WO1995019456A1 - Method for depositing a film consisting of a metal or semi-metal and an oxide thereof - Google Patents

Method for depositing a film consisting of a metal or semi-metal and an oxide thereof Download PDF

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Publication number
WO1995019456A1
WO1995019456A1 PCT/FR1995/000046 FR9500046W WO9519456A1 WO 1995019456 A1 WO1995019456 A1 WO 1995019456A1 FR 9500046 W FR9500046 W FR 9500046W WO 9519456 A1 WO9519456 A1 WO 9519456A1
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Prior art keywords
metal
substrate
semi
alkyl
enclosure
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PCT/FR1995/000046
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French (fr)
Inventor
Pierre Goudmand
Odile Dessaux
Brigitte Mutel
Abdellah Ben Taleb
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Universite Des Sciences Et Technologies De Lille
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Priority to AU15390/95A priority Critical patent/AU1539095A/en
Publication of WO1995019456A1 publication Critical patent/WO1995019456A1/en

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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/452—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species

Definitions

  • the present invention relates to a process for depositing on a substrate, at room temperature, a layer of metal or semi-metal and their oxide belonging to the groups Ilb, Illa, IVa and Va, such as for example zinc.
  • a layer of zinc on a substrate two methods are currently known: physical vapor deposition and chemical vapor deposition.
  • the metal is sprayed onto a substrate or sprayed onto a hot substrate. In both cases, the substrate must be flat.
  • the method is limited to metals with a low melting point and the layers obtained are often porous and have poor adhesion with the substrate.
  • a chemical compound is thermally decomposed from the metal to be deposited upon contact with the heated substrate. This method is limited to substrates withstanding a high temperature.
  • a laser beam is focused on a small surface of the substrate.
  • the metallic compound is decomposed in the vicinity of the focal point of the laser beam.
  • the object of the present invention is to remedy the drawbacks of known methods, by proposing a method which makes it possible to produce deposits, at room temperature, very adherent, on all substrates.
  • the invention thus relates to a method for depositing on a substrate, a layer of metal or semi-metal and their oxide belonging to the groups Ilb, Illa, IVa and Va of the classification of the elements, in which one carries out in an enclosure in which is located said substrate a cold plasma differed from nitrogen consisting essentially of free nitrogen atoms, for pretreating said substrate.
  • this process is characterized in that after pretreatment of said substrate with said cold plasma differed from nitrogen, a volatile alkyl of said metal or semi-metal is introduced into the enclosure so as to decompose said alkyl and to produce on said substrate a layer consisting of a mixture of said metal or semi-metal and their oxide.
  • the above process makes it possible to produce, in an area remote from the discharge area, a plasma consisting essentially of free nitrogen atoms.
  • the nitrogen plasma has the effect of treating the surface of the substrate to make it adherent with respect to the coating applied subsequently.
  • the alkyl of the volatile metal or semi-metal introduced into the enclosure is broken down into metal or semi-metal and organic compound.
  • the metal or semi-metal thus formed is deposited on the substrate.
  • the deposition can be carried out on metals, alloys, ceramics, polymers, composite materials or glasses, to obtain conductive surfaces or to obtain a decorative or protective coating against corrosion or abrasion.
  • said volatile alkyl is chosen from the following compounds: Group:
  • Ilb Zn (CH 3 ) 2 , Zn (C 2 H 5 ) 2 , Cd (CH 3 ) 2 , Cd (C 2 H 5 ) 2 Illa: Al (CH 3 ) 3 , Al (C 2 H 5 ) 3 , Ga (CH 3 ) 3 , Ga (C 2 H 5 ) 3 IVa: Ge (CH 3 ) 4 , Sn (CH 3 ) 4 , Pb (C 2 H 5 ) 4 , Pb (CH 3 ) 4
  • those of zinc are preferred, since zinc coatings are of great industrial importance.
  • a deposit of zinc it was found in particular that the deposit of zinc on the wall of the treatment enclosure did not deactivate the cold nitrogen-deferred plasma, contrary to what is observed when a compound of a transition metal such as nickel is used.
  • the plasma is preferably produced from pure or practically pure nitrogen, that is to say that may contain traces of impurities such as oxygen or water vapor.
  • said cold nitrogen delayed plasma pretreatment is carried out for a period of between one and ten minutes.
  • This pretreatment has the effect of cleaning and making the surface of the substrate very adherent with respect to the layer of metal applied following this treatment.
  • the cold nitrogen-deferred plasma is maintained for a sufficient time to remove all traces of said alkyl in the enclosure .
  • FIG. 1 is a diagram of the device for implementing the method according to one invention
  • FIG. 2 is a diagram in partial section of the treatment enclosure, showing the injector of the volatile alkyl compound of metal or semi-metal and the substrate to receive the layer of metal or semi-metal and their oxide .
  • FIG. 3 is a plan view of the end of the injector
  • FIG. 4 is a perspective view of one injector
  • FIG. 5 is an Auger spectrum of zinc and its oxide obtained by the process.
