compounds are described, for example, in EP 1 382 632 A1.
VI) Weiterhin können Copolymere auf Basis von styrenoxidbasierten Oxyalkylen- glykol- oder Polyalkylenoxid-Alkenylethern und ungesättigten Carbonsäure-, vorzugsweise Dicarbonsäure-Derivaten eingesetzt werden, mit a) 1 bis 80 Mol-% mindestens einer der Baugruppen der Formel (8a), (8b), (8c) und/oder (8d) VI) Furthermore, copolymers based on styrene-based oxyalkylene glycol or polyalkylene oxide alkenyl ethers and unsaturated carboxylic acid derivatives, preferably dicarboxylic acid derivatives, can be used, with a) from 1 to 80 mol% of at least one of the structural groups of the formula (8a), (8b ), (8c) and / or (8d)
-CH2- CR1- -CH 2 - CR 1 -
(CH2)P - O - (SO)i - (CmH,mO)n - (CmH,mO)0-R2 -CH2- CR1 - (CH 2) P - O - (SO) i - (C m H, m O) n - (C m H, m O) 2 -R 0 -CH 2 - CR 1 -
O - ((CH2)q - 0)t - (SO)i -(CmH,mO)n - (CmH,mO)0-R2 -CH2- CR1 - O - ((CH 2) q - 0) t - (SO) i - (C m H, m O) n - (C m H, m O) 0 -R 2 -CH 2 - CR 1 -
COO - (SO)i - (CmH,mO)n - (CmH,mO)0-R2 COO - (SO) i - (C m H, m O) n - (C m H, m O) 2 -R 0
-CH2- CR1 - -CH 2 - CR 1 -
CONH - (SO)i -(CmH,mO)n - (CmH,mO)0-R2 CONH - (SO) i - (C m H, m O) n - (C m H, m O) 2 -R 0
worin wherein
1  1
R = H, aliphatischer Kohlenwasserstoffrest mit 1 bis 5 C-Atomen, p = 1 -4, q = 0-6, t = 0-4, i = 1 -6, 1 = 1 -2, m = 2-18 sind,  R = H, aliphatic hydrocarbon radical having 1 to 5 C atoms, p = 1 -4, q = 0-6, t = 0-4, i = 1 -6, 1 = 1 -2, m = 2-18 .
wobei der Index am H-Atom durch das Produkt aus I und m gebildet wird, n = 0-100, o = 0-100, SO = Styrenoxid, wherein the index at the H atom is formed by the product of I and m, n = 0-100, o = 0-100, SO = styrene oxide,
wobei (SO), und die Alkylenoxidderivate statistisch oder blockartig im Polyether verteilt sein können, bevorzugterweise liegen die Gruppen aber blockartig aufgebaut und in der Reihenfolge wherein (SO), and the alkylene oxide derivatives may be randomly or blockily distributed in the polyether, but preferably the groups are block-like and in the order
- (SO) - [(CmH,mO)n-(CmH|mO)0] - R2 vor. - (SO) - [(C m H, m O) n - (C m H | m O) 0 ] - R 2 .
