EP1169492B1 - Method of producing thin, poorly soluble coatings - Google Patents

Method of producing thin, poorly soluble coatings Download PDF

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Publication number
EP1169492B1
EP1169492B1 EP00934914A EP00934914A EP1169492B1 EP 1169492 B1 EP1169492 B1 EP 1169492B1 EP 00934914 A EP00934914 A EP 00934914A EP 00934914 A EP00934914 A EP 00934914A EP 1169492 B1 EP1169492 B1 EP 1169492B1
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Prior art keywords
layer
precursor
reactant gas
layers
hydroxide
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German (de)
French (fr)
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EP1169492A2 (en
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Christian-Herbert Fischer
Hans-Jürgen Muffler
Martha Christina Lux-Steiner
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Hahn Meitner Institut Berlin GmbH
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Hahn Meitner Institut Berlin GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S501/00—Compositions: ceramic
    • Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
    • Y10S501/906—Thorium oxide containing

Definitions

  • the invention relates to a method for producing thin, sparingly soluble Coatings on substrates with any morphology. In doing so prefers ceramic and oxide layers, but also metallic as well further chalcogenidic layers can be produced.
  • Ceramic materials are inorganic, non-metallic, poorly soluble in water and at least 30% crystalline. However, they can be expanded by the group of glasses, glass ceramics and inorganic binders.
  • the ceramic materials are divided into the two large groups “functional ceramics” and “structural ceramics”. Structural ceramics consider materials based on oxides and silicates as well as carbides, nitrides, borides and silicides (MoSi 2 ) of main group elements.
  • oxide ceramics can be understood to mean all ceramic materials which essentially (> 90%) consist of single-phase and single-component metal oxides. In contrast, all materials based on ceramics made from the boron, carbon, nitrogen, silicon and possibly oxygen system are called “non-oxide ceramics". Oxide-ceramic materials are polycrystalline materials made from pure oxides or oxide compounds; they have a high purity and are usually free of glass phase. In addition to the high-melting metal oxides, such as aluminum, zirconium, magnesium, titanium and beryllium oxide, and calcium oxide, magneto-ceramic materials and materials with a high dielectric constant, piezoceramic, can also be included.
  • high-melting metal oxides such as aluminum, zirconium, magnesium, titanium and beryllium oxide, and calcium oxide
  • magneto-ceramic materials and materials with a high dielectric constant, piezoceramic can also be included.
  • oxide ceramic materials include, for example, chromite with a coarse structure and perovskite, ferrites and garnets with a fine structure.
  • Hardly soluble layers have so far been possible, for example, by sputtering or Evaporation using the sol-gel technique, chemical bath deposition or deposition from the vapor phase (Metal Organic Chemical Vapor Deposition MOCVD) can be applied to surfaces.
  • chemical bath deposition or deposition from the vapor phase Metal Organic Chemical Vapor Deposition MOCVD
  • MOCVD Metal Organic Chemical Vapor Deposition
  • ZnO films with good quality can also be produced by direct electrode deposition from aqueous solutions at a low process temperature (see: "reparation Of ZnO Films By Electrodepositon From Aqueous Solution” by S.Peulon at al., 13th European Photovoltaic Solar Energy Conference , 23-27 October 1995, Nice, France, 1750-52).
  • sol-gel technique cf. "Micostructure of TiO 2 and ZnO Films Fabricated by the Sol-Gel-Method" by Y.Ohya et al., J.Am.Ceram.Soc. 79 [4] 825-30 (1996)
  • the object of the present invention is also to enable the production of further surface layers in other material compositions.
  • the process should still be simple in its sequence, also in ecological and economic terms.
  • an expanded range of applications should be achieved through the materials that can then be used.
  • a qualitatively improved coating with improved utilization of the materials used compared to the known coatings with chalcogenide structure should also be aimed at as a sub-item in this problem area.
  • films of sparingly soluble can Oxides and generally of such compounds that can be converted a dry solid starting compound with a gaseous reactant form simply be made.
  • This is crucial the first hydrolysis to achieve a homogeneous Dried starting substance layer by a moist surface Reactant gas to form hydroxides or complexes, for example Amine complexes when using moist ammonia gas as the reactant gas.
  • the reactant gas can also be another, preferentially reacting steam or possibly for water vapor alone act.
  • steam With the designation "steam” always moist gases, i.e. on Mixture of gaseous water, basic gas and in most cases an inert carrier gas.
  • Moist ammonia gas is generated by simply "bubbling" nitrogen through a wash bottle aqueous ammonia solution. The generation of metallic layers by Fumigation accordingly requires treatment with reducing effects Gases.
  • thermal after fumigation Treatment is then by elimination of water - and also with complexes by ligand elimination - the desired ceramic or oxidic Surface layers or other end layers created.
  • the thermal Treatment of the hydroxide or complex layers can be done in a separate Process step after gassing with the reactant gas, for example by heating the layers in an oven. But it can also during the process of gassing by increasing the process temperature be effected. By applying a higher temperature the optional cleaning step may omitted, because this already undesirable Substances can be removed from the film. In particular Cases can even be brought about without using a targeted one Temperature increase immediately form an oxide.
  • the thermal treatment can affect both extend necessary fumigations.
  • the thermal treatment for education The respective final layer can also be removed in individual cases be understood by disruptive components. In the preparation of metallic layers, this is used to create unwanted by-products to remove.
  • the starting substance is a metal compound, for example metal halides such as ZnCl 2 or AlCl 3 , of the metal whose oxide, ceramic (for example ZnO, Al 2 O 3 ) or metal is desired as the end product for the coating.
  • the correspondingly dissolved metal salt is then applied to the substrate, dried (if necessary up to a defined residual moisture) and reacted with gaseous reactants.
  • Layers produced with the method according to the invention can Solar technology used in the manufacture of many components of solar cells Find.
  • materials technology a coating can be used by everyone possible smooth, rough and porous substrates. Still allowed the process through the use of starting material mixtures or different starting substances and their alternating use, also the production of homogeneously doped layers and mixed layers and the generation of multilayers.
  • the thin, heavy ones can be used soluble coatings especially wherever there is an extended Surface protection is required. This can be purely mechanical and chemical protection of the surface, but also about influencing their physical and chemical surface properties, such as for example conductivity, reflection and absorption behavior or Catalysis or chemisorption.
  • the Chalcogenization step for the formation of sulfides, selenides or tellurides in that described in the older German application DE 198 31 214 ILGAR processes also changed the crystal structure in certain cases.
  • the increased energy requirement during the crystal transformation can in the sense of well-known tempering of course also directly through an increased Process temperature provided during the chalcogenization step become.
  • the substrate can already be illuminated with a Halogen lamp is sufficient.
  • An implementation of the chalcogenization step inside a furnace is also possible.
  • the measures mentioned lead to purer and higher quality thin films with a simultaneous reduction in quantity of the chalcogen-containing reactant gas to be used and reduce the deposition time, as on rinsing steps, the time costs and reduce the quality of the end product can be.
  • the hydroxide reaction is introduced there are no starting material residues more to expect, the by-products that occur here are relatively volatile and with a suitable temperature selection in the last Process step removable.
  • FIG. 1 shows the production of a zinc oxide layer on an amorphous substrate S , which is clamped in a substrate holder SH that can be moved in three-dimensional space.
  • the substrate holder SH has a cover C to cover the individual baths.
  • a suitable starting substance P precursor
  • this is a solution bath LB with the dissolved metal compound zinc chloride ZnCl 2 .
  • a starting substance layer PL here ZnCl 2 , on the substrate surface.
  • the ZnCl 2 layer is first dried in a vessel V in a second process step II , for example by introducing a gas stream GS. This can be inert nitrogen.
  • a gas stream GS This can be inert nitrogen.
  • the dried starting substance layer PLD is again gassed in the vessel V with a moist reactant gas RG, here moist ammonia gas.
  • the moist ammonia gas is produced by simply introducing nitrogen N 2 into a wash bottle B in which there are concentrated ammonia solution NH 4 OH and water H 2 O.
  • a hydroxide layer HL has formed on the substrate S , in the exemplary embodiment zinc hydroxide Zn (OH) 2 .
  • Different vessels V can also be used for drying and gassing.
  • a fourth method step IV the substrate S provided with the zinc hydroxide Zn (OH) 2 is introduced into an oven H.
  • the Zn (OH) 2 is thermally converted into zinc oxide ZnO by elimination of water by supplying energy.
  • This oxide or ceramic layer OL / CL covers the entire accessible surface of the substrate, including the inner surface, safely and exerts its functionality there.
  • a subsequent rinsing and drying process step is optional and not shown here. Depending on the desired layer thickness, the process steps mentioned can be cycled through several times.
  • FIG. 2 schematically shows the process sequence according to the invention for producing other chalcogenide coatings using the example of cadmium sulfide CdS.
  • Process steps and reference numerals which are not further explained here can be found in the description of FIG. 1.
  • a further process step IIIa follows which the hydroxide layer HL (Cd (OH) 2 ) formed is brought into contact with an additional reactant gas CRG (here hydrogen sulfide H 2 S) containing chalcogen hydrogen compounds.
  • CRG hydrogen sulfide H 2 S
  • This process step IIIa the chalcogenization step, produces a chalcogenide coating CHL in the form of cadmium sulfide (CdS) on the substrate S.
  • the process temperature TP is increased, for example by carrying out the process steps in a muffle furnace H, in order to improve the material conversion.
  • the thermal treatment in process step IV therefore extends to both fumigations III, IIIa.

