WO2010070127A1 - Method for selectively masking a substrate during an electropolymerisation process - Google Patents
Method for selectively masking a substrate during an electropolymerisation process Download PDFInfo
- Publication number
- WO2010070127A1 WO2010070127A1 PCT/EP2009/067588 EP2009067588W WO2010070127A1 WO 2010070127 A1 WO2010070127 A1 WO 2010070127A1 EP 2009067588 W EP2009067588 W EP 2009067588W WO 2010070127 A1 WO2010070127 A1 WO 2010070127A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- polymer film
- process according
- polymerization
- electro
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
Definitions
- the present invention relates to a method of selectively masking an area of a substrate on which a polymer film is deposited by electropolymerization.
- the substrate is a conductive and oxidizable material, while the electropolymerization is advantageously an electrolysis in which said substrate constitutes the anode.
- the invention also relates to a method for coating this substrate, in addition to the polymer film thus deposited, with at least one other thin element, for example a self-assembled monolayer element, the latter being grafted into a reservation previously arranged in the polymer film by implementing such masking.
- at least one other thin element for example a self-assembled monolayer element
- the functionalization of the surface of an electrically conductive substrate, by chemical or electrochemical means has applications in several fields, in particular in the electronics industry, for the production of components coated with thin layers having different electrical properties, in particular conductivity, as well as in the field of sensors.
- the technique of adhesive tapes is simple but difficult to implement because it presents risks of deposition of impurities on the areas to be protected, as well as contamination of the chemical bath; it requires a subsequent cleaning step, tedious and expensive.
- the technique of masking resins is effective, but also presents a risk of pollution of the substrate. It is long and expensive because it requires several successive stages of impregnation of the resin on the areas to be protected, insolation for the resin crosslinking, removal of the mask, and generally final cleaning.
- the object of the invention is to propose an alternative masking technique that does not have these drawbacks, because of its simplicity of implementation. its non-polluting character, while precisely defining the perimeter to be masked.
- Ultrasounds are vibratory waves whose frequency range extends from about twenty kHz (kilohertz) to several tens of MHz (megahertz).
- the former are used to circulate information through a medium for non-destructive testing purposes.
- the latter whose power, as an indication, has a value greater than about 1 Watt, and whose frequency range, still as an indication, is between 20 kHz and 10 MHz.
- HIFUs High Intensity Focused Utrasound
- this is therefore a method for saving at least a given area of the surface of a substrate of material conductive and oxidizable, during an electro-polymerization process for depositing a polymer film on the surface of this substrate
- this process consists of performing this electropolymerization simultaneously exposing the zone to be masked to a focused beam of power ultrasound, having a power of value greater than 1 Watt.
- the focused beam of ultrasonic waves has a power greater than 10 Watts
- the frequency of the ultrasonic waves is between 20 kHz and 10 MHz
- the electro-polyme ⁇ sation process is an electrolysis in which the substrate constitutes an anode, the deposited polymer film is polypyrrole or polythiophene,
- the electrolyte used contains oxalate ions which promote the polymerization on the non-irradiated surface areas by ultrasound,
- the substrate is an oxidizable metal, for example copper.
- the invention also relates to a method for coating a substrate with a polymer film and at least one other thin element, for example a self-assembled monolayer element, which is a graft in a reservation in the polymer film
- This method comprises a first step which consists in masking the zone of the substrate intended to receive said element, as in the manner described above, and a second step which consists in applying this element against the bare zone, because previously masked, of the substrate.
- a liquid II may consist of a self-assembled monolayer metal or organic element, for example an organothiol, which is grafted onto the substrate by soaking it in an alcoholic solution of organothiol
- FIG. 1 is an illustrative diagram of the masking process
- FIG. 2 represents on a larger scale, and partially, the substrate coated with a polymer film at the end of this operation
- FIG. 3 is a diagram which shows a subsequent step of dipping the substrate in a bath in order to apply a self-assembled monolayer element to a bare zone thereof,
- FIG. 4 represents the substrate coated with the polymer film in which the self-assembled monolayer element is grafted at the end of this second operation.