R2 = H, ein aliphatischer, gegebenenfalls verzweigter Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, ein cycloaliphatischer Kohlenwasserstoff mit 5 bis 8 C-Atomen, ein Arylrest mit 6 bis 14 C-Atomen, der gegebenenfalls substituiert ist oder ein Phosphorsäureester-, (vorzugsweise Monoester), Sulfat- oder Sulfonatderivat sein kann. 1 bis 90 Mol-% Baugruppen der Formel (9) R 2 = H, an aliphatic, optionally branched hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon having 5 to 8 C atoms, an aryl radical having 6 to 14 C atoms, which is optionally substituted or a Phosphorsäureester- ( preferably monoester), sulphate or sulphonate derivative. From 1 to 90 mol% of the formula (9)
R1 R 1
I  I
— CH— C—  - CH- C-
S wobei  S being
S = -H, -COOMa, -COOR3 bedeutet, M = Wasserstoff, ein- oder zweiwertiges Metallkation, Ammoniumion, organischer Aminrest, S = -H, -COOM a , -COOR 3 , M = hydrogen, monovalent or divalent metal cation, ammonium ion, organic amine radical,
a = 1 oder für den Fall, dass M ein zweiwertiges Metallkation 14 ist, R3 = ein aliphatischer, gegebenenfalls verzweigter a = 1 or in the case that M is a divalent metal cation 14, R 3 = an aliphatic, optionally branched
Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, ein cycloaliphatischer Hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic
Kohlenwasserstoff mit 5 bis 8 C-Atomen, ein Arylrest mit 6 bis 14 C-Hydrocarbon having 5 to 8 carbon atoms, an aryl radical having 6 to 14 carbon atoms
Atomen ist, Atoms is,
T = -U1-R4 oder -U1-(CmH,mO)n-(CmH|mO)0-R2, T = -U 1 -R 4 or -U 1 - (C m H, m O) n - (C m H | m O) 0 -R 2 ,
U1 =-COO-, -CONH-, -CONR3-, -O-, -CH20-, U 1 = -COO-, -CONH-, -CONR 3 -, -O-, -CH 2 O-,
R4 = H, Ma, R3 oder -Q1-NQ2Q3 ist, R 4 = H, M a , R 3 or -Q 1 -NQ 2 Q 3 ,
wobei in which
Q1 ein zweiwertiger Alkylenrest mit 2 bis 24 Kohlenstoffatomen, Q2 und Q3 - aliphatische und/oder alicyclische Alkylreste mit 1 bis 12 Kohlenstoffatomen sind, gegebenenfalls oxidiert zu Q 1 is a divalent alkylene radical having 2 to 24 carbon atoms, Q 2 and Q 3 are aliphatic and / or alicyclic alkyl radicals having 1 to 12 carbon atoms, optionally oxidized to
-Q1 -N(+)O(-)Q2Q3 -Q 1 -N ( + ) O (-) Q 2 Q 3
und and
m, n, I, o, R1 und R2 die oben genannte Bedeutung aufweisen, 10 Mol-% Baugruppen der Formel (10) m, n, I, o, R 1 and R 2 have the abovementioned meaning, 10 mol% of groups of the formula (10)
R1 R 1
I  I
— CH— C—  - CH- C-
S 1 wobei S 1 being
T1 = -U1-(CmH,mO)n-(CmH|mO)o-R5 bedeutet, T 1 = -U 1 - (C m H, m O) n - (C m H | m O) o -R 5 means
R5 = R4 oder - CH2 - CH - U2 - C = CH R 5 = R 4 or - CH 2 - CH - U 2 - C = CH
I I I  I II
.1 _1 wobei U2 = -OOC -, -NHOC-, -O-, -0-CH2- ist, Where U 2 = -OOC -, -NHOC-, -O-, -O-CH 2 -,
wobei m, n, I, o, S, R1, R2 und U1 die oben genannte Bedeutung aufweisen. Solche Verbindungen sind beispielsweise in DE 103 48 825 A1 beschrieben. where m, n, I, o, S, R 1 , R 2 and U 1 have the abovementioned meaning. Such compounds are described for example in DE 103 48 825 A1.
(VII) Weiterhin können Polyacrylsäuren mit einem gewichtsmittleren Molekulargewicht Mw von bevorzugt 200 bis 2.000.000 g/mol, besonders bevorzugt einem Mw von 1.000 bis 50.000 g/mol und ihre Salze eingesetzt werden. (VII) Further, polyacrylic acids having a weight-average molecular weight M w of preferably 200 to 2,000,000 g / mol, particularly preferably an M w of 1,000 to 50,000 g / mol, and their salts can be used.
Die erfindungsgemäße Formulierung kann weiterhin nicht nur direkt mit oder ohne Zusatz von Additiven zur Herstellung ZnO-haltiger Schichten eingesetzt werden, sondern die Formulierung kann auch eingebettet in Matrixbildner wie z.B. PMMA, Polystyrol, PP, PE, PC oder PVC für die Herstellung ZnO-haltiger Schichten eingesetzt werden. The formulation according to the invention can furthermore not only be used directly with or without the addition of additives for producing ZnO-containing layers, but the formulation can also be embedded in matrix formers, such as e.g. PMMA, polystyrene, PP, PE, PC or PVC can be used for the production of ZnO-containing layers.