Abstract

For making ceramic or oxidic layers (CL/OL) on substrates (S), the method according to the invention therefore provides that following application (I) and drying (II) of a suitable precursor (P) the formed precursor layer (PLD) is gassed (III) with a moist reactant gas (RG) for conversion into a corresponding hydroxide or complex layer (HL) and then thermally treated (IV) for forming a ceramic or oxidic layer (CL/OL). For the alternative production of other chalcogenidic layers of increased material conversion additional gassing is carried out with a reactant gas containing chalcogen hydrogen. Metallic layers may alternatively be made by use of a reducing reactant gas. The methods in accordance with the invention may be used wherever surfaces, even those of shaded structures, must be protected or modified or provided with functional layers, particularly in solar and materials technology.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung dünner, schwer löslicher Beschichtungen auf Substraten mit beliebiger Morphologie. Dabei sollen bevorzugt keramische und oxidische Schichten, aber auch metallische sowie weitere chalkogenidische Schichten herstellbar sein.The invention relates to a method for producing thin, sparingly soluble Coatings on substrates with any morphology. In doing so prefers ceramic and oxide layers, but also metallic as well further chalcogenidic layers can be produced.

Nach der Definition (vgl. "Technische Keramik" Herausgeber B. Thier, Vulkan Verlag, Essen 1988, Seiten 2 bis 25.) der Deutschen Keramischen Gesellschaft sind keramische Werkstoffe anorganisch, nichtmetallisch, in Wasser schwer löslich und zu wenigstens 30% kristallin. Sie können aber durch die Gruppe der Gläser, Glaskeramiken und anorganischen Bindemittel erweitert werden. Unterteilt werden die keramischen Werkstoffe in die beiden großen Gruppen "Funktionskeramik" und "Strukturkeramik". Bei der Strukturkeramik betrachtet man Werkstoffe auf Basis von Oxiden und Silikaten sowie von Carbiden, Nitriden, Boriden und Siliziden (MoSi2) von Hauptgruppenelementen.According to the definition (cf. "Technical Ceramics" published by B. Thier, Vulkan Verlag, Essen 1988, pages 2 to 25) of the German Ceramic Society, ceramic materials are inorganic, non-metallic, poorly soluble in water and at least 30% crystalline. However, they can be expanded by the group of glasses, glass ceramics and inorganic binders. The ceramic materials are divided into the two large groups "functional ceramics" and "structural ceramics". Structural ceramics consider materials based on oxides and silicates as well as carbides, nitrides, borides and silicides (MoSi 2 ) of main group elements.

Bei systematischer Betrachtungsweise können unter "Oxidkeramik" alle keramischen Werkstoffe verstanden werden, die im Wesentlichen (>90%) aus einphasigen und einkomponentigen Metalloxiden bestehen. Im Gegensatz dazu bezeichnet man alle Werkstoffe auf Basis keramisch hergestellter Materialien aus dem System Bor, Kohlenstoff, Stickstoff, Silizium und u.U. Sauerstoff als "Nichtoxidkeramiken". Oxidkeramische Werkstoffe sind polykristalline Materialien aus reinen Oxiden oder Oxidverbindungen; sie weisen eine hohe Reinheit auf und sind in der Regel frei von Glasphase. Neben den hochschmelzenden Metalloxiden, wie z.B. Aluminium-, Zirkon-, Magnesium-, Titan- und Berylliumoxid, und Kalziumoxid kann man auch magnetkeramische Werkstoffe und Stoffe mit hoher Dielektrizitätskonstante, Piezokeramik, dazurechnen. Üblich ist aber die Beschränkung auf die hochschmelzenden Oxide. Siliziumdioxid (SiO2) wird jedoch nicht unter die Oxidkeramik klassifiziert. Deshalb und auch in Berücksichtigung weiterer Oxide, die geeignet sind, aber nicht zu den keramischen Werkstoffen gehören, bezieht sich die Erfindung auch auf die Herstellung sowohl von keramischen als auch von oxidischen Schichten. Bei den oxidkeramischen Werkstoffen unterscheidet man weiterhin zwischen einfachen Oxiden und komplexen Oxiden. Hierzu zählen beispielsweise Chromit mit grobem Gefüge und Perowskite, Ferrite und Granate mit feinem Gefüge.From a systematic point of view, "oxide ceramics" can be understood to mean all ceramic materials which essentially (> 90%) consist of single-phase and single-component metal oxides. In contrast, all materials based on ceramics made from the boron, carbon, nitrogen, silicon and possibly oxygen system are called "non-oxide ceramics". Oxide-ceramic materials are polycrystalline materials made from pure oxides or oxide compounds; they have a high purity and are usually free of glass phase. In addition to the high-melting metal oxides, such as aluminum, zirconium, magnesium, titanium and beryllium oxide, and calcium oxide, magneto-ceramic materials and materials with a high dielectric constant, piezoceramic, can also be included. However, the limitation to the high-melting oxides is common. However, silicon dioxide (SiO 2 ) is not classified under oxide ceramics. For this reason and also in consideration of other oxides that are suitable but do not belong to the ceramic materials, the invention also relates to the production of both ceramic and oxide layers. In the case of oxide ceramic materials, a distinction is still made between simple oxides and complex oxides. These include, for example, chromite with a coarse structure and perovskite, ferrites and garnets with a fine structure.