  • the reference numbers indicated in the figures designate the following parts of the device:
  • the discharge plasma is produced by a microwave generator 4 and 5 (2450 MHz) coupled to a multimode coupler 6 mounted on waveguide RG 112 / U, marketed by SAIREM, allowing the obtaining nitrogen discharge in a wide pressure range (10 -1 -1000 hPa) and with a transmitted coupling between 95 and 100%.
  • the discharge plasma produced in a quartz tube 3 with an internal diameter of 30mm, is expanded in a 5.2 1 pyrex reactor (internal diameter
  • the plas agene gas used is nitrogen of U quality (Air Liquide).
  • the precursor is diethyl zinc (DEZ).
  • the DEZ is introduced into the cold delayed nitrogen plasma (PFDA) formed in the enclosure 13 via an injector 10 inclined at 45 ° with respect to the plasma flow (see FIG. 2), the injection takes place doing in the direction of flow.
  • the injector 10 is constituted by a tube 8mm in internal diameter, wound in a spiral of 7.5cm in diameter and pierced with nine orifices 15 of 2mm in diameter spaced 3cm (see Figures 3 and 4).
  • the pressures are measured by means of a Pirani gauge.
  • the nitrogen flow (U Air Liquide quality) is regulated and controlled by a mass flow meter.
  • the flow of DEZ is regulated by a micrometric valve.
  • the samples 14 on which a zinc deposit must be made are placed in the reactor
  • the size of the reactor and the injector makes it possible to process several samples simultaneously.
  • a vacuum of about 10 -1 hPa is made in the installation using the pumping device. Nitrogen is then admitted (U Air Liquide quality) under a pressure of 4 hPa with a flow rate of 13.8 Nl / min. Then the discharge is initiated with an incident microwave power of 400. The coupler is adjusted so as to obtain 100% coupling. As soon as the discharge begins, a yellow luminescence, characteristic of the recombination of the nitrogen atoms, extends into the reaction chamber and downstream of it to the pump.
  • the samples are submitted to the PFDA for 1 to 5 minutes.
  • the aim of this pre-treatment is to clean the parts to be treated and increase their adhesiveness when it comes to polymeric materials.
  • the DEZ is injected.
  • the yellow luminescence (S-,) characteristic of the PFDA disappears downstream of the injector, giving way to a blue luminescence (S 2 ).
  • the flow of DEZ is controlled by the geometry of the chemiluminescent reaction PFDA-DEZ.
  • the conditions necessary to obtain a blue gray metallic deposit correspond to the presence of blue luminescence in the form of a flame at the center of which the samples to be treated are embedded. For a nitrogen flow of 13.8 Nl / min, such conditions correspond to a partial pressure of DEZ of 0.1 hPa.
  • the appearance of a blue gray metallic deposit can be observed on the sample, thus only on the walls of the reactor; but the latter does not deactivate the gas plas a faux.
  • the reactor is cleaned by the PFDA for 5 minutes after deposition.
  • FIG. 5 shows by way of example the Auger spectrum of a layer of zinc and its oxide deposited according to the method according to the invention. Peaks A and B respectively characterize the presence of Zn and ZnO.
  • the deposit obtained on polypropylene is conductive: resistance equal to 2000 ⁇ . 3.
  • a deposit of zinc was carried out at ambient temperature on various substrates.
  • Zn metal is obtained by breaking the bond between Zn and the alkyl radicals of DEZ under the action of the active species of PFDA.
  • the homogeneity of the deposit depends on the nature of the substrate.
  • the agents contaminating the surface of the substrate were in all cases eliminated.
  • the maximum percentage of metallic Zn with respect to zinc oxide is 35% for an aluminum substrate, and 60% for the polypropylene substrate.
  • the thickness of the deposit obtained does not depend on the substrate and is of the order of 70 ⁇ .

Abstract

A method for depositing on a substrate (14) a film consisting of a metal or semi-metal and an oxide thereof belonging to groups IIb, IIIa, IVa and Va of the periodic table, wherein a remote cold nitrogen plasma essentially consisting of free nitrogen atoms is generated in an enclosure (13) in order to pretreat the substrate, and once said substrate (14) has been pretreated with said remote cold nitrogen plasma, a volatile alkyl of said metal or semi-metal (10) is fed into the enclosure (13) in order to decompose said alkyl and form on said substrate (14) a film consisting of a mixture of the metal or semi-metal and the oxide thereof.

Description

Procède pour déposer, une couche de métal ou de semi-metal et de leur oxyde.Proceeds to deposit a layer of metal or semi-metal and their oxide.
La présente invention concerne un procédé pour déposer sur un substrat, à la température ambiante, une couche de métal ou de semi-métal et de leur oxyde appartenant aux groupes Ilb, Illa, IVa et Va, tel que par exemple le zinc. Pour appliquer une couche de zinc sur un substrat, on connaît actuellement deux méthodes: dépôt physique en phase vapeur et dépôt chimique en phase vapeur.The present invention relates to a process for depositing on a substrate, at room temperature, a layer of metal or semi-metal and their oxide belonging to the groups Ilb, Illa, IVa and Va, such as for example zinc. To apply a layer of zinc on a substrate, two methods are currently known: physical vapor deposition and chemical vapor deposition.
