EP1448808A2 - Verfahren zur herstellung dünner, schwer löslicher beschichtungen - Google Patents
Verfahren zur herstellung dünner, schwer löslicher beschichtungenInfo
- Publication number
- EP1448808A2 EP1448808A2 EP02798256A EP02798256A EP1448808A2 EP 1448808 A2 EP1448808 A2 EP 1448808A2 EP 02798256 A EP02798256 A EP 02798256A EP 02798256 A EP02798256 A EP 02798256A EP 1448808 A2 EP1448808 A2 EP 1448808A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- cation
- chemical reaction
- solid
- starting materials
- activation
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- 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
Definitions
- the invention relates to a process for the production of thin, sparingly soluble coatings as the end product of a chemical reaction between at least one cation and an anion donor as starting materials on substrates with any morphology at a process temperature well below a thermal activation of the chemical reaction of the starting materials depending on of the desired layer thickness to be carried out cyclically.
- CBD chemical Bath Deposition
- deposition solutions are used as a chemical bath, in which the cation and anion donors are dissolved as solid starting materials.
- the chemical reaction of the cation and anion donors takes place in the entire liquid mixture by thermal decomposition of at least one of the starting materials from the liquid phase to the end product with separation into one in the liquid mixture immersed substrate (cf.
- the majority of the starting materials used in the chemical bath react to the end product without contributing to the coating of the substrate. Because of this irreversible reaction, the chemical bath can only be used once, so that larger amounts of chemicals that cannot be used any longer are created and the process is relatively inefficient.
- Cation dispensers in the form of a metal compound are first dissolved in a solvent and applied by dipping or spraying onto a substrate of any morphology, where the metal ions are adsorptively attached to the surface without chemical conversion Reactant gas is fed as an anion donor onto the pretreated surface, thereby triggering the chemical reaction with the adsorbed cation donor, the process temperature being well below a thermal activation of the chemical reaction of the starting materials (pyrolysis) usually in the room temperature range, but can also be higher depending on the metal compound used.
- a thermal activation of the chemical reaction of the starting materials pyrolysis
- there is also no clogging of pores since the anion-donating reactant gas, which penetrates even the smallest of pores, converts the cation-donating starting material to the end product via a solid-gas reaction.
- both the cation donor and the anion donor are in their form in the form of dry solids Initial form used. All of the components required to form the coating to be produced are now contained in the solids.
- highly toxic components which are contained in the reactant gas in the known ILGAR process are, in the process according to the invention, shifted to the solid phase at least after they have been applied to the substrate and, if necessary, dried, and are therefore considerably easier to process than in the gas phase ,
- the chemical reaction to the end product thus takes place between two or more dry and solid solids in the presence of an activation gas which serves exclusively to activate the chemical reaction at the predetermined, relatively low process temperature and has no part in the end product.
- the method according to the invention agrees with the known ILGAR method, but differs significantly from the other known methods, in which a thermal treatment is always required to form the end product.
- the activation gas in the process according to the invention serves exclusively to modify at least one solid involved in the chemical reaction to the end product in order to increase its reactivity.
- the chemical reaction to form the end product now takes place at the predetermined moderate process temperature at which there is no chemical reaction between the starting materials without the activation gas being supplied.
- all toxic compounds which are generally required for a high quality of the coating to be produced are used in solid starting form.
- the process according to the invention can also be referred to significantly as the SPRAG process for "Solid Precursor Reaction by Activation Gas”.
- the essential characteristic elements of the process can already be referred to in the process name: solid (easy to handle) starting materials and (targeted) induction of the reaction by an activation gas.
- the advantages of the SPRAG process according to the invention include all the advantages of the ILGAR process, including low process costs due to moderate, uncritical process conditions, simple setting of the layer thickness by the number of cycles to be run through from the nm to the ⁇ m range, and high ones Reproducibility of layers produced, full utilization of the material used, no need for a vacuum, homogeneous deposition following the surface of the substrate, so that even the smallest pores can be coated homogeneously, low process temperatures and easy automation of the process for large-scale applications.