Schwer lösliche Schichten können bislang beispielsweise durch Sputtern oder Aufdampfen, mittels der Sol-Gel-Technik, der chemischen Badabscheidung oder der Deposition aus der Dampfphase (Metal Organic Chemical Vapor Deposition MOCVD) auf Oberflächen aufgebracht werden. Aus dem Aufsatz "Laser annealing of zinc oxide thin film deposited by spray-CVD" von G.K.Bhaumik et al., Elsevier Materials Science and Engineering B52 (1998) 25-31, ist es bekannt, einen polykristallinen ZnO-Film auf Quarz- und SiliziumSubstraten mittels der "Sprüh-CVD-Methode" aufzubringen. Der aufgebrachte Film kann dann zur Verbesserung seiner Kristallstruktur durch Laserbestrahlung erhitzt werden. Die Anlagerung von undotierten ZnO-Filmen durch Sprühpyrolyse mit wässriger Zinknitratlösung ist aus dem Aufsatz "Optical and electrical properties of undoped ZnO films grown by spray pyrolyse of zinc nitrate solution" von S.A. Studenikin et al., J.of Appl.Phys. Vol.83, No.4, 15.Feb.1998, 2104 -11) bekannt. Der Schwerpunkt dieses Aufsatzes liegt in der Ermittlung der Zusammenhänge zwischen der Pyrolysetemperatur und den strukturellen, elektrischen und optischen Eigenschaften des ZnO-Films. Unterschiedliche Temperaturen wurden durch Erhitzen der Probensubstrate, beispielsweise in Stickstoff bei 400°C, erreicht.Hardly soluble layers have so far been possible, for example, by sputtering or Evaporation using the sol-gel technique, chemical bath deposition or deposition from the vapor phase (Metal Organic Chemical Vapor Deposition MOCVD) can be applied to surfaces. From the essay "Laser annealing of zinc oxide thin film deposited by spray-CVD" by G.K.Bhaumik et al., Elsevier Materials Science and Engineering B52 (1998) 25-31, it is known to use a polycrystalline ZnO film on quartz and silicon substrates by means of the "spray CVD method". The angry one Film can then improve its crystal structure through laser radiation be heated. The addition of undoped ZnO films through Spray pyrolysis with aqueous zinc nitrate solution is from the article "Optical and electrical properties of undoped ZnO films grown by spray pyrolysis of zinc nitrate solution "by S.A. Studenikin et al., J.of Appl.Phys. Vol.83, No.4, Feb. 15, 1998, 2104-11). The focus of this article is on the determination of the relationships between the pyrolysis temperature and the structural, electrical and optical properties of the ZnO film. Different temperatures were obtained by heating the sample substrates, for example in nitrogen at 400 ° C.

Beim Sputtern (vgl. für ZnO: "Use of a helicon wave excited plasma of aluminium-doped ZnO thin-film sputtering" von K.Yamaya et al., Appl. Phys. During sputtering (cf. for ZnO: "Use of a helicon wave excited plasma of aluminum-doped ZnO thin-film sputtering "by K.Yamaya et al., Appl. Phys.

Lett. 72(2), 12.Jan.1998, 235-37) werden Atome aus einer Metallkathode durch aufprallende lonen einer Gasentladung herausgelöst ("Kathodenzerstäubung"). Das zerstäubte Metall schlägt sich dann auf einer Oberfläche als gleichmäßige Schicht nieder. Mit Molekularstrahlepitaxie unter Benutzung von sauerstoffhaltigem Plasma bei Anwesenheit eines Mikrowellenfeldes können einkristalline ZnO-Dünnschichten auf c-planarem Saphir hergestellt werden (vgl. "Plasma assisted molecular beam epitaxy of ZnO on c-plane sapphire : Growth and characterisation" von Y.Chen et al., J.of Appl.Phys., Vol.84, No.7, 1.Oct.1998, 3912-18). ZnO-Fime mit guter Qualität können auch durch direkte Elektrodeposition aus wässrigen Lösungen bei einer niedrigen Prozesstemperatur hergestellt werden (vgl.: "reparation Of ZnO Films By Electrodepositon From Aqueous Solution" von S.Peulon at al., 13th Europ. Photovoltaic Solar Energy Conference, 23-27 October 1995, Nice, France, 1750-52). Bei der Sol-Gel-Technik (vgl. "Micostructure of TiO2 and ZnO Films Fabricated by the Sol-Gel-Method" von Y.Ohya et al., J.Am.Ceram.Soc. 79[4] 825-30 (1996)) erstarren als Sol vorliegende Kolloid-Lösungen unter Reaktion mit Wasser und Entzug von Lösungsmittel mit den fest adsorbierten Lösungsmittelresten zu einem Gel, das an Oberflächen angelagert und getrocknet werden kann.Lett. 72 (2), January 12, 1998, 235-37) atoms are released from a metal cathode by impacting ions of a gas discharge ("cathode sputtering"). The atomized metal is then deposited on a surface as a uniform layer. With molecular beam epitaxy using oxygen-containing plasma in the presence of a microwave field, single-crystalline ZnO thin layers can be produced on c-planar sapphire (cf. "Plasma assisted molecular beam epitaxy of ZnO on c-plane sapphire: Growth and characterization" by Y.Chen et al ., J.of Appl.Phys., Vol. 84, No.7, October 1, 1998, 3912-18). ZnO films with good quality can also be produced by direct electrode deposition from aqueous solutions at a low process temperature (see: "reparation Of ZnO Films By Electrodepositon From Aqueous Solution" by S.Peulon at al., 13th European Photovoltaic Solar Energy Conference , 23-27 October 1995, Nice, France, 1750-52). In the sol-gel technique (cf. "Micostructure of TiO 2 and ZnO Films Fabricated by the Sol-Gel-Method" by Y.Ohya et al., J.Am.Ceram.Soc. 79 [4] 825-30 (1996)) solidify colloid solutions present as sol under reaction with water and removal of solvent with the firmly adsorbed solvent residues to form a gel that can be attached to surfaces and dried.

Beim Verfahren der chemischen Badabscheidung (Chemical Bath Deposition CBD, vgl. für ZnO/CdS/CIS/Mo-Strukturen: "Effects of Cd-Free Buffer Layer For CuInSe2 Thin Solar Cells" von T.Nii et al., First WCPEC; Dec.5-9, 1994; Hawaii, 254-57) werden bei der Herstellung von schwer löslichen Metallchalkogenid-Schichten die beiden unterschiedlichen Varianten "SILAR-Verfahren" (Successive lonic Layer Adsorption and Reaction) und "Chalkogeno-Harnstoffverfahren" unterschieden.In the process of chemical bath deposition (Chemical Bath Deposition CBD, cf. for ZnO / CdS / CIS / Mo structures: "Effects of Cd-Free Buffer Layer For CuInSe 2 Thin Solar Cells" by T.Nii et al., First WCPEC; Dec.5-9, 1994; Hawaii, 254-57) a distinction is made between the two different variants "SILAR process" (Successive lonic Layer Adsorption and Reaction) and "Chalcogeno-urea process" in the production of poorly soluble metal chalcogenide layers.