Dans la première méthode, on vaporise le métal sur un substrat ou on le pulvérise sur un substrat chaud. Dans les deux cas, le substrat doit être plan.In the first method, the metal is sprayed onto a substrate or sprayed onto a hot substrate. In both cases, the substrate must be flat.
Dans le cas de la vaporisation, la méthode est limitée à des métaux à bas point de fusion et les couches obtenues sont souvent poreuses et présentent une faible adhésion avec le substrat.In the case of vaporization, the method is limited to metals with a low melting point and the layers obtained are often porous and have poor adhesion with the substrate.
Dans le cas de la pulvérisation, il est nécessaire d'utiliser un vide poussé et par conséquent un équipement coûteux. Dans la seconde méthode, on distingue la méthode thermique et la méthode par laser.In the case of spraying, it is necessary to use a high vacuum and therefore expensive equipment. In the second method, a distinction is made between the thermal method and the laser method.
Dans le premier cas, on décompose thermiquement un composé chimique du métal à déposer dès son contact avec le substrat chauffé. Cette méthode est limitée à des substrats supportant une température élevée.In the first case, a chemical compound is thermally decomposed from the metal to be deposited upon contact with the heated substrate. This method is limited to substrates withstanding a high temperature.
Dans le deuxième cas, un faisceau laser est focalisé sur une petite surface du substrat. Le composé métallique est décomposé au voisinage du point de focalisation du faisceau laser. Cette méthode exige un appareillage coûteux et met en oeuvre des températures élevées qui risquent de dégrader le substrat. De plus, cette méthode est limitée aux dépôts de petites surfaces.In the second case, a laser beam is focused on a small surface of the substrate. The metallic compound is decomposed in the vicinity of the focal point of the laser beam. This method requires expensive equipment and uses high temperatures which risk degrading the substrate. Moreover, this method is limited to deposits from small areas.
Le but de la présente invention est de remédier aux inconvénients des méthodes connues, en proposant un procédé qui permet de réaliser des dépôts, à température ambiante, très adhérents, sur tous substrats.The object of the present invention is to remedy the drawbacks of known methods, by proposing a method which makes it possible to produce deposits, at room temperature, very adherent, on all substrates.
L'invention vise ainsi un procédé pour déposer sur un substrat, une couche de métal ou de semi-métal et de leur oxyde appartenant aux groupes Ilb, Illa, IVa et Va de la classification des éléments, dans lequel on réalise dans une enceinte dans laquelle se trouve ledit substrat un plasma froid différé d'azote constitué essentiellement d'atomes d'azote libres, pour prétraiter ledit substrat.The invention thus relates to a method for depositing on a substrate, a layer of metal or semi-metal and their oxide belonging to the groups Ilb, Illa, IVa and Va of the classification of the elements, in which one carries out in an enclosure in which is located said substrate a cold plasma differed from nitrogen consisting essentially of free nitrogen atoms, for pretreating said substrate.
Suivant l'invention, ce procédé est caractérisé en ce q 'après prétraitement dudit substrat par ledit plasma froid différé d'azote, on introduit dans l'enceinte un alkyl volatil dudit métal ou semi- métal de façon à décomposer ledit alkyl et à réaliser sur ledit substrat une couche constituée par un mélange dudit métal ou semi-métal et de leur oxyde.According to the invention, this process is characterized in that after pretreatment of said substrate with said cold plasma differed from nitrogen, a volatile alkyl of said metal or semi-metal is introduced into the enclosure so as to decompose said alkyl and to produce on said substrate a layer consisting of a mixture of said metal or semi-metal and their oxide.
Le procédé pour former le plasma différé d'azote a été décrit notamment dans le brevet français n° 2 616 088.The process for forming the delayed nitrogen plasma has been described in particular in French Patent No. 2,616,088.
Contrairement aux plasmas obtenus par un procédé différent, le procédé ci-dessus permet de réaliser dans une zone éloignée de la zone de décharge, un plasma constitué essentiellement par des atomes d'azote libres.Unlike plasmas obtained by a different process, the above process makes it possible to produce, in an area remote from the discharge area, a plasma consisting essentially of free nitrogen atoms.
Un tel plasma n'échauffe pratiquement pas le substrat. Dans le procédé décrit dans le brevet français ci-dessus, le plasma d'azote a pour effet de traiter la surface du substrat pour la rendre adhérente vis-à-vis du revêtement appliqué ultérieurement.Such a plasma practically does not heat the substrate. In the process described in the French patent above, the nitrogen plasma has the effect of treating the surface of the substrate to make it adherent with respect to the coating applied subsequently.
Dans le cas du procédé conforme à la présente invention, l'alkyl du métal ou semi-métal volatil introduit dans l'enceinte est décomposé en métal ou semi-métal et composé organique. Le métal ou semi-métal ainsi formé se dépose sur le substrat. Le dépôt peut être effectué sur des métaux, des alliages, des céramiques, des polymères, des matériaux composites ou des verres, pour obtenir des surfaces conductrices ou pour obtenir un revêtement décoratif ou de protection contre la corrosion ou l'abrasion.In the case of the process according to the present invention, the alkyl of the volatile metal or semi-metal introduced into the enclosure is broken down into metal or semi-metal and organic compound. The metal or semi-metal thus formed is deposited on the substrate. The deposition can be carried out on metals, alloys, ceramics, polymers, composite materials or glasses, to obtain conductive surfaces or to obtain a decorative or protective coating against corrosion or abrasion.