- the SPRAG process then comes with greater procedural safety by avoiding highly toxic gases and a further cost reduction, in particular by minimizing complex safety and suction measures.
- the SPRAG process according to the invention can be modified by various further process steps.
- a simple application of the cation and anion donors to the substrate can be made possible by dissolving the cation and anion donors in solid form in a preferably volatile solvent before the application of the Solid mixture on the substrate without causing a chemical reaction in the solution, • applying the solution of the solid mixture to the substrate by immersing the substrate or spraying onto the substrate, and • drying the starting layer before gassing with the
- the application of the dissolved cation and anion donors, which have a solid starting form, over a starting solution is also to be classified as significantly less critical.
- the solvent can be volatile, it can also be water.
- the removal of the solvent for drying the adsorption layer can take place spontaneously by evaporation at room temperature.
- the wetted substrate can also be heated or with an inert gas, for example noble gases or molecular nitrogen. air, too.
- the solvent is removed without a chemical change in the cation and anion donors. In particular, no chemical reaction is triggered between them.
- the solid mixture can not only be applied in dissolved form by dipping or spraying, methods for vapor deposition or printing (screen printing method) can also be used.
- rinse liquid
- a rinsing liquid which may be water, for example
- the substrate can be dried again in the manner described above.
- a common method is also to carry out a second rinsing step, in which the rinsing liquid that remains is taken up by a suitable, volatile solvent and is thereby removed from the coating surface. This solvent remaining on the coating then evaporates quickly on its own or with a forced effect from outside.
- a crystalline end product is formed in the thin coating, which is insoluble in the starting solution.
- This after-treatment step is a known measure for improving the quality.
- annealing is usually the first process step in which heat is applied to the coating from the outside.
- the tempering takes place only after the desired layer structure has been completed, so that it can also be seen here that the heat supply no longer has any influence on the course of the chemical reaction.
- the annealing temperature is again chosen to be significantly below the thermal activation temperature.
- the SPRAG process according to the invention can be characterized by a process temperature in the region of room temperature or by an increased process temperature when gassing with the activation gas, but which is well below the thermal activation of the chemical reaction of the starting materials exclusively to enlarge the crystallites that form in the coating.
- a process temperature in the region of room temperature or by an increased process temperature when gassing with the activation gas but which is well below the thermal activation of the chemical reaction of the starting materials exclusively to enlarge the crystallites that form in the coating.
- a major advantage of the SPRAG process according to the invention is the shift of the highly toxic components from the gas phase to the solid phase.
- the activation gas To activate the chemical reaction between the solids involved, the activation gas must be selected in a suitable manner - also from the point of view of toxicity.
- the method can therefore be characterized by the use of a moist, basic or acidic, preferably non-toxic or only slightly toxic, activation gas, which is chemically converted via an intermediate reaction to at least one cation or anion donor by converting it into a reactive form modified that the reaction to the end product is initiated, but no components of the gas are released to the end product.
- a basic activation gas is used if at least one of the starting substances is not chemically resistant to alkalis.
- moist, acid-reacting activation gases are used if at least one of the starting substances is not chemically resistant to acids.
- moist activation gases in particular provide the ionized groups, which particularly easily chemically modify the cation or anion donors in an intermediate reaction in such a way that a chemical reaction is triggered to form the desired end product.
- this end product does not contain any components of the activation gas.
- the activation gas is consumed in the course of the reaction.
- another continuation of the invention which is characterized by the use of an activation gas in the function of a catalyst, which only lowers the activation energy of the chemical reaction between the cation and anion donors.
- Such a gaseous catalyst itself is not involved in the actual reaction or in an intermediate stage, so that it is also not consumed.