Gegenstand der Veröffentlichung "CuInS2 as an extremely thin absorber in an eta solar cell" von J. Möller et al. (Conference Proceedings of the 2nd World Conference and Exhibition on Photovoltaic Solar Energy Conversion, 6. - 10. Juli 1998, Seiten 209 - 211, XP 002110735 Vienna) ist ein von den oben genannten Methoden ausgehendes Verfahren zur verbesserten Herstellung dünner Metallchalkogenid-Schichten unter Angabe von verschiedenen Materialzusammensetzungen Bei diesem Verfahren wird zunächst eine Lösung einer Metallverbindung auf ein Substrat aufgebracht, sodass sich dort Ionen anlagern. Dem Substrat wird dann in einem Trocknungsprozess das Lösungsmittel entzogen. Danach wird ein chalkogenwasserstoffhaltiges Gas mit der angelagerten lonenschicht in Kontakt gebracht, um eine Reaktion mit den Metallionen hervorzurufen. Mit diesem Verfahren können homogene Metallchalkogenid-Schichten in gleichbleibender Qualität einfach hergestellt werden. Anwendung finden solche Schichten beispielsweise als Absorber- oder Pufferschichten in Solarzellen. Von dem in diesem Aufsatz beschriebenen Verfahren, das mit ILGAR-Verfahren (lonic Layer Gas Reaction) bezeichnet werden kann, geht die Erfindung als nächstliegendem Stand der Technik aus.Subject of the publication "CuInS 2 as an extremely thin absorber in an eta solar cell" by J. Möller et al. (Conference Proceedings of the 2nd World Conference and Exhibition on Photovoltaic Solar Energy Conversion, July 6-10, 1998, pages 209-211, XP 002110735 Vienna) is a method based on the above-mentioned methods for the improved production of thin metal chalcogenide layers Specification of different material compositions With this method, a solution of a metal compound is first applied to a substrate so that ions accumulate there. The solvent is then removed from the substrate in a drying process. A chalcogen-containing gas is then brought into contact with the attached ion layer to cause a reaction with the metal ions. With this process, homogeneous metal chalcogenide layers of consistent quality can be easily produced. Such layers are used, for example, as absorber or buffer layers in solar cells. The invention is based on the method described in this article, which can be referred to as the ILGAR method (lonic layer gas reaction), as the closest prior art.

Gegenüber diesem bekannten Verfahren soll es Aufgabe der vorliegenden Erfindung sein, auch die Herstellung weiterer Oberflächenschichten in anderen Materialzusammensetzungen zu ermöglichen. Dabei soll das Verfahren trotzdem einfach in seinem Ablauf sein, auch in ökologischer und ökonomischer Hinsicht. Weiterhin soll durch die dann einsetzbaren Materialien ein erweitertes Anwendungsspektrum erreicht werden. Eine qualitativ verbesserte Beschichtung bei einer verbesserten Ausnutzung der eingesetzten Stoffe gegenüber den bekannten Beschichtungen mit Chalkogenid-Struktur ist als Unterpunkt in diesem Problemfeld ebenfalls anzustreben.Compared to this known method, the object of the present invention is also to enable the production of further surface layers in other material compositions. The process should still be simple in its sequence, also in ecological and economic terms. Furthermore, an expanded range of applications should be achieved through the materials that can then be used. A qualitatively improved coating with improved utilization of the materials used compared to the known coatings with chalcogenide structure should also be aimed at as a sub-item in this problem area.

Als Lösung für das angegebene Hauptproblem ist deshalb ein Verfahren zur Herstellung dünner, schwer löslicher Beschichtungen auf Substraten mit beliebiger Morphologie vorgesehen mit den in Abhängigkeit von der gewünschten Schichtdicke zyklisch durchzuführenden nachfolgenden Verfahrensschritten zur Herstellung keramischer oder oxidischer Schichten :

  • I. Aufbringen zumindest einer geeigneten Ausgangssubstanz zum Schichtaufbau auf die Substratoberfläche,
  • II. Trocknen der gebildeten Ausgangssubstanz-Schicht in einem inerten Gasstrom oder durch Verdunstung,
  • III. Begasung der getrockneten Ausgangssubstanz-Schicht mit einem feuchten Reaktantgas zur Umwandlung in eine entsprechende Hydroxid- oder Komplex-Schicht,
  • IV. thermische Behandlung der gebildeten Hydroxid- oder Komplex-Schicht zur Bildung der jeweiligen Endschicht und anschließend
    in Abhängigkeit vom Auftreten nicht umgesetzter Ausgangskomponenten oder unerwünschter Nebenprodukte:
  • V. Spülen zu deren Entfernung und anschließendes Trocknen.
    • A solution for the production of thin, sparingly soluble coatings on substrates with any morphology is therefore provided as a solution to the stated main problem, with the following process steps to be carried out cyclically depending on the desired layer thickness for the production of ceramic or oxide layers:
  • I. applying at least one suitable starting substance for the layer structure to the substrate surface,
  • II. Drying the starting substance layer formed in an inert gas stream or by evaporation,
  • III. Fumigation of the dried starting substance layer with a moist reactant gas for conversion into a corresponding hydroxide or complex layer,
  • IV. Thermal treatment of the hydroxide or complex layer formed to form the respective final layer and then
    depending on the occurrence of unreacted starting components or undesired by-products:
  • V. Rinse to remove and then dry.

    • Eine andere Lösung der Problemstellung zur alternativen Herstellung metallischer Schichten ist durch ein analoges Verfahren mit mit den nachfolgenden Verfahrensschritten vorgesehen :

  • I. Aufbringen zumindest einer geeigneten Ausgangssubstanz zum Schichtaufbau auf die Substratoberfläche,
  • II. Trocknen der gebildeten Ausgangssubstanz-Schicht in einem inerten Gasstrom oder durch Verdunstung,
  • III. Begasung der getrockneten Ausgangssubstanz-Schicht mit einem feuchten, reduzierend wirkend Reaktantgas zur Bildung einer metallischen Schicht und
  • IV. thermische Behandlung der gebildeten Metall-Schicht zur Entfernung nicht umgesetzter Ausgangskomponenten oder unerwünschter Nebenprodukte.
    • Another solution to the problem of alternative production of metallic layers is provided by an analogous process with the following process steps:
  • I. applying at least one suitable starting substance for the layer structure to the substrate surface,
  • II. Drying the starting substance layer formed in an inert gas stream or by evaporation,
  • III. Fumigation of the dried starting substance layer with a moist, reducing reactant gas to form a metallic layer and
  • IV. Thermal treatment of the metal layer formed to remove unreacted starting components or unwanted by-products.

    • Eine weitere Lösung der Problemstellung ist zur alternativen Herstellung anderer chalkogenidischer Beschichtungen ist außerdem durch ein analoges Verfahren mit mit den nachfolgenden Verfahrensschritten vorgesehen :

  • I. Aufbringen zumindest einer geeigneten Ausgangssubstanz zum Schichtaufbau auf die Substratoberfläche,
  • II. Trocknen der gebildeten Ausgangssubstanz-Schicht in einem inerten Gasstrom oder durch Verdunstung,
  • III. Begasung der getrockneten Ausgangssubstanz-Schicht mit einem feuchten Reaktantgas zur Umwandlung in eine entsprechende Hydroxid- oder Komplex-Schicht,
  • IIIa. Begasung der Hydroxid- oder Komplex-Schicht mit einem zusätzlichen, Chalkogenwasserstoffverbindungen enthaltenden Reaktantgaszur Bildung der chalkogenidischen Endschicht und
  • IV. thermische Behandlung der gebildeten Hydroxid- oder Komplex-Schicht und/oder der chalkogenidischen Endschicht.
    • A further solution to the problem for the alternative production of other chalcogenide coatings is also provided by an analogous process with the following process steps:
  • I. applying at least one suitable starting substance for the layer structure to the substrate surface,
  • II. Drying the starting substance layer formed in an inert gas stream or by evaporation,
  • III. Fumigation of the dried starting substance layer with a moist reactant gas for conversion into a corresponding hydroxide or complex layer,
  • IIIa. Fumigation of the hydroxide or complex layer with an additional reactant gas containing chalcogen hydrogen compounds to form the final chalcogenide layer and
  • IV. Thermal treatment of the hydroxide or complex layer formed and / or the chalcogenide final layer.

    • Vorteilhafte Weiterbildungen der erfindungsgemäßen Verfahrens zur alternativen Herstellung von keramischen und oxidischen, metallischen oder andereren chalkogenidischen Schichten sind den einzelnen Unteransprüchen zu entnehmen. Deren Inhalt wird im Folgenden im Zusammenhang mit den allgemeinen Ausführungen zu der Erfindung implizit erläutert.Advantageous developments of the inventive method for alternative production of ceramic and oxide, metallic or other chalcogenidic layers are the individual subclaims refer to. Their content is described below in connection with the general explanations of the invention implicitly explained.