Die erfindungsgemäße Formulierung ist eine wässrige Formulierung. Zur Erzielung positiver Eigenschaften können in der Formulierung jedoch ein oder mehrere weitere Lösemittel in für Lösemittel bzw. für Additive typischen Mengen vorliegen. The formulation according to the invention is an aqueous formulation. In order to achieve positive properties, however, one or more other solvents may be present in the formulation in typical amounts for solvents or for additives.
Bevorzugt handelt es sich dabei um organische Lösemittel, insbesondere um Alkohole, Ether und Ethoxyalkohole. Besonders bevorzugt sind sekundäre und tertiäre Alkohole. Diese Substanzen eignen sich besonders gut als Additive zur Erzielung gut verdruckbarer Formulierungen. These are preferably organic solvents, in particular alcohols, ethers and ethoxy alcohols. Especially preferred are secondary and tertiary alcohols. These substances are particularly well suited as additives for obtaining formulations which are easy to print.
Gegenstand der Erfindung ist weiterhin eine Verfahren zur Herstellung einer ZnO- haltigen Schicht, bei dem eine erfindungsgemäße Formulierung auf ein Substrat aufgebracht und daran anschließend thermisch konvertiert wird, und die nach diesem Verfahren herstellbaren ZnO-haltigen Schichten. Entsprechende Schichten sind bevorzugt halbleitend. Wie der Fachmann das Entstehen halbleitender Schichten steuern kann, ist bekannt. The invention further provides a process for producing a ZnO-containing layer, in which a formulation of the invention is applied to a substrate and subsequently thermally converted, and the ZnO-containing layers obtainable by this process. Corresponding layers are preferably semiconducting. How one skilled in the art can control the formation of semiconducting layers is known.
Bei dem Substrat kann es sich um ein Si- oder Si/Si02-Wafer, ein Glassubstrat oder ein Polymersubstrat (insbesondere eine Polymerfolie), letztere insbesondere auf der Basis von PET, PE, PEN, PEI, PEEK, PI, PC, PEA, PA oder PP, handeln. The substrate may be an Si or Si / SiO 2 wafer, a glass substrate or a polymer substrate (in particular a polymer film), the latter in particular based on PET, PE, PEN, PEI, PEEK, PI, PC, PEA , PA or PP, act.
Das Aufbringen der erfindungsgemäßen Formulierung auf das Substrat kann durch Tauchbeschichtung, Slot-Die Coating, Spin-Coating, Aufsprühen oder verschiedene Druckverfahren (Flexo-Druck, Gravur-Druck, Ink-Jet-Druck, Sieb-Druck, Tampon- Druck oder Offset-Druck) erfolgen. The application of the formulation of the invention on the substrate can by dip coating, slot-the coating, spin coating, spraying or various Printing process (flexographic printing, gravure printing, ink-jet printing, screen printing, tampon printing or offset printing).
Die thermische Konvertierung erfolgt bevorzugt bei Temperaturen von 120 bis 450 °C, weiter bevorzugt 125 bis 400°C. Ganz besonders bevorzugt erfolgt die thermische Konvertierung bei Temperaturen von 125 bis 300 °C. Dabei kann die thermische Konvertierung durch den Einsatz von Heizplatten, Öfen, Laser und UV- und/oder Mikrowellenstrahlung erfolgen. Der große Vorteil der vorliegenden The thermal conversion is preferably carried out at temperatures of 120 to 450 ° C, more preferably 125 to 400 ° C. Most preferably, the thermal conversion takes place at temperatures of 125 to 300 ° C. The thermal conversion can be done by the use of hot plates, ovens, laser and UV and / or microwave radiation. The big advantage of the present
Erfindung ist, dass die Wahl einer geringen Verarbeitungstemperatur von bis zu 300 °C die Verwendung von Polymersubstraten, insbesondere Polymerfolien, ermöglicht. Invention is that the choice of a low processing temperature of up to 300 ° C allows the use of polymer substrates, in particular polymer films.
Im Anschluss an die thermische Konvertierung kann die aus der erfindungsgemäßen Formulierung hergestellte ZnO-haltige Schicht nachbehandelt werden. So können die Eigenschaften der hergestellten ZnO-haltigen Schicht durch eine Nachbehandlung mit reduzierenden bzw. oxidierenden Atmosphären, durch Feuchtigkeit, Plasmabehandlung, Laserbehandlung, UV-Bestrahlung noch weiter verbessert werden. Subsequent to the thermal conversion, the ZnO-containing layer produced from the formulation according to the invention can be aftertreated. Thus, the properties of the produced ZnO-containing layer can be further improved by post-treatment with reducing or oxidizing atmospheres, by moisture, plasma treatment, laser treatment, UV irradiation.