Selon une version préférée de l'invention, ledit alkyl volatil est choisi parmi les composés suivants: Groupe:According to a preferred version of the invention, said volatile alkyl is chosen from the following compounds: Group:
Ilb: Zn(CH3)2,Zn(C2H5)2,Cd(CH3)2,Cd(C2H5)2 Illa: Al(CH3) 3,Al (C2H5) 3 ,Ga(CH3) 3 ,Ga(C2H5) 3 IVa: Ge(CH3) 4,Sn(CH3) 4,Pb(C2H5) 4,Pb(CH3) 4 Ilb: Zn (CH 3 ) 2 , Zn (C 2 H 5 ) 2 , Cd (CH 3 ) 2 , Cd (C 2 H 5 ) 2 Illa: Al (CH 3 ) 3 , Al (C 2 H 5 ) 3 , Ga (CH 3 ) 3 , Ga (C 2 H 5 ) 3 IVa: Ge (CH 3 ) 4 , Sn (CH 3 ) 4 , Pb (C 2 H 5 ) 4 , Pb (CH 3 ) 4
Va: Sb(CH3)3,Bi(CH3)3 Va: Sb (CH 3 ) 3 , Bi (CH 3 ) 3
Parmi ces composés, ceux du zinc sont préférés, étant donné que les revêtements de zinc ont une grande importance industrielle. Dans le cas d'un dépôt de zinc, on a constaté en particulier que le dépôt de zinc sur la paroi de l'enceinte de traitement ne désactivait pas le plasma froid différé d'azote, contrairement à ce que l'on observe lorsqu'on utilise un composé d'un métal de transition tel que le nickel.Among these compounds, those of zinc are preferred, since zinc coatings are of great industrial importance. In the case of a deposit of zinc, it was found in particular that the deposit of zinc on the wall of the treatment enclosure did not deactivate the cold nitrogen-deferred plasma, contrary to what is observed when a compound of a transition metal such as nickel is used.
Le plasma est de préférence produit à partir d'azote pur ou pratiquement pur, c'est-à-dire pouvant contenir des traces d'impuretés telles que 1'oxygyène ou la vapeur d'eau. De préférence également, ledit prétraitement par plasma froid différé d'azote est réalisé pendant une durée comprise entre une et dix minutes.The plasma is preferably produced from pure or practically pure nitrogen, that is to say that may contain traces of impurities such as oxygen or water vapor. Preferably also, said cold nitrogen delayed plasma pretreatment is carried out for a period of between one and ten minutes.
Ce prétraitement a pour effet de nettoyer et rendre la surface du substrat très adhérente vis-à-vis de la couche de métal appliquée à la suite de ce traitement. De préférence également, après arrêt de l'introduction de l'alkyl volatil de métal ou de semi- métal dans l'enceinte, le plasma froid différé d'azote est maintenu pendant une durée suffisante pour éliminer toute trace dudit alkyl dans l'enceinte.This pretreatment has the effect of cleaning and making the surface of the substrate very adherent with respect to the layer of metal applied following this treatment. Preferably also, after stopping the introduction of the volatile metal or semi-metal alkyl into the enclosure, the cold nitrogen-deferred plasma is maintained for a sufficient time to remove all traces of said alkyl in the enclosure .
D'autres particularités et avantages de 1 ' invention apparaîtront encore dans la description ci- après.Other features and advantages of the invention will become apparent from the description below.
Aux dessins annexés donnés à titre d'exemples non limitatifs:In the appended drawings given by way of nonlimiting examples:
- la figure 1 est un schéma du dispositif pour la mise en oeuvre du procédé conforme à 1 ' invention;- Figure 1 is a diagram of the device for implementing the method according to one invention;
- la figure 2 est un schéma en coupe partielle de l'enceinte de traitement, montrant l'injecteur du composé alkyl volatil de métal ou de semi-métal et le substrat devant recevoir la couche de métal ou de semi-métal et de leur oxyde.- Figure 2 is a diagram in partial section of the treatment enclosure, showing the injector of the volatile alkyl compound of metal or semi-metal and the substrate to receive the layer of metal or semi-metal and their oxide .