- the gaseous catalyst remains unchanged, so that it is used again and again as an activation gas can be. The procedural costs can be reduced again by this measure.
- a solid and dry metal compound as a cation donor and a solid and dry chalcogen compound as an anion donor in the solid can be used in particular.
- a metal component is deposited in the coating to be produced.
- advantageous metal chalcogenide layers are then formed, as are known from DE 198 31 214 A1 together with their advantages.
- the chalcogen required in the process according to the invention which can be sulfur, but in particular also the highly toxic selenium, has a solid form in the starting material, so that it is relatively safe to use, which also applies to the loosened form.
- the SPRAG process according to the invention can be used to produce coatings which are sparingly soluble and chemically stable, and in some cases even extremely chemically resistant to reactive substances.
- a metal salt in particular a metal chloride (MeCl 2 ), a chalcogen compound, a urea compound, in particular selenourea ((NH 2 ) 2CSe) or thiourea ((NH 2 ) 2 CS), and humid ammonia gas (NH 3 / H 2 O)
- a metal salt in particular a metal chloride (MeCl 2 ), a chalcogen compound, a urea compound, in particular selenourea ((NH 2 ) 2CSe) or thiourea ((NH 2 ) 2 CS), and humid ammonia gas (NH 3 / H 2 O)
- Ammonia is one of the toxic, but not one of the highly toxic gases and can therefore be safely handled with little technological effort. Details on the procedure can be found in the special description section.
- the SPRAG process according to the invention can also be used to produce plastic layers by using organic compounds, for example monomers, in the dry solid mixture as a function of cation and anion donors as the desired coating.
- organic compounds for example monomers
- These coatings also have the advantage of high chemical stability, ie chemical resistance to reactive substances, and cover any substrate with any morphology with a homogeneous layer down to the smallest pores.
- moist HCl gas can then be used as the activation gas.
- the use of dry activation gases which are different in the individual process cycles and which are suitable in each case, in particular in a periodically recurring sequence for multilayer formation is also advantageously possible.
- the simultaneous use of different cation and anion donors as starting materials makes it possible to produce multinary and / or doped coatings and compound mixtures in the coatings.
- the SPRAG method according to the invention can be used to easily design almost any layer sequences in the most varied of material combinations and with the most varied of properties, so that the field of applications for the coatings which can be produced can be found in the most varied of areas.
- the SPRAG process according to the invention is used to produce a thin, difficultly soluble zinc selenide coating as the end product as follows:
- a float glass is used as the substrate with any morphology. This is cleaned in 2-propanol for 10 min in an ultrasonic bath and then dried in a stream of nitrogen.
- the substrate is immersed in the solution of the starting materials at a speed of 10 mm / s. After 10 s in the solution it is pulled out at a speed of 2 mm / s. Because of the volatile solvent acetonitrile, a dry, firmly adhering and homogeneous thin layer of the solid mixture is present as a starting layer on the substrate after the substrate has been pulled out of the solution, so that an additional drying step can be dispensed with.
- the substrate with the dry starting layer is then gassed with the activation gas “moist ammonia” (NH 3 + H 2 0) for 60 s by passing a carrier gas, here N 2 , through an ammonia solution. This fumigation takes place at room temperature.
- the activation gas triggers the chemical reaction between the cation donor zinc perchlorate adsorbed on the substrate and the anion donor adsorbed on the substrate Selenourea.
- the activation gas "moist ammonia” is involved in an intermediate reaction step, but not in the end product.
- the reactants are:
- the OH groups come from the damp ammonia. After this intermediate reaction, selenium anions are released. They react with the zinc cations to the desired end product:
- By-product in the selected manufacturing example includes ammonium perchlorate NH 4 CIO 4 , which can be easily removed by a rinsing step.
- the two process steps were repeated 90 times until the desired layer thickness was reached; the number of process cycles is accordingly 90.
- ZnSe single crystals is shifted to higher excitation energies.