Die erfindungsgemäßen Formulierungen können bevorzugt zur Herstellung elektronischer Bauteile eingesetzt werden. Insbesondere eignen sich die erfindungsgemäßen Formulierungen für die Herstellung von Transistoren - insbesondere TFTs - , optoelektronischen Bauteilen und Sensoren. Insbesondere TFTs, die unter Einsatz der erfindungsgemäßen Formulierungen hergestellt werden, eigenen sich besonders für den Einsatz in LCDs oder in Schaltkreisen für RFI D-Tags. The formulations according to the invention can preferably be used for the production of electronic components. In particular, the formulations according to the invention are suitable for the production of transistors - in particular TFTs -, optoelectronic components and sensors. In particular, TFTs prepared using the formulations of the invention are particularly suitable for use in LCDs or in circuits for RFI D tags.
Gegenstand der vorliegenden Erfindung ist somit ebenfalls ein elektronisches Bauteil, insbesondere ein Transistor, ein optoelektronisches Bauteil und ein Sensor, die jeweils mindestens eine, bevorzugt halbleitende, ZnO-haltige Schicht, die nach den zuvor beschriebenen Verfahren hergestellt wurde, enthalten. Beispiele: The subject matter of the present invention is thus likewise an electronic component, in particular a transistor, an optoelectronic component and a sensor, each of which contains at least one, preferably semiconductive, ZnO-containing layer which has been produced by the methods described above. Examples:
Erfindungsgemäßes Beispiel 1 : Aus Nitratsalzen des Zinks, des Galliums, und des Indiums im molaren Verhältnis 66,5 : 28,5 : 5 wird mit vollständig entsalztem Wasser 15 mL einer Lösung der Gesamtkonzentration 0,5 mol/L angesetzt. Anschließend erfolgt mit 10 mL 2,5 mol/L NaOH eine Fällung. Der Niederschlag wird durch Zentrifugation (4.500 rpm, 10 Minuten) abgetrennt und die flüssige Phase verworfen. Der Niederschlag wird in vollständig entsalztem Wasser dispergiert, gerührt und erneut zentrifugiert, Inventive Example 1: From nitrate salts of zinc, gallium, and indium in a molar ratio of 66.5: 28.5: 5, 15 ml of a solution of the total concentration 0.5 mol / l are prepared with completely demineralized water. This is followed by precipitation with 10 ml of 2.5 mol / L NaOH. The precipitate is separated by centrifugation (4,500 rpm, 10 minutes) and the liquid phase discarded. The precipitate is dispersed in completely demineralized water, stirred and centrifuged again,
Anschließend wird die flüssige Phase verworfen. Dieser Schritt wird noch viermal wiederholt. Schließlich wird der zurückbleibende Niederschlag in 28 %iger wässriger Ammoniaklösung mindestens 1 h unter Entstehen einer gesättigten Lösung gerührt. Erfindungsgemäßes Beispiel 2:  Subsequently, the liquid phase is discarded. This step is repeated four more times. Finally, the remaining precipitate is stirred in 28% aqueous ammonia solution for at least 1 h to give a saturated solution. Inventive Example 2:
Aus Nitratsalzen des Zinks und des Galliums im molaren Verhältnis 70 : 30 wird mit vollständig entsalztem Wasser 15 mL einer Lösung der Gesamtkonzentration 0,5 mol/L angesetzt. Anschließend erfolgt mit 10 mL 2,5 mol/L NaOH eine Fällung. Der Niederschlag wird durch Zentrifugation (4.500 rpm, 10 Minuten) abgetrennt und die flüssige Phase verworfen. Der Niederschlag wird in vollständig entsalztem Wasser dispergiert, gerührt und erneut zentrifugiert, Anschließend wird die flüssige Phase verworfen. Dieser Schritt wird noch viermal wiederholt. Schließlich wird der zurückbleibende Niederschlag in 28 %iger wässriger Ammoniaklösung mindestens 1 h unter Entstehen einer gesättigten Lösung gerührt. From nitrate salts of zinc and gallium in a molar ratio of 70:30, 15 ml of a solution of the total concentration of 0.5 mol / l are used with completely demineralized water. This is followed by precipitation with 10 ml of 2.5 mol / L NaOH. The precipitate is separated by centrifugation (4,500 rpm, 10 minutes) and the liquid phase discarded. The precipitate is dispersed in completely demineralized water, stirred and centrifuged again. Subsequently, the liquid phase is discarded. This step is repeated four more times. Finally, the remaining precipitate is stirred in 28% aqueous ammonia solution for at least 1 h to give a saturated solution.
