EP1169492B1 - Procede de realisation de revetements minces et difficilement solubles - Google Patents

Procede de realisation de revetements minces et difficilement solubles 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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EP
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Prior art keywords
layer
precursor
reactant gas
layers
hydroxide
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Expired - Lifetime
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EP00934914A
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German (de)
English (en)
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EP1169492A2 (fr
Inventor
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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Priority to SI200030030T priority Critical patent/SI1169492T1/xx
Publication of EP1169492A2 publication Critical patent/EP1169492A2/fr
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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.

Claims (9)

  1. Procédé pour fabriquer des revêtements minces et difficilement solubles sur des substrats (S) d'une morphologie quelconque avec les étapes de procédé suivantes à réaliser cycliquement en fonction de l'épaisseur de couche souhaitée pour fabriquer des couches en céramique ou par oxydation (CL / OL) :
    I. application d'au moins une substance de départ (P) adaptée à la constitution de couches sur la surface du substrat (S),
    II. séchage de la couche de substance de départ (PL) dans un courant de gaz inerte (GS) ou par évaporation,
    III. exposition au gaz de la couche de substance de départ séchée (PLD) avec un gaz réactif (RG) humide pour la transformation en une couche d'hydroxyde ou de complexe (HL) correspondante,
    IV. traitement thermique de la couche d'hydroxyde ou de complexe (HL) formée pour la formation de la couche finale (CL / OL) correspondante puis,
    en fonction de la présence de composants de départ non transformés ou de produits secondaires non désirés :
    V. balayage pour les éliminer et séchage consécutif.
  2. Procédé pour fabriquer des revêtements minces et difficilement solubles sur des substrats (S) d'une morphologie quelconque avec les étapes de procédé suivantes à réaliser cycliquement en fonction de l'épaisseur de couche souhaitée pour fabriquer des couches métalliques :
    I. application d'au moins une substance de départ (P) adaptée à la constitution de couches sur la surface du substrat (S),
    II. séchage de la couche de substance de départ (PL) dans un courant de gaz inerte (GS) ou par évaporation,
    III. exposition au gaz de la couche de substance de départ séchée (PLD) avec un gaz réactif (RG) humide qui a un effet réducteur pour la formation d'une couche métallique,
    IV. traitement thermique de la couche métallique formée pour éliminer des composants de départ non transformés ou des produits secondaires non désirés.
  3. Procédé pour fabriquer des revêtements minces et difficilement solubles sur des substrats (S) d'une morphologie quelconque avec les étapes de procédé suivantes à réaliser cycliquement en fonction de l'épaisseur de couche souhaitée pour fabriquer d'autres revêtements en chalcogénure (CHL) :
    I. application d'au moins une substance de départ (P) adaptée à la constitution de couches sur la surface du substrat (S),
    II. séchage de la couche de substance de départ (PL) dans un courant de gaz inerte (GS) ou par évaporation,
    III. exposition au gaz de la couche de substance de départ séchée (PLD) avec un gaz réactif (RG) humide pour la transformation en une couche d'hydroxyde ou de complexe (HL) correspondante,
    IIIa exposition au gaz de la couche d'hydroxyde ou de complexe (HL) avec un gaz réactif (CRG) supplémentaire qui contient des combinaisons d'hydrogène et de chalcogène pour la formation de la couche finale (CHL) en chalcogénure et
    IV. traitement thermique de la couche d'hydroxyde ou de complexe (HL) et/ou de la couche finale (CHL) en chalcogénure formée.
  4. Procédé selon l'une des revendications 1 à 3,
    caractérisé en ce que
    le traitement thermique (IV) est Obtenu soit par chauffage séparé de chaque couche après sa formation soit par augmentation de la température du processus (TP) lors de sa formation.
  5. Procédé selon l'une des revendications 1 à 4,
    caractérisé en ce que
    la substance de départ (P), au moins au nombre d'une, est présente sous forme de solution avec un solvant de préférence facilement volatil et l'application de la solution sur le substrat (S) a lieu par immersion (LB) ou par pulvérisation.
  6. Procédé selon l'une des revendications 1 à 5,
    caractérisé en ce que
    la substance de départ (P) est un sel.
  7. Procédé selon l'une des revendications 1 à 6,
    caractérisé en ce que
    le gaz réactif (RG) humide est un gaz de préférence réagissant comme une base ou de l'eau gazéiforme.
  8. Procédé selon l'une des revendications 1 à 7,
    caractérisé en ce que
    la substance de départ (P) est un mélange de différents composés.
  9. Procédé selon l'une des revendications 1 à 8,
    caractérisé en ce que
    différentes substances de départ (P) sont utilisées dans les cycles de procédés particuliers notamment selon une succession récurrente.
EP00934914A 1999-04-06 2000-04-06 Procede de realisation de revetements minces et difficilement solubles Expired - Lifetime EP1169492B1 (fr)