- FIG. 1 shows an electrolysis tank 1 containing an electrolyte 3 inside which is immersed and immobilized - by means of suitable mounting members, not shown - a substrate 2 in the form of a plate and a counter electrode 40, for example of annular shape
- the counter electrode 40 and the substrate 2 are both made of electrically conductive material, for example metal, the substrate 2 is also made of oxidizable material
- an electric current generator is connected by its negative pole to the counter electrode 40 - which therefore serves as a cathode - and by its positive pole to the substrate 2 - which therefore acts as anode - in a possible implementation of the invention
- the constituent wafer of the substrate 2 is made of copper, and it is desired to deposit a thin film of polypyrrole on one of its faces, its other face is optionally, but not necessarily, protected by a layer 2b of suitable material, which can
- the electrolyte 3 is of the kind usually used to carry out the electropensation of pyrrole on an oxidizable metal, for example an aqueous solution of sodium or potassium oxalate having a pH of 5.
- the current density used is between 1 mA / cm 2 and 100 mA / cm 2
- a piezoelectric transducer HIFU 5 is used.
- This transducer is adapted to generate ultrasonic waves 6 according to a focused beam 60 which converges (through the central opening of the annular counter-electrode 40) towards the face 2a. of the submerged substrate wafer 2, and which is compliant and adjusted to accurately irradiate the zone 7, and only this zone
- the frequency and power used are, for example, respectively 750 kHz and 10 W for a transducer having a diameter of 5 cm.
- Ultrasonic irradiation and electrolysis are conducted simultaneously. This irradiation prevents the deposition of the polymer on the zone 7, according to the desired purpose.
- the duration of the operation is a few seconds.
- the thickness of the film 8 is a few microns.
- the process is very simple and very fast.
- the masking of the zone 7 is obtained without contact of a material mask (such as ribbon or resin) with the substrate 2 or the electrolyte 3, so that any risk of pollution or deposition of impurities is eliminated, without need subsequent cleaning.
- FIG. 3 shows a subsequent step for inserting a self-assembled monolayer element on the substrate, against the bare zone 7.
- Such an element is usually designated by SAM, from the English “Self Assembled Monolayer”.
- the assembly 20 consisting of the substrate 2 and the film 8 is immersed in an alcoholic solution of organothiol contained in a tank 10.
- the self-assembled monolayer is chemically bonded to the surface 2a in the bare area 7, and in this area only.
- SAM monolayer concept can be applied to various molecules capable of grafting onto a metal part, among which the organothiol is, by way of example, the organosilane, or more generally any other metallic or organic element.
- organothiol is, by way of example, the organosilane, or more generally any other metallic or organic element.
- metals that may be suitable for the substrate include, for example, iron, zinc, nickel or aluminum, without this statement being limiting.
- a polymer film there may be mentioned, as monomeric molecules that can be used for electropolymerization, in addition to pyrrole, aniline or thiophene, for example.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
Procédé de masquage sélectif d'un substrat au cours d'un processus d'électro- polymérisation Method of selectively masking a substrate during an electropolymerization process
La présente invention concerne un procédé de masquage sélectif d'une zone d'un substrat sur lequel on dépose un film de polymère par électropolymérisation.The present invention relates to a method of selectively masking an area of a substrate on which a polymer film is deposited by electropolymerization.
Le substrat est un matériau conducteur et oxydable, tandis que l' électro-polymérisation est avantageusement une électrolyse dans laquelle ledit substrat constitue l'anode.The substrate is a conductive and oxidizable material, while the electropolymerization is advantageously an electrolysis in which said substrate constitutes the anode.