Vergleichsbeispiel 3: Comparative Example 3
Aus dem Nitratsalz des Zinks wird mit vollständig entsalztem Wasser 15 mL einer Lösung der Gesamtkonzentration 0,5 mol/L angesetzt. Anschließend erfolgt mit 10 mL 2,5 mol/L NaOH eine Fällung. Der Niederschlag wird durch Zentrifugation (4.500 rpm, 10 Minuten) abgetrennt und die flüssige Phase verworfen. Der Niederschlag wird in vollständig entsalztem Wasser dispergiert, gerührt und erneut zentrifugiert, Anschließend wird die flüssige Phase verworfen. Dieser Schritt wird noch viermal wiederholt. Schließlich wird der zurückbleibende Niederschlag in 28 %iger wässriger Ammoniaklösung mindestens 1 h unter Entstehen einer gesättigten Lösung gerührt. From the nitrate salt of zinc, 15 mL of a solution of total concentration 0.5 mol / L is added with completely demineralized water. This is followed by precipitation with 10 ml of 2.5 mol / L NaOH. The precipitate is separated by centrifugation (4,500 rpm, 10 minutes) and the liquid phase discarded. The precipitate is dispersed in completely demineralized water, stirred and centrifuged again. Subsequently, the liquid phase is discarded. This step will be four more times repeated. Finally, the remaining precipitate is stirred in 28% aqueous ammonia solution for at least 1 h to give a saturated solution.
Siliciumwafer mit einer 230 nm dicken Si02-Schicht und vorstrukturierten Source- und Drain-Kontakten aus ITO werden über Spin coating (100 μΙ, 3.000 rpm, 30 s) mit den Lösungen gemäß Beispiel 1 , 2 oder 3 beschichtet. Anschließend wird die jeweilige Schicht bei 160 °C getempert. Unter Verwendung der resultierenden Schichten hergestellte TFTS mit Bottom Gate- und Bottom Contact-Konfiguration weisen die in Tabelle 1 aufgeführten elektrischen Daten auf: Silicon wafers with a 230 nm thick Si0 2 layer and prestructured source and drain contacts made of ITO are coated by spin coating (100 μΙ, 3,000 rpm, 30 s) with the solutions according to Example 1, 2 or 3. Subsequently, the respective layer is annealed at 160 ° C. Bottom gate and bottom contact TFTS fabricated using the resulting layers have the electrical data listed in Table 1:
Tabelle 1 : Table 1 :

Claims

Patentansprüche: claims:
1 . Ammoniakalische Formulierung umfassend 1 . Comprising ammoniacal formulation
a) mindestens eine Hydroxo-Zink-Verbindung, und  a) at least one hydroxo-zinc compound, and
b) mindestens eine Verbindung eines Elements der 3. Hauptgruppe.  b) at least one compound of an element of the 3rd main group.
2. Formulierung nach Anspruch 1 , dadurch gekennzeichnet, dass die Hydroxo-Zink- Verbindung ein einziges Zentralion aufweist, bei dem es sich um Zink handelt 3. Formulierung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die 2. Formulation according to claim 1, characterized in that the hydroxo-zinc compound has a single central ion, which is zinc 3. Formulation according to claim 1 or 2, characterized in that the
Hydroxo-Zink-Verbindung ausschließlich Hydroxo- und ggf. Ammin-Liganden aufweist.  Hydroxo-zinc compound exclusively Hydroxo- and possibly Ammin ligands has.
4. Formulierung nach einem der vorhergehenden Ansprüche, dadurch 4. Formulation according to one of the preceding claims, characterized
gekennzeichnet, dass die Hydroxo-Zink-Verbindung Zn(OH)x(NH3)y (2"x)+ mitcharacterized in that the hydroxo-zinc compound Zn (OH) x (NH 3 ) y (2 "x) + with
1 < x < 2 und 1 < y < 6 ist. 1 <x <2 and 1 <y <6.