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)

Application Number Priority Date Filing Date Title
DE19916403 1999-04-06
DE19916403A DE19916403C1 (de) 1999-04-06 1999-04-06 Verfahren zur Herstellung dünner, schwer löslicher Beschichtungen
PCT/DE2000/001173 WO2000060135A2 (fr) 1999-04-06 2000-04-06 Procede de realisation de revetements minces et difficilement solubles

Publications (2)

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EP1169492A2 EP1169492A2 (fr) 2002-01-09
EP1169492B1 true EP1169492B1 (fr) 2002-09-25

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US (1) US8158204B1 (fr)
EP (1) EP1169492B1 (fr)
JP (2) JP4275319B2 (fr)
KR (1) KR20010113877A (fr)
CN (1) CN1268786C (fr)
AT (1) ATE224965T1 (fr)
AU (1) AU757674B2 (fr)
CA (1) CA2367342A1 (fr)
DE (2) DE19916403C1 (fr)
DK (1) DK1169492T3 (fr)
ES (1) ES2183798T3 (fr)
HU (1) HU222653B1 (fr)
PL (1) PL193049B1 (fr)
PT (1) PT1169492E (fr)
RU (1) RU2250932C2 (fr)
WO (1) WO2000060135A2 (fr)

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DE10142913B4 (de) 2001-08-27 2004-03-18 Hahn-Meitner-Institut Berlin Gmbh Vertikale Transistoranordnung mit einem flexiblen, aus Kunststofffolien bestehenden Substrat und Verfahren zu deren Herstellung
DE10160504C2 (de) * 2001-11-30 2003-11-13 Hahn Meitner Inst Berlin Gmbh Verfahren zur Herstellung dünner, schwer löslicher Beschichtungen
DE10258727A1 (de) * 2002-12-05 2004-06-24 Schott Glas Ofen
DE10339824B4 (de) * 2003-08-24 2005-07-07 Hahn-Meitner-Institut Berlin Gmbh Beschichtungsverfahren zur Deposition und Fixierung von Partikeln auf einer Substratoberfläche und Solarzellen mit funkionellem Schichtenaufbau
KR100863932B1 (ko) * 2007-07-10 2008-11-18 주식회사 코미코 세라믹 용사 코팅층의 수화 처리 방법과, 이를 이용한정전척 제조 방법 그리고 상기 수화 처리 방법에 형성된세라믹 용사 코팅층을 갖는 기판 구조물 및 정전척
DE102008017077B4 (de) 2008-04-01 2011-08-11 Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Verfahren zur Herstellung einer n-halbleitenden Indiumsulfid-Dünnschicht
DE102009037371B3 (de) * 2009-08-13 2011-03-17 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Beschichtungsvorrichtung mit Ultraschallzerstäuber
CN103489962B (zh) * 2013-10-07 2017-01-04 复旦大学 大面积制备半导体量子点的方法

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DE19916403C1 (de) 2000-10-12
ATE224965T1 (de) 2002-10-15
RU2250932C2 (ru) 2005-04-27
HUP0200790A2 (en) 2002-07-29
CN1268786C (zh) 2006-08-09
DE50000568D1 (de) 2002-10-31
PL193049B1 (pl) 2007-01-31
PL350799A1 (en) 2003-02-10
AU757674B2 (en) 2003-02-27
JP4275319B2 (ja) 2009-06-10
CN1346412A (zh) 2002-04-24
PT1169492E (pt) 2003-02-28
EP1169492A2 (fr) 2002-01-09
CA2367342A1 (fr) 2000-10-12
AU5060000A (en) 2000-10-23
JP2009084153A (ja) 2009-04-23
WO2000060135A2 (fr) 2000-10-12
KR20010113877A (ko) 2001-12-28
WO2000060135A3 (fr) 2001-04-19
US8158204B1 (en) 2012-04-17
ES2183798T3 (es) 2003-04-01
DK1169492T3 (da) 2003-02-03
HU222653B1 (hu) 2003-09-29
JP2003530284A (ja) 2003-10-14

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