- la figure 3 est une vue en plan de l'extrémité de l'injecteur;- Figure 3 is a plan view of the end of the injector;
- la figure 4 est une vue en perspective de 1 ' injecteur;- Figure 4 is a perspective view of one injector;
- la figure 5 est un spectre Auger du zinc et de son oxyde obtenus par le procédé. Les références numériques indiquées sur les figures désignent les parties ci-après du dispositif:- Figure 5 is an Auger spectrum of zinc and its oxide obtained by the process. The reference numbers indicated in the figures designate the following parts of the device:
1 bouteille d'azote qualité U 2 débitmètre massique de régulation de l'azote 3 tube à décharge (quartz) 4 alimentation du magnétron1 bottle of U-quality nitrogen 2 mass flow meter for nitrogen regulation 3 discharge tube (quartz) 4 magnetron supply
5 magnétron 6 coupleur multimode 7 bouteille de diéthyl zinc 8 vanne micrométrique de réglage 9 jauge Pirani et son boîtier de contrôle5 magnetron 6 multimode coupler 7 bottle of diethyl zinc 8 micrometric adjustment valve 9 Pirani gauge and its control box
10 injecteur de l'alkyl volatil de métal ou de se i métal 11) pompe à palettes10 volatile alkyl metal or metal injector 11) vane pump
12) robinet12) tap
13) enceinte de traitement13) treatment enclosure
14) substrat à traiter Le plasma de décharge est produit par un générateur micro-onde 4 et 5 (2450 MHz) couplé à un coupleur multimode 6 monté sur guide d'ondes RG 112/U, commercialisé par la Société SAIREM, permettant l'obtention de décharge dans l'azote dans une large gamme de pression (10-1-1000 hPa) et avec un couplage transmis compris entre 95 et 100%. pincident14) substrate to be treated The discharge plasma is produced by a microwave generator 4 and 5 (2450 MHz) coupled to a multimode coupler 6 mounted on waveguide RG 112 / U, marketed by SAIREM, allowing the obtaining nitrogen discharge in a wide pressure range (10 -1 -1000 hPa) and with a transmitted coupling between 95 and 100%. p incident
Le plasma de décharge, produit dans un tube de quartz 3 de 30mm de diamètre intérieur, est détendu dans un réacteur en pyrex de 5,2 1 (diamètre intérieurThe discharge plasma, produced in a quartz tube 3 with an internal diameter of 30mm, is expanded in a 5.2 1 pyrex reactor (internal diameter
105mm) 13 par l'intermédiaire d'une pompe à palettes de débit nominal 35 m3/h 11.105mm) 13 via a vane pump with nominal flow 35 m 3 / h 11.
Le gaz plas agène utilisé est de l'azote de qualité U (Air Liquide) .The plas agene gas used is nitrogen of U quality (Air Liquide).
Le précurseur est du diéthyl zinc (DEZ) .The precursor is diethyl zinc (DEZ).
Le DEZ est introduit dans le plasma froid différé d'azote (PFDA) formé dans l'enceinte 13 par l'intermédiaire d'un injecteur 10 incliné à 45° par rapport au flux du plasma (voir figure 2), l'injection se faisant dans le sens du flux. L'injecteur 10 est constitué par un tube de 8mm de diamètre interne, enroulé en une spirale de 7,5cm de diamètre et percé de neuf orifices 15 de 2mm de diamètre espacés de 3cm (voir figures 3 et 4) .The DEZ is introduced into the cold delayed nitrogen plasma (PFDA) formed in the enclosure 13 via an injector 10 inclined at 45 ° with respect to the plasma flow (see FIG. 2), the injection takes place doing in the direction of flow. The injector 10 is constituted by a tube 8mm in internal diameter, wound in a spiral of 7.5cm in diameter and pierced with nine orifices 15 of 2mm in diameter spaced 3cm (see Figures 3 and 4).
Les pressions sont mesurées par l'intermédiaire d'une jauge de Pirani. Le débit d'azote (qualité U Air Liquide) est régulé et contrôlé par l'intermédiaire d'un débitmètre massique. Le débit du DEZ est régulé par une vanne micrométrique. Les échantillons 14 sur lesquels doit être effectué un dépôt de zinc sont placés dans le réacteurThe pressures are measured by means of a Pirani gauge. The nitrogen flow (U Air Liquide quality) is regulated and controlled by a mass flow meter. The flow of DEZ is regulated by a micrometric valve. The samples 14 on which a zinc deposit must be made are placed in the reactor
13 parallèlement à la spirale de l'injecteur 10 et à une distance comprise entre 1 et 3 cm de celui-ci (voir figure 2) .13 parallel to the spiral of the injector 10 and at a distance of between 1 and 3 cm from the latter (see FIG. 2).
La taille du réacteur et de l'injecteur permet de traiter plusieurs échantillons simultanément. On effectue un vide d'environ 10-1 hPa dans l'installation à l'aide du dispositif de pompage. On admet ensuite l'azote (qualité U Air Liquide) sous une pression de 4 hPa avec un débit de 13,8 Nl/min. Puis la décharge est amorcée avec une puissance micro-onde incidente de 400 . Le coupleur est réglé de manière à obtenir un couplage de 100%. Dès l'amorçage de la décharge, une luminescence jaune, caractéristique de la recombinaison des atomes d'azote s'étend dans la chambre réactionnelle et en aval de celle-ci jusqu'à la pompe.The size of the reactor and the injector makes it possible to process several samples simultaneously. A vacuum of about 10 -1 hPa is made in the installation using the pumping device. Nitrogen is then admitted (U Air Liquide quality) under a pressure of 4 hPa with a flow rate of 13.8 Nl / min. Then the discharge is initiated with an incident microwave power of 400. The coupler is adjusted so as to obtain 100% coupling. As soon as the discharge begins, a yellow luminescence, characteristic of the recombination of the nitrogen atoms, extends into the reaction chamber and downstream of it to the pump.