- XRD X-ray diffraction
- the ZnSe coating produced was annealed at a moderate temperature in a stream of nitrogen for one hour.
- the choice of the moderate temperature prevents a subsequent thermal reaction of any starting materials that may still be present, since no rinsing step was carried out. However, if this is done, it can be assumed that there are no longer any cation or anion donors, so that the temperature for tempering can also be significantly higher.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemically Coating (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Chemical Vapour Deposition (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compounds Of Unknown Constitution (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10160504 | 2001-11-30 | ||
DE10160504A DE10160504C2 (de) | 2001-11-30 | 2001-11-30 | Verfahren zur Herstellung dünner, schwer löslicher Beschichtungen |
PCT/DE2002/004457 WO2003048404A2 (de) | 2001-11-30 | 2002-11-29 | Verfahren zur herstellung dünner, schwer löslicher beschichtungen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1448808A2 true EP1448808A2 (de) | 2004-08-25 |
EP1448808B1 EP1448808B1 (de) | 2007-05-02 |
Family
ID=7708607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02798256A Expired - Lifetime EP1448808B1 (de) | 2001-11-30 | 2002-11-29 | Verfahren zur herstellung dünner, schwer löslicher beschichtungen |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1448808B1 (de) |
AT (1) | ATE361380T1 (de) |
DE (2) | DE10160504C2 (de) |
ES (1) | ES2284972T3 (de) |
WO (1) | WO2003048404A2 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0524066D0 (en) * | 2005-11-25 | 2006-01-04 | Chiron Srl | 741 ii |
DE102009037371B3 (de) * | 2009-08-13 | 2011-03-17 | Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh | Beschichtungsvorrichtung mit Ultraschallzerstäuber |
DE102011050684A1 (de) * | 2011-05-27 | 2012-11-29 | Karlsruher Institut für Technologie | Vorrichtung und Verfahren zur Herstellung von hoch porösen, kristallinen Oberflächenbeschichtungen |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5908608A (en) * | 1996-11-08 | 1999-06-01 | Spectra Science Corporation | Synthesis of metal chalcogenide quantum |
JPH1167677A (ja) * | 1997-08-15 | 1999-03-09 | Star Micronics Co Ltd | オキシ硫化錫膜及びその製造方法 |
DE19831214C2 (de) * | 1998-03-19 | 2003-07-03 | Hahn Meitner Inst Berlin Gmbh | Verfahren und Anordnung zur Herstellung dünner Metallchalkogenid-Schichten |
DE19916403C1 (de) * | 1999-04-06 | 2000-10-12 | Hahn Meitner Inst Berlin Gmbh | Verfahren zur Herstellung dünner, schwer löslicher Beschichtungen |
-
2001
- 2001-11-30 DE DE10160504A patent/DE10160504C2/de not_active Expired - Fee Related
-
2002
- 2002-11-29 ES ES02798256T patent/ES2284972T3/es not_active Expired - Lifetime
- 2002-11-29 WO PCT/DE2002/004457 patent/WO2003048404A2/de active IP Right Grant
- 2002-11-29 DE DE50210087T patent/DE50210087D1/de not_active Expired - Lifetime
- 2002-11-29 EP EP02798256A patent/EP1448808B1/de not_active Expired - Lifetime
- 2002-11-29 AT AT02798256T patent/ATE361380T1/de not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO03048404A3 * |
Also Published As
Publication number | Publication date |
---|---|
DE10160504A1 (de) | 2003-06-12 |
DE10160504C2 (de) | 2003-11-13 |
WO2003048404A2 (de) | 2003-06-12 |
DE50210087D1 (de) | 2007-06-14 |
ES2284972T3 (es) | 2007-11-16 |
EP1448808B1 (de) | 2007-05-02 |
WO2003048404A3 (de) | 2003-11-27 |
ATE361380T1 (de) | 2007-05-15 |
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