    Mit den erfindungsgemäßen Verfahren können Filme von schwer löslichen Oxiden und generell von solchen Verbindungen, die sich durch Umsetzung einer trockenen festen Ausgangsverbindung mit einer gasförmigen Reaktionskomponente bilden, einfach hergestellt werden. Ausschlaggebend hierfür ist die zunächst erfolgende Hydrolyse der zur Erzielung einer homogenen Oberfläche getrockneten Ausgangssubstanz-Schicht durch ein feuchtes Reaktantgas zur Bildung von Hydroxiden oder Komplexen, beispielsweise Amminkomplexe bei Verwendung von feuchtem Ammoniak-Gas als Reaktantgas. Bei dem Reaktantgas kann es sich aber auch um einen anderen, bevorzugt basisch reagierenden Dampf oder u.U. um Wasserdampf allein handeln. Mit der Bezeichnung "Dampf" sollen immer feuchte Gase, d.h. ein Gemisch aus gasförmigem Wasser, basischem Gas und in den meisten Fällen einem inerten Trägergas, gemeint sein. Feuchtes Ammoniak-Gas entsteht durch einfaches "Durchblubbern" von Stickstoff durch eine Waschflasche mit wässriger Ammoniaklösung. Die Erzeugung metallischer Schichten durch Begasung erfordert entsprechend eine Behandlung mit reduzierend wirkenden Gasen.With the method according to the invention, films of sparingly soluble can Oxides and generally of such compounds that can be converted a dry solid starting compound with a gaseous reactant form, simply be made. This is crucial the first hydrolysis to achieve a homogeneous Dried starting substance layer by a moist surface Reactant gas to form hydroxides or complexes, for example Amine complexes when using moist ammonia gas as the reactant gas. The reactant gas can also be another, preferentially reacting steam or possibly for water vapor alone act. With the designation "steam" always moist gases, i.e. on Mixture of gaseous water, basic gas and in most cases an inert carrier gas. Moist ammonia gas is generated by simply "bubbling" nitrogen through a wash bottle aqueous ammonia solution. The generation of metallic layers by Fumigation accordingly requires treatment with reducing effects Gases.

    Durch die der Begasung nachfolgende Durchführung einer thermischen Behandlung werden dann durch Wasserabspaltung - und bei Komplexen auch durch Ligandenabspaltung - die gewünschten keramischen oder oxidischen Oberflächen-Schichten oder anderen Endschichten erzeugt. Die thermische Behandlung der Hydroxid- oder Komplex-Schichten kann in einem separaten Verfahrensschritt nach der Begasung mit dem Reaktantgas erfolgen, beispielsweise durch Erhitzen der Schichten in einem Ofen. Sie kann aber auch prozessbegleitend bei der Begasung durch eine Erhöhung der Prozesstemperatur bewirkt werden. Durch Anwendung einer höheren Temperatur kann der optionale Reinigungsschritt u.U. entfallen, da dadurch bereits unerwünschte Substanzen aus dem Film entfernt werden können. In bestimmten Fällen kann sich sogar auch ohne Anwendung einer gezielt herbeigeführten Temperaturerhöhung unmittelbar ein Oxid bilden. Bei der Herstellung von chalkogenidischen Schichten kann sich die thermische Behandlung auf beide erforderliche Begasungen erstrecken. Die thermische Behandlung zur Bildung der jeweiligen Endschicht kann im Einzelfall auch im Sinne einer Entfernung von störenden Komponenten verstanden werden. Bei der Herstellung metallischer Schichten wird diese dazu benutzt, unerwünschte Nebenprodukte zu entfernen.By carrying out a thermal after fumigation Treatment is then by elimination of water - and also with complexes by ligand elimination - the desired ceramic or oxidic Surface layers or other end layers created. The thermal Treatment of the hydroxide or complex layers can be done in a separate Process step after gassing with the reactant gas, for example by heating the layers in an oven. But it can also during the process of gassing by increasing the process temperature be effected. By applying a higher temperature the optional cleaning step may omitted, because this already undesirable Substances can be removed from the film. In particular Cases can even be brought about without using a targeted one Temperature increase immediately form an oxide. In the manufacture of chalcogenide layers, the thermal treatment can affect both extend necessary fumigations. The thermal treatment for education The respective final layer can also be removed in individual cases be understood by disruptive components. In the preparation of metallic layers, this is used to create unwanted by-products to remove.

    In der Regel handelt es sich bei der Ausgangssubstanz um eine Metallverbindung, beispielsweise Metallhalogenide wie ZnCl2 oder AlCl3, desjenigen Metalls, dessen Oxid, Keramik (z.B. ZnO, Al2O3) oder Metall als Endprodukt für die Beschichtung gewünscht ist. Das entsprechend gelöste Metallsalz wird dann auf das Substrat aufgebracht, getrocknet (ggfs. bis zu einer definierten Restfeuchte) und mit gasförmigen Reaktionspartnern umgesetzt. As a rule, the starting substance is a metal compound, for example metal halides such as ZnCl 2 or AlCl 3 , of the metal whose oxide, ceramic (for example ZnO, Al 2 O 3 ) or metal is desired as the end product for the coating. The correspondingly dissolved metal salt is then applied to the substrate, dried (if necessary up to a defined residual moisture) and reacted with gaseous reactants.

    Mit den erfindungsgemäßen Verfahren hergestellte Schichten können in der Solartechnik bei der Herstellung vieler Komponenten von Solarzellen Verwendung finden. In der Werkstofftechnik kann eine Beschichtung von allen möglichen glatten, rauen und porösen Substraten erfolgen. Weiterhin erlaubt das Verfahren durch den Einsatz von Ausgangssubstanz-Mischungen oder unterschiedlicher Ausgangssubstanzen und deren alternierender Verwendung, auch die Herstellung von homogen dotierten Schichten und Mischschichten sowie die Erzeugung von Multischichten. Einsetzbar sind die dünnen, schwer löslichen Beschichtungen insbesondere überall dort, wo ein erweiterter Oberflächenschutz gefragt ist. Hierbei kann es sich rein um den mechanischen und chemischen Schutz der Oberfläche handeln, aber auch um die Beeinflussung ihrer physikalischen und chemischen Oberflächeneigenschaften, wie beispielsweise Leitfähigkeit, Reflexions- und Absorptionsverhalten bzw. Katalyse oder Chemiesorption.Layers produced with the method according to the invention can Solar technology used in the manufacture of many components of solar cells Find. In materials technology, a coating can be used by everyone possible smooth, rough and porous substrates. Still allowed the process through the use of starting material mixtures or different starting substances and their alternating use, also the production of homogeneously doped layers and mixed layers and the generation of multilayers. The thin, heavy ones can be used soluble coatings especially wherever there is an extended Surface protection is required. This can be purely mechanical and chemical protection of the surface, but also about influencing their physical and chemical surface properties, such as for example conductivity, reflection and absorption behavior or Catalysis or chemisorption.