Les échantillons sont soumis au PFDA durant 1 à 5 minutes. Ce pré-traitement a pour objectif le nettoyage des pièces à traiter et l'augmentation de leur adhésivité lorsqu'il s'agit de matériaux polymères.The samples are submitted to the PFDA for 1 to 5 minutes. The aim of this pre-treatment is to clean the parts to be treated and increase their adhesiveness when it comes to polymeric materials.
Puis, le DEZ est injecté. Dès l'arrivée de ce gaz dans le réacteur 13, la luminescence jaune (S-,) caractéristique du PFDA disparaît en aval de l'injecteur, laissant place à une luminescence bleue (S2) . Le débit de DEZ est contrôlé par la géométrie de la réaction chimiluminescente PFDA-DEZ. Les conditions nécessaires pour obtenir un dépôt métallique gris bleu correspondent à la présence de la luminescence bleue en forme de flamme au centre de laquelle sont noyés les échantillons à traiter. Pour un débit d'azote de 13,8 Nl/min, de telles conditions correspondent à une pression partielle de DEZ de 0,1 hPa. Dès l'injection de DEZ, l'apparition d'un dépôt métallique de couleur gris bleu peut être observé sur l'échantillon, ainsi que sur les parois du réacteur; mais ce dernier ne désactive pas le gaz plas agène.Then, the DEZ is injected. As soon as this gas arrives in the reactor 13, the yellow luminescence (S-,) characteristic of the PFDA disappears downstream of the injector, giving way to a blue luminescence (S 2 ). The flow of DEZ is controlled by the geometry of the chemiluminescent reaction PFDA-DEZ. The conditions necessary to obtain a blue gray metallic deposit correspond to the presence of blue luminescence in the form of a flame at the center of which the samples to be treated are embedded. For a nitrogen flow of 13.8 Nl / min, such conditions correspond to a partial pressure of DEZ of 0.1 hPa. As soon as DEZ is injected, the appearance of a blue gray metallic deposit can be observed on the sample, thus only on the walls of the reactor; but the latter does not deactivate the gas plas agène.
Pour stopper le dépôt, on coupe l'alimentation DEZ. Il est important de stopper rapidement cette injection, la présence d'un défaut deTo stop the deposition, cut the DEZ power supply. It is important to quickly stop this injection, the presence of a defect in
DEZ par rapport à l'azote conduisant à l'apparition d'un dépôt poudreux au-dessus du dépôt métallique.DEZ with respect to nitrogen leading to the appearance of a powdery deposit above the metal deposit.
Dans le souci d'éliminer toute trace de DEZ dans le réacteur 13 avant sa remise à l'air, le réacteur est nettoyé par le PFDA durant 5 minutes après le dépôt.In order to eliminate any trace of DEZ in the reactor 13 before it is put back into the air, the reactor is cleaned by the PFDA for 5 minutes after deposition.
On donne ci-après quelques exemples de dépôts de zinc obtenus sur divers substrats.Some examples of zinc deposits obtained on various substrates are given below.
1. Dépôt sur aluminium (injection de DEZ durant 5 min)1. Deposit on aluminum (injection of DEZ for 5 min)
. disque de 5 cm2 , traité 5 min par PFDA pour nettoyage Etat du substrat avant dépôt . présence d'agents contaminants (N,C,P,Na) sur une épaisseur de 14 Â. 5 cm 2 disc, treated 5 min by PFDA for cleaning State of the substrate before deposit. presence of contaminating agents (N, C, P, Na) over a thickness of 14 Å
. présence d'une couche d'oxyde (Al203) de. presence of an oxide layer (Al 2 0 3 ) of
40 Â d'épaisseur Analyse du dépôt après une remise à 1'air de 10 min En dessous d'une couche de contamination de 540 Â thick Analysis of the deposit after a 10 min air release Below a contamination layer of 5
 dans laquelle on détecte outre le Zn métallique et ZnO, la présence de C et de N, on obtient une couche homogène d'un mélange de Zn et de ZnO (dans les proportions respectives de 35% et 65%) ayant une épaisseur de 70  et ne présentant pas de traces d'agents contaminants (C et N) . Il convient de noter que les agents contaminants fixés à la surface du substrat avant le dépôt ne se retrouvent pas à 1'interface dépôt-substrat. La figure 5 montre à titre d'exemple le spectre Auger d'une couche de zinc et de son oxyde déposée selon le procédé selon l'invention. Les pics A et B caractérisent respectivement la présence de Zn et de ZnO. in which, in addition to the metallic Zn and ZnO, the presence of C and N is detected, a homogeneous layer of a mixture of Zn and ZnO (in the respective proportions of 35% and 65%) having a thickness of 70  and not showing traces of contaminating agents (C and N). It should be noted that the contaminating agents attached to the surface of the substrate before deposition are not found at the deposition-substrate interface. FIG. 5 shows by way of example the Auger spectrum of a layer of zinc and its oxide deposited according to the method according to the invention. Peaks A and B respectively characterize the presence of Zn and ZnO.