L'invention concerne également un procédé pour revêtir ce substrat, en plus du film polymère ainsi déposé, d'au moins un autre élément mince, par exemple un élément monocouche auto-assemblé, celui-ci étant greffé dans une réservation préalablement ménagée dans le film polymère par mise en œuvre d'un tel masquage.The invention also relates to a method for coating this substrate, in addition to the polymer film thus deposited, with at least one other thin element, for example a self-assembled monolayer element, the latter being grafted into a reservation previously arranged in the polymer film by implementing such masking.
La fonctionnalisât ion de la surface d'un substrat électriquement conducteur, par voie chimique ou électrochimique, trouve des applications dans plusieurs domaines, notamment dans l'industrie électronique, pour la réalisation de composants revêtus de couches minces ayant des propriétés électriques différentes, en particulier de conductivité, ainsi que dans le domaine des capteurs.The functionalization of the surface of an electrically conductive substrate, by chemical or electrochemical means, has applications in several fields, in particular in the electronics industry, for the production of components coated with thin layers having different electrical properties, in particular conductivity, as well as in the field of sensors.
Pour ce faire, il est nécessaire de procéder à une ou plusieurs étapes de masquage de certaines zones de cette surface.To do this, it is necessary to perform one or more steps of masking certain areas of this surface.
Classiquement, pour la galvanoplastie, deux méthodes sont mises en œuvre à ce jour, utilisant des rubans adhésifs ou des résines de masquage.Conventionally, for electroplating, two methods are implemented to date, using adhesive tapes or masking resins.
La technique des rubans adhésifs est simple mais d'une mise en œuvre délicate car elle présente des risques de dépôt d'impuretés sur les zones à protéger, ainsi que de contamination du bain chimique ; elle nécessite une étape subséquente de nettoyage, fastidieuse et coûteuse. La technique des résines de masquage est efficace, mais présente également un risque de pollution du substrat. Elle est longue et coûteuse car elle nécessite plusieurs étapes successives d'imprégnation de la résine sur les zones à protéger, d'insolation en vue de la réticulation de la résine, d'élimination du masque, et généralement de nettoyage final. L'invention a pour objectif de proposer une technique alternative de masquage ne présentant pas ces inconvénients, du fait de sa simplicité de mise en œuvre et de son caractère non polluant, tout en définissant avec précision le périmètre à masquer.The technique of adhesive tapes is simple but difficult to implement because it presents risks of deposition of impurities on the areas to be protected, as well as contamination of the chemical bath; it requires a subsequent cleaning step, tedious and expensive. The technique of masking resins is effective, but also presents a risk of pollution of the substrate. It is long and expensive because it requires several successive stages of impregnation of the resin on the areas to be protected, insolation for the resin crosslinking, removal of the mask, and generally final cleaning. The object of the invention is to propose an alternative masking technique that does not have these drawbacks, because of its simplicity of implementation. its non-polluting character, while precisely defining the perimeter to be masked.
Les ultrasons sont des ondes vibratoires dont la gamme de fréquence s'étend d'une vingtaine de kHz (kilohertz) à plusieurs dizaines de MHz (mégahertz).Ultrasounds are vibratory waves whose frequency range extends from about twenty kHz (kilohertz) to several tens of MHz (megahertz).
On fait usuellement une distinction entre les ultrasons dits « de faible puissance et de très haute fréquence » et les ultrasons dits « de puissance ».A distinction is usually made between so-called "low power and very high frequency" ultrasound and so-called "power" ultrasound.
Les premiers sont notamment utilisés pour faire circuler de l'information à travers un milieu à des fins de contrôles non destructifs. Les seconds, dont la puissance, à titre indicatif, a une valeur supérieure à 1 Watt environ, et dont la gamme de fréquence, toujours à titre indicatif, est comprise entre 20 kHz et 10 MHz.The former are used to circulate information through a medium for non-destructive testing purposes. The latter, whose power, as an indication, has a value greater than about 1 Watt, and whose frequency range, still as an indication, is between 20 