    Als weitere Vorteile gegenüber bekannten Verfahren sind außerdem zu nennen :

    • niedrige Kosten, da moderate, unkritische Prozessparameter, kein Vakuum
    • Unempfindlichkeit gegen Variation der Prozessparameter
    • einfache Schichtdickeneinstellung durch Anzahl der zu durchlaufenden Zyklen
    • hohe Reproduzierbarkeit hergestellter Schichten
    • homogene Beschichtung von Substraten mit beliebiger Oberfläche
    • Beschichtung auch von abgeschatteten inneren Oberflächen
    • vollständige Ausnutzung des Ausgangsmaterials und
    • einfache Automatisierbarkeit.
    Further advantages over known methods are also to be mentioned:
    • low costs because of moderate, uncritical process parameters, no vacuum
    • Insensitivity to variation of the process parameters
    • Simple layer thickness setting through the number of cycles to be run
    • high reproducibility of manufactured layers
    • homogeneous coating of substrates with any surface
    • Coating also of shaded inner surfaces
    • full utilization of the raw material and
    • easy automation.

    Ausgehend von der Kristallstruktur einer Ausgangsverbindung wird beim Chalkogenisierungsschritt zur Bildung von Sulfiden, Seleniden oder Telluriden bei dem in der älteren deutschen Anmeldung DE 198 31 214 beschriebenen ILGAR-Verfahren in bestimmten Fällen auch die Kristallstruktur verändert. Starting from the crystal structure of a starting compound, the Chalcogenization step for the formation of sulfides, selenides or tellurides in that described in the older German application DE 198 31 214 ILGAR processes also changed the crystal structure in certain cases.

    Dieses bedarf aber einer Umwandlungsenergie, die bei der Durchführung des ILGAR-Verfahrens bei Raumtemperatur nur in begrenztem Maße vorhanden ist. Dies führt dort zu einem verringerten Umsatz des Ausgangsmaterials zum Endprodukt bzw. zu einer langsameren Reaktionsgeschwindigkeit, sodass Reste der Ausgangsverbindung im hergestellten Metallchalkogenid-Dünnfilm eingelagert bleiben und nur durch zusätzlich vorgesehene Spülschritte entfernt werden können. Mit einer Verringerung der Filmqualität und einer erhöhten Abscheidedauer ist somit beim ILGAR-Verfahren zu rechnen.However, this requires a conversion energy which is necessary for the implementation of the ILGAR process at room temperature only available to a limited extent is. There, this leads to a reduced turnover of the starting material End product or at a slower reaction rate, so that Residues of the starting compound in the metal chalcogenide thin film produced remain stored and only removed by additional rinsing steps can be. With a decrease in film quality and an increased Deposition time can therefore be expected with the ILGAR process.

    Bei den erfindungsgemäßen Verfahren kann demgegenüber eine Verbesserung erzielt werden. Hierzu ist zur alternativen Herstellung anderer chalkogenidischer Beschichtungen vorgesehen, dass diese nach der Umwandlung der getrockneten Ausgangssubstanz-Schicht in eine entsprechende Hydroxid- oder Komplex-Schicht mit einem zusätzlichen, Chalkogenwasserstoffverbindungen enthaltenden Reaktantgas begast werden. Durch diesen Reaktionsweg über die Bildung eines Metallhydroxids und Integration des Heizprozesses können deutlich höhere Umsätze erzielt werden, wodurch weniger Rückstände des Ausgangsmaterials im Endprodukt auftreten. Bei den Chalkogeniden auf Basis von Schwefel, Selen oder Tellur kann dabei ebenfalls feuchtes Ammoniak-Gas (NH3) als zusätzliches Reaktantgas eingesetzt werden. Als mögliche Erklärung für diesen Effekt kann die niedrigere Aktivierungsenergie durch diesen Zwischenschritt angesehen werde. Zudem besitzen viele Metallhydroxide keine Kristallstruktur, sondern sind amorph. Dadurch sind sie weniger kompakt und lassen das Reaktantgas besser in die zu chalkogenisierende Schicht eindringen.In contrast, an improvement can be achieved in the methods according to the invention. For this purpose, for the alternative production of other chalcogenide coatings, it is provided that after conversion of the dried starting substance layer into a corresponding hydroxide or complex layer, it is gassed with an additional reactant gas containing chalcogen hydrogen compounds. This reaction path via the formation of a metal hydroxide and integration of the heating process enables significantly higher sales to be achieved, as a result of which fewer residues of the starting material occur in the end product. For the chalcogenides based on sulfur, selenium or tellurium, moist ammonia gas (NH 3 ) can also be used as an additional reactant gas. The lower activation energy through this intermediate step can be seen as a possible explanation for this effect. In addition, many metal hydroxides do not have a crystal structure, but are amorphous. This makes them less compact and allows the reactant gas to penetrate better into the chalcogenizing layer.

    Der erhöhte Energiebedarf während der Kristallumwandlung kann im Sinne der allgemein bekannten Temperung natürlich auch direkt durch eine erhöhte Prozesstemperatur während des Chalkogenisierungsschritts bereitgestellt werden. Hierbei kann bereits das Beleuchten des Substrats mit einer Halogenlampe ausreichen. Eine Durchführung des Chalkogenisierungsschritts innerhalb eines Ofens ist ebenfalls möglich. Die genannten Maßnahmen führen zu reineren und höherwertigen Dünnfilmen bei gleichzeitiger Mengenverringerung des einzusetzenden chalkogenwasserstoffhaltigen Reaktantgases und reduzieren die Depositionszeit, da u.U. auf Spülschritte, die Zeit kosten und die Qualität des Endproduktes vermindern können, verzichtet werden kann. Bei Einführung der Hydroxid-Reaktion sind keine Ausgangsmaterial-Rückstände mehr zu erwarten, die hier auftretenden Nebenprodukte sind relativ leicht flüchtig und bei geeigneter Temperaturwahl im letzten Prozessschritt entfernbar. Soll die Kristallitgröße des Endprodukts unter Beibehaltung hohen Umsatzes dagegen klein bleiben, darf die Temperatur nur so gering wie nötig erhöht werden, sodass in einem solchen Fall die Kombination des Hydroxidschrittes mit einer geringfügig erhöhten Prozesstemperatur sinnvoll ist. Nano-Kristallite bekommen zunehmend Bedeutung in Forschung und Technik, weil sie zu Quantum-Size-Effekten im Dünnfilm führen, die Einfluss auf die optischen und elektrischen Eigenschaften des Materials haben.The increased energy requirement during the crystal transformation can in the sense of well-known tempering of course also directly through an increased Process temperature provided during the chalcogenization step become. In this case, the substrate can already be illuminated with a Halogen lamp is sufficient. An implementation of the chalcogenization step inside a furnace is also possible. The measures mentioned lead to purer and higher quality thin films with a simultaneous reduction in quantity of the chalcogen-containing reactant gas to be used and reduce the deposition time, as on rinsing steps, the time costs and reduce the quality of the end product can be. When the hydroxide reaction is introduced there are no starting material residues more to expect, the by-products that occur here are relatively volatile and with a suitable temperature selection in the last Process step removable. If the crystallite size of the final product is below Maintaining high sales, however, remain small, the temperature must only be increased as little as necessary so that in such a case the Combination of the hydroxide step with a slightly increased one Process temperature makes sense. Nano-crystallites are getting increasingly Importance in research and technology because they lead to quantum-size effects in Lead thin film, which affect the optical and electrical properties of the material.

    Ausbildungsformen der Erfindung werden nachfolgend anhand der schematischen Figuren näher erläutert. Dabei zeigt:

    Figur 1
    den erfindungsgemäßen Prozessablauf bei der Herstellung einer keramischen Beschichtung in einer geeigneten Anordnung und
    Figur 2
    den erfindungsgemäßen Prozessablauf bei der Herstellung einer chalkogenidischen Beschichtung.
    Forms of embodiment of the invention are explained in more detail below with reference to the schematic figures. It shows:
    Figure 1
    the process flow according to the invention in the production of a ceramic coating in a suitable arrangement and
    Figure 2
    the process flow according to the invention in the production of a chalcogenide coating.