2. Dépôt sur polypropylène (injection de DEZ durant 5 min) . disque de 5 cm2 , traité par PFDA pour nettoyage et augmentation de 1 'adhésivité. Etat du substrat avant dépôt . traces d'agents contaminants tels que Na, S et O2. Deposit on polypropylene (injection of DEZ for 5 min). 5 cm 2 disc, treated with PFDA for cleaning and increased adhesiveness. State of the substrate before deposit. traces of contaminating agents such as Na, S and O
. taux d'azote greffé trois fois plus important que sur Al. Analyse du dépôt après une remise à 1 'air de 10 min. En dessous d'une couche de contamination dans laquelle on détecte la présence de C et de N, on obtient un dépôt non homogène composé de 3 couches successives, d'épaisseur totale égale à 70 Â, à savoir: dans la première couche [Zn]<[ZnO] (concentration de Zn inférieure à celle de ZnO) dans la deuxième couche [Zn]>[ZnO] (concentration. level of nitrogen grafted three times higher than on Al. Analysis of the deposit after a return to the air for 10 min. Below a contamination layer in which the presence of C and N is detected, a non-homogeneous deposit is obtained composed of 3 successive layers, of total thickness equal to 70 Å, namely: in the first layer [Zn ] <[ZnO] (lower Zn concentration than ZnO) in the second layer [Zn]> [ZnO] (concentration
60 % 40 % de Zn supérieure à celle de ZnO) dans la troisième couche [Zn]<[ZnO] (concentration de Zn inférieure à celle de ZnO) .60% 40% of Zn higher than that of ZnO) in the third layer [Zn] <[ZnO] (concentration of Zn lower than that of ZnO).
On note 1'absence d'agents contaminants dans chacune de ces couches. Il convient de remarquer que l'azote greffé à la surface du polypropylène lors de son traitement par PFDA est toujours présent à l'interface, alors que les agents contaminants (Na et S) ont disparu.The absence of contaminating agents in each of these layers is noted. It should be noted that the nitrogen grafted on the surface of the polypropylene during its treatment with PFDA is still present at the interface, while the contaminating agents (Na and S) have disappeared.
Le dépôt obtenu sur le polypropylène est conducteur: résistance égale à 2000 Ω. 3. Dépôt sur acier inoxydable Un dépôt adhérent de Zn/ZnO a été obtenu sur acier inox Z7 CN 18-09 (C = 0,07%, Cr = 18%, Ni = 9%) . Ce dépôt n'a pas été analysé. Conformément au procédé selon l'invention, un dépôt de zinc a été réalisé à température ambiante sur divers substrats.The deposit obtained on polypropylene is conductive: resistance equal to 2000 Ω. 3. Deposit on stainless steel An adherent deposit of Zn / ZnO was obtained on stainless steel Z7 CN 18-09 (C = 0.07%, Cr = 18%, Ni = 9%). This deposit has not been analyzed. In accordance with the process according to the invention, a deposit of zinc was carried out at ambient temperature on various substrates.
La formation de Zn métal est obtenue par rupture de la liaison entre le Zn et les radicaux alkyles du DEZ sous l'action des espèces actives du PFDA.The formation of Zn metal is obtained by breaking the bond between Zn and the alkyl radicals of DEZ under the action of the active species of PFDA.
L'homogénéité du dépôt dépend de la nature du substrat. Les agents contaminant la surface du substrat ont été dans tous les cas éliminés.The homogeneity of the deposit depends on the nature of the substrate. The agents contaminating the surface of the substrate were in all cases eliminated.
Dans les conditions opératoires des exemples cités ci-dessus, le pourcentage maximum de Zn métallique par rapport à l'oxyde de zinc est de 35% pour un substrat aluminium, et de 60% pour le substrat polypropylène.Under the operating conditions of the examples cited above, the maximum percentage of metallic Zn with respect to zinc oxide is 35% for an aluminum substrate, and 60% for the polypropylene substrate.
Pour une injection de DEZ durant 5 min, l'épaisseur du dépôt obtenu ne dépend pas du substrat et est de l'ordre de 70 Â.For an injection of DEZ for 5 min, the thickness of the deposit obtained does not depend on the substrate and is of the order of 70 Å.
Bien entendu l'invention n'est pas limitée aux exemples que l'on vient de décrire.Of course, the invention is not limited to the examples which have just been described.
Ainsi les exemples relatifs aux dépôts de zinc peuvent s'appliquer à tous les métaux des groupes Ilb, Illa, IVa et Va. Thus the examples relating to zinc deposits can be applied to all the metals of groups Ilb, Illa, IVa and Va.