5. Formulierung nach einem der vorhergehenden Ansprüche, dadurch 5. Formulation according to one of the preceding claims, characterized
gekennzeichnet, dass sie die mindestens eine Hydroxo-Zink-Verbindung in Anteilen von 50 bis 99,95 Mol-% bezogen auf die Gesamtstoffmenge von in that it contains the at least one hydroxo-zinc compound in proportions of from 50 to 99.95 mol%, based on the total amount of substance of
Zinkionen und Atomen/Ionen des Elements der 3. Hauptgruppe aufweist. Zinc ions and atoms / ions of the element of the 3rd main group has.
6. Formulierung nach einem der vorhergehenden Ansprüche, dadurch 6. Formulation according to one of the preceding claims, characterized
gekennzeichnet, dass die mindestens eine Verbindung eines Elements der 3. Hauptgruppe eine Verbindung von Aluminium (AI), Gallium (Ga) oder Indium (In) ist.  in that the at least one compound of an element of the 3rd main group is a compound of aluminum (AI), gallium (Ga) or indium (In).
7. Formulierung nach einem der vorhergehenden Ansprüche, dadurch 7. Formulation according to one of the preceding claims, characterized
gekennzeichnet, dass sie mindestens zwei Verbindungen von Elementen der 3. Hauptgruppe umfasst.  characterized in that it comprises at least two compounds of elements of the 3rd main group.
8. Formulierung nach Anspruch 7, dadurch gekennzeichnet, dass sie mindestens eine Gallium-Verbindung und mindestens eine Indium-Verbindung aufweist. 8. A formulation according to claim 7, characterized in that it comprises at least one gallium compound and at least one indium compound.
9. Formulierung nach einem der vorhergehenden Ansprüche, dadurch 9. Formulation according to one of the preceding claims, characterized
gekennzeichnet, dass sie a) durch Auflösen der Nitratsalze von Zink und mindestens einem Element der 3. Hauptgruppe in dreiwertiger Oxidationsstufe, b) Ausfällen eines hydroxidhaltigen Niederschlages mit einer Hydroxidbase, c) Abtrennen des Lösemittels und d) Aufnahme des Niederschlages in  characterized in that they are a) by dissolving the nitrate salts of zinc and at least one element of the 3rd main group in a trivalent oxidation state, b) precipitating a hydroxide-containing precipitate with a hydroxide base, c) separating off the solvent and d) taking up the precipitate in
ammoniakalischem Wasser herstellbar ist.  ammoniacal water can be produced.
10. Verfahren zur Herstellung einer ZnO-haltigen Schicht, dadurch gekennzeichnet, dass eine Formulierung nach den Ansprüchen 1 bis 9 auf ein Substrat aufgebracht und daran anschließend thermisch konvertiert wird. 10. A method for producing a ZnO-containing layer, characterized in that a formulation according to claims 1 to 9 applied to a substrate and subsequently thermally converted.
1 1 . Verwendung einer Formulierung nach einem der Ansprüche 1 bis 9 zur 1 1. Use of a formulation according to any one of claims 1 to 9 for
Herstellung elektronischer Bauteile, insbesondere zur Herstellung von  Production of electronic components, in particular for the production of
Transistoren, optoelektronischen Bauteilen und Sensoren.  Transistors, optoelectronic components and sensors.
12. Elektronisches Bauteil, enthaltend mindestens eine ZnO-haltige Schicht, die nach einem Verfahren nach Anspruch 10 hergestellt wurde. 12. An electronic component comprising at least one ZnO-containing layer, which was prepared by a method according to claim 10.
13. Elektronisches Bauteil nach Anspruch 12, dadurch gekennzeichnet, dass es ein Transistor ist. 13. Electronic component according to claim 12, characterized in that it is a transistor.
14. Elektronisches Bauteil nach Anspruch 12, dadurch gekennzeichnet, dass es ein optoelektronisches Bauteil ist. 14. Electronic component according to claim 12, characterized in that it is an optoelectronic component.
15. Elektronisches Bauteil nach Anspruch 12, dadurch gekennzeichnet, dass es ein Sensor ist. 15. Electronic component according to claim 12, characterized in that it is a sensor.
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