    Die Figur 1 zeigt die Herstellung einer Zinkoxidschicht auf einem amorphen Substrat S, das in einen im dreidimensionalen Raum verfahrbaren Substrathalter SH eingespannt ist. Zum Abdecken der einzelnen Bäder weist der Substrathalter SH einen Deckel C auf. Im einem ersten Verfahrensschritt I wird das Substrat S in eine geeignete Ausgangssubstanz P (Precursor) eingetaucht. Im gewählten Ausführungsbeispiel handelt es sich dabei um ein Lösungsbad LB mit der gelösten Metaliverbindung Zinkchlorid ZnCl2. Nach dem Herausziehen befindet sich eine Ausgangssubstanzschicht PL, hier ZnCl2, auf der Substratoberfläche. FIG. 1 shows the production of a zinc oxide layer on an amorphous substrate S , which is clamped in a substrate holder SH that can be moved in three-dimensional space. The substrate holder SH has a cover C to cover the individual baths. In a first method step I , the substrate S is immersed in a suitable starting substance P (precursor). In the selected exemplary embodiment, this is a solution bath LB with the dissolved metal compound zinc chloride ZnCl 2 . After pulling out, there is a starting substance layer PL, here ZnCl 2 , on the substrate surface.

    Die ZnCl2-Schicht wird in einem Gefäß V in einem zweiten Verfahrensschritt II zunächst getrocknet, beispielsweise durch Einleiten eines Gasstromes GS. Hierbei kann es sich um inerten Stickstoff handeln. In einem dritten Verfahrensschritt III wird dann wiederum im Gefäß V die getrocknete Ausgangssubstanzschicht PLD mit einem feuchten Reaktantgas RG, hier feuchtes Ammoniakgas, begast. Das feuchte Ammoniakgas wird durch einfaches Einleiten von Stickstoff N2 in eine Waschflasche B, in der sich konzentrierte Ammoniaklösung NH4OH und Wasser H2O befinden, hergestellt. Nach der Begasung hat sich auf dem Substrat S eine Hydroxidschicht HL gebildet, im Ausführungsbeispiel Zinkhydroxid Zn(OH)2. Zur Trocknung und Begasung können auch unterschiedliche Gefäße V eingesetzt werden.The ZnCl 2 layer is first dried in a vessel V in a second process step II , for example by introducing a gas stream GS. This can be inert nitrogen. In a third process step III , the dried starting substance layer PLD is again gassed in the vessel V with a moist reactant gas RG, here moist ammonia gas. The moist ammonia gas is produced by simply introducing nitrogen N 2 into a wash bottle B in which there are concentrated ammonia solution NH 4 OH and water H 2 O. After gassing, a hydroxide layer HL has formed on the substrate S , in the exemplary embodiment zinc hydroxide Zn (OH) 2 . Different vessels V can also be used for drying and gassing.

    In einem vierten Verfahrensschritt IV wird das mit dem Zinkhydroxid Zn(OH)2 versehene Substrat S in einen Ofen H eingebracht. Durch Energiezufuhr wird in diesem Verfahrensschritt IV das Zn(OH)2 durch Wasserabspaltung in Zinkoxid ZnO thermisch umgewandelt. Diese oxidische bzw. keramische Schicht OL/CL belegt das Substrat an seiner gesamten zugänglichen Oberfläche, auch der inneren, sicher und übt dort seine Funktionalität aus. Ein anschließender Verfahrensschritt des Spülens und Trocknens ist optional und hier nicht weiter dargestellt. Je nach gewünschter Schichtdicke können die genannten Verfahrensschritte mehrfach zyklisch durchlaufen werden.In a fourth method step IV , the substrate S provided with the zinc hydroxide Zn (OH) 2 is introduced into an oven H. In this process step IV, the Zn (OH) 2 is thermally converted into zinc oxide ZnO by elimination of water by supplying energy. This oxide or ceramic layer OL / CL covers the entire accessible surface of the substrate, including the inner surface, safely and exerts its functionality there. A subsequent rinsing and drying process step is optional and not shown here. Depending on the desired layer thickness, the process steps mentioned can be cycled through several times.

    In Figur 2 ist der erfindungsgemäße Verfahrensablauf zur Herstellung anderer chalkogenidischer Beschichtungen am Beispiel von Cadmiumsulfid CdS schematisch dargestellt. Hier nicht weiter erläuterte Verfahrensschritte und Bezugszeichen sind der Beschreibung zur Figur 1 zu entnehmen. Nach der Durchführung der Verfahrensschritte I bis III mit Adsorption P (CdCl2), Trocknung PLD (CdCl2), Begasung (N2+NH3) und Hydroxid-Bildung HL (Cd(OH)2) erfolgt ein weiterer Verfahrensschritt IIIa, bei dem die gebildete Hydroxid-Schicht HL (Cd(OH)2) mit einem zusätzlichen, Chalkogenwasserstoffverbindungen enthaltenden Reaktantgas CRG (hier Schwefelwasserstoff H2S) in Kontakt gebracht wird. Durch diesen Verfahrensschritt IIIa, dem Chalkogenisierungsschritt, wird eine chalkogenidische Beschichtung CHL in Form von Cadmiumsulfid (CdS) auf dem Substrat S erzeugt. Während der Durchführung der Verfahrensschritte II-IIIa ist die Prozesstemperatur TP, beispielsweise durch eine Durchführung der Verfahrensschritte in einem Muffelofen H, zur Verbesserung des Stoffumsatzes erhöht. Die thermische Behandlung im Verfahrensschritt IV erstreckt sich hier also auf beide Begasungen III, IIIa. FIG. 2 schematically shows the process sequence according to the invention for producing other chalcogenide coatings using the example of cadmium sulfide CdS. Process steps and reference numerals which are not further explained here can be found in the description of FIG. 1. After carrying out process steps I to III with adsorption P (CdCl 2 ), drying PLD (CdCl 2 ), gassing (N 2 + NH 3 ) and hydroxide formation HL (Cd (OH) 2 ), a further process step IIIa follows which the hydroxide layer HL (Cd (OH) 2 ) formed is brought into contact with an additional reactant gas CRG (here hydrogen sulfide H 2 S) containing chalcogen hydrogen compounds. This process step IIIa, the chalcogenization step, produces a chalcogenide coating CHL in the form of cadmium sulfide (CdS) on the substrate S. During the execution of process steps II-IIIa , the process temperature TP is increased, for example by carrying out the process steps in a muffle furnace H, in order to improve the material conversion. The thermal treatment in process step IV therefore extends to both fumigations III, IIIa.