Claims

REVENDICATIONS
1. Procédé pour déposer sur un substrat (14) , une couche de métal ou de semi-métal et de leur oxyde appartenant aux groupes Ilb, Illa, IVa et Va de la classification des éléments, dans lequel on réalise dans une enceinte (13) dans laquelle se trouve ledit substrat un plasma froid différé d'azote constitué essentiellement d'atomes d'azote libres, pour prétraiter ledit substrat, caractérisé en ce qu'après prétraitement dudit substrat (14) par ledit plasma froid différé d'azote, on introduit dans l'enceinte (13) un alkyl volatil dudit métal ou semi-métal (10) de façon à décomposer ledit alkyl et à réaliser sur ledit substrat (14) une couche constituée par un mélange dudit métal ou semi-métal et de leur oxyde.1. Method for depositing on a substrate (14), a layer of metal or semi-metal and their oxide belonging to the groups Ilb, Illa, IVa and Va of the classification of the elements, in which one carries out in an enclosure (13 ) in which is located said substrate a cold delayed nitrogen plasma consisting essentially of free nitrogen atoms, for pretreating said substrate, characterized in that after pretreatment of said substrate (14) with said cold delayed nitrogen plasma, a volatile alkyl of said metal or semi-metal (10) is introduced into the enclosure (13) so as to decompose said alkyl and to produce on said substrate (14) a layer consisting of a mixture of said metal or semi-metal and their oxide.
2. Procédé conforme à la revendication 1, caractérisé en ce que ledit alkyl volatil est choisi parmi les composés suivants: Groupe:2. Method according to claim 1, characterized in that said volatile alkyl is chosen from the following compounds: Group:
Ilb: Zn(CH3)2,Zn(C2H5)2,Cd(CH3)2,Cd(C2H5)2 Illa: Al(CH3)3,Al(C2H5)3,Ga(CH3)3,Ga(C2H5)3 IVa: Ge(CH3)4,Sn(CH3)4,Pb(C2H5)4,Pb(CH3)4 Va: Sb(CH3)3,Bi(CH3)3. Ilb: Zn (CH 3 ) 2 , Zn (C 2 H 5 ) 2 , Cd (CH 3 ) 2 , Cd (C 2 H 5 ) 2 Illa: Al (CH 3 ) 3 , Al (C 2 H 5 ) 3 , Ga (CH 3 ) 3 , Ga (C 2 H 5 ) 3 IVa: Ge (CH 3 ) 4 , Sn (CH 3 ) 4 , Pb (C 2 H 5 ) 4 , Pb (CH 3 ) 4 Va: Sb (CH 3 ) 3 , Bi (CH 3 ) 3 .
3. Procédé conforme à la revendication 1, caractérisé en ce que le plasma est produit à partir d'azote pur ou pratiquement pur.3. Method according to claim 1, characterized in that the plasma is produced from pure or practically pure nitrogen.
4. Procédé conforme à l'une des revendications 1 à 3, caractérisé en ce que le prétraitement dudit substrat (14) par ledit plasma froid différé d'azote est réalisé pendant une durée comprise entre une et dix minutes.4. Method according to one of claims 1 to 3, characterized in that the pretreatment of said substrate (14) with said cold plasma differed from nitrogen is carried out for a period of between one and ten minutes.
5. Procédé conforme à la revendication 4, caractérisé en ce qu'après introduction de l'alkyl volatil de métal ou de semi-métal dans l'enceinte (13) , le plasma froid différé d'azote est maintenu pendant une durée suffisante pour éliminer toute trace dudit alkyl dans l'enceinte.5. Method according to claim 4, characterized in that after introduction of the volatile alkyl of metal or semi-metal into the enclosure (13), the cold delayed nitrogen plasma is maintained for sufficient time to remove all traces of said alkyl in the enclosure.
6. Procédé conforme à l'une des revendications 1 à 5, caractérisé en ce que l'alkyl volatil de métal ou de semi-métal est injecté dans l'enceinte (13) au moyen d'un injecteur (10) incliné de 45° par rapport au sens de la circulation de l'azote dans ladite enceinte.6. Method according to one of claims 1 to 5, characterized in that the volatile metal or semi-metal alkyl is injected into the enclosure (13) by means of an injector (10) inclined by 45 ° with respect to the direction of circulation of nitrogen in said enclosure.
7. Procédé conforme à la revendication 6, caractérisé en ce que l'extrémité de l'injecteur comporte une tubulure en forme de spirale située dans un plan perpendiculaire à l'injecteur, cette tubulure présentant une série d'ouvertures (15) de sortie pour ledit alkyl volatil de métal ou de semi-métal. 7. Method according to claim 6, characterized in that the end of the injector comprises a spiral-shaped tube situated in a plane perpendicular to the injector, this tube having a series of outlet openings (15) for said volatile metal or semi-metal alkyl.
8. Procédé conforme à l'une des revendications 1 à 7, caractérisé en ce que le substrat (14) est en métal, alliage, céramique, polymère, matériau composite ou verre. 8. Method according to one of claims 1 to 7, characterized in that the substrate (14) is made of metal, alloy, ceramic, polymer, composite material or glass.
PCT/FR1995/000046 1994-01-14 1995-01-13 Method for depositing a film consisting of a metal or semi-metal and an oxide thereof WO1995019456A1 (en)

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WO1997010287A1 (en) * 1995-09-15 1997-03-20 Sommer Revetements France S.A. Method for obtaining a floor covering and product thus obtained
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GB2328692A (en) * 1997-08-18 1999-03-03 Agfa Gevaert Nv Metal deposition using plasma treatment

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