    BezugszeichenlisteLIST OF REFERENCE NUMBERS

    BB
    Waschflaschebubbler
    CC
    Deckelcover
    CHLCHL
    chalkogenidische Schichtchalcogenide layer
    CLCL
    keramische Schichtceramic layer
    CRGCRG
    Chalkogenwasserstoffverbindungen enthaltendes ReaktantgasReactant gas containing chalcogen hydrogen compounds
    HH
    Ofenoven
    HLHL
    Hydroxidschichthydroxide
    LBLB
    Lösungsbadsolution bath
    OLOIL
    oxidische Schichtoxide layer
    PP
    Ausgangssubstanzstarting substance
    PLPL
    AusgangssubstanzschichtStarting material layer
    PLDPLD
    getrocknete Ausgangssubstanzschichtdried starting substance layer
    RGRG
    feuchtes Reaktantgas moist reactant gas
    SS
    Substratsubstratum
    SHSH
    Substrathaltersubstrate holder
    TPTP
    Prozesstemperaturprocess temperature
    VV
    Gefäßvessel

    Claims (9)

    1. Process for the preparation of thin, sparingly soluble coatings on substrates (S) having any desired morphology, which process comprises the following process steps for the preparation of ceramic or oxidic layers (CL/OL), which steps are to be carried out cyclically in dependence on the desired layer thickness:
      I. application of at least one suitable precursor (P) for layer formation to the substrate surface (S),
      II. drying of the resulting precursor layer (PL) in an inert gas stream (GS) or by evaporation,
      III. gassing of the dried precursor layer (PLD) with a moist reactant gas (RG) in order to convert it into a corresponding hydroxide or complex layer (HL),
      IV. thermal treatment of the resulting hydroxide or complex layer (HL) in order to form the respective final layer (CL/OL), and then
      in dependence on the occurrence of unreacted precursor components or undesired by-products:
      V. rinsing for the removal thereof, and subsequent drying.
    2. Process for the preparation of thin, sparingly soluble coatings on substrates (S) having any desired morphology, which process comprises the following process steps for the preparation of metallic layers, which steps are to be carried out cyclically in dependence on the desired layer thickness:
      I. application of at least one suitable precursor (P) for layer formation to the substrate surface (S),
      II. drying of the resulting precursor layer (PL) in an inert gas stream (GS) or by evaporation,
      III. gassing of the dried precursor layer (PLD) with a moist reactant gas (RG) having a reducing action, in order to form a metallic layer, and
      IV. thermal treatment of the resulting metal layer in order to remove unreacted precursor components or undesired by-products.
    3. Process for the preparation of thin, sparingly soluble coatings on substrates (S) having any desired morphology, which process comprises the following process steps for the preparation of other chalcogenidic coatings (CHL), which steps are to be carried out cyclically in dependence on the desired layer thickness:
      I. application of at least one suitable precursor (P) for layer formation to the substrate surface (S),
      II. drying of the resulting precursor layer (PL) in an inert gas stream (GS) or by evaporation,
      III. gassing of the dried precursor layer (PLD) with a moist reactant gas (RG) in order to convert it into a corresponding hydroxide or complex layer (HL),
      IIIa. gassing of the hydroxide or complex layer (HL) with an additional reactant gas containing hydrogen chalcogenide compounds (CRG) in order to form the chalcogenidic final layer (CHL), and
      IV. thermal treatment of the resulting hydroxide or complex layer (HL) and/or of the chalcogenidic final layer (CHL).
    4. Process according to any one of claims 1 to 3,
      characterised in that
      the thermal treatment (IV) is carried out either by separately heating the layer in question after its formation or by increasing the process temperature (TP) during its formation.
    5. Process according to any one of claims 1 to 4,
      characterised in that
      the precursor (P), of which there is at least one, is in the form of a solution with a preferably readily volatile solvent, and the solution is applied to the substrate (S) by immersion (LB) or spraying.
    6. Process according to any one of claims 1 to 5,
      characterised in that
      the precursor (P) is a salt.
    7. Process according to any one of claims 1 to 6,
      characterised in that
      the moist reactant gas (RG) is a gas that preferably reacts basic, or is gaseous water.
    8. Process according to any one of claims 1 to 7,
      characterised in that
      the precursor (P) is a mixture of various compounds.
    9. Process according to any one of claims 1 to 8,
      characterised in that
      different precursors (P) are used in the individual process cycles, especially in recurring sequence.
    EP00934914A 1999-04-06 2000-04-06 Method of producing thin, poorly soluble coatings Expired - Lifetime EP1169492B1 (en)

    Priority Applications (1)

    Application Number Priority Date Filing Date Title
    SI200030030T SI1169492T1 (en) 1999-04-06 2000-04-06 Method of producing thin, poorly soluble coatings

    Applications Claiming Priority (3)

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    DE19916403A DE19916403C1 (en) 1999-04-06 1999-04-06 Process for the production of thin, poorly soluble coatings
    DE19916403 1999-04-06
    PCT/DE2000/001173 WO2000060135A2 (en) 1999-04-06 2000-04-06 Method of producing thin, poorly soluble coatings

    Publications (2)

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    EP1169492B1 true EP1169492B1 (en) 2002-09-25

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    AT (1) ATE224965T1 (en)
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    DE10142913B4 (en) 2001-08-27 2004-03-18 Hahn-Meitner-Institut Berlin Gmbh Vertical transistor arrangement with a flexible substrate consisting of plastic films and method for the production thereof
    DE10160504C2 (en) * 2001-11-30 2003-11-13 Hahn Meitner Inst Berlin Gmbh Process for the production of thin, poorly soluble coatings
    DE10258727A1 (en) * 2002-12-05 2004-06-24 Schott Glas oven
    DE10339824B4 (en) * 2003-08-24 2005-07-07 Hahn-Meitner-Institut Berlin Gmbh Coating process for the deposition and fixation of particles on a substrate surface and solar cells with funkionellem layer structure
    KR100863932B1 (en) * 2007-07-10 2008-11-18 주식회사 코미코 Method of hydrating a ceramic spray-coating layer, method of manufacturing a electrostatic chuck using the method and substrate structure and electrostatic chuck having the ceramic spray-coating layer manufactured by the hydrating method
    DE102008017077B4 (en) 2008-04-01 2011-08-11 Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Process for the preparation of an n-semiconducting indium sulfide thin film
    DE102009037371B3 (en) * 2009-08-13 2011-03-17 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Coating device for substrate, comprises atomizing chamber, in which coating solution or coating dispersion is converted into aerosol by series of ultrasound sources having ultrasonic atomizer
    CN103489962B (en) * 2013-10-07 2017-01-04 复旦大学 Large area prepares the method for semiconductor-quantum-point

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    US4242374A (en) * 1979-04-19 1980-12-30 Exxon Research & Engineering Co. Process for thin film deposition of metal and mixed metal chalcogenides displaying semi-conductor properties
    JPS63103886A (en) * 1986-10-21 1988-05-09 日本碍子株式会社 Metallizing paste and metallization of ceramics therewith
    US5106828A (en) * 1987-07-20 1992-04-21 North American Philips Corporation Method for fabricating superconductors by sol-gel process
    DE69325055T2 (en) * 1992-07-08 2000-03-09 Yeda Res & Dev Oriented polycrystalline thin films made of transition metal chalcogenides
    JP2535790B2 (en) * 1994-09-08 1996-09-18 工業技術院長 Method for producing tungsten bronze and coating composite thereof
    US5686368A (en) * 1995-12-13 1997-11-11 Quantum Group, Inc. Fibrous metal oxide textiles for spectral emitters
    JPH10128115A (en) * 1996-11-01 1998-05-19 Cosmo Sogo Kenkyusho:Kk Carried noble metal catalyst and its preparation
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    RU2250932C2 (en) 2005-04-27
    CN1268786C (en) 2006-08-09
    US8158204B1 (en) 2012-04-17
    JP4275319B2 (en) 2009-06-10
    DK1169492T3 (en) 2003-02-03
    ATE224965T1 (en) 2002-10-15
    AU5060000A (en) 2000-10-23
    ES2183798T3 (en) 2003-04-01
    WO2000060135A3 (en) 2001-04-19
    KR20010113877A (en) 2001-12-28
    JP2009084153A (en) 2009-04-23
    PL350799A1 (en) 2003-02-10
    PT1169492E (en) 2003-02-28
    AU757674B2 (en) 2003-02-27
    HUP0200790A2 (en) 2002-07-29
    JP2003530284A (en) 2003-10-14
    PL193049B1 (en) 2007-01-31
    DE19916403C1 (en) 2000-10-12
    CA2367342A1 (en) 2000-10-12
    WO2000060135A2 (en) 2000-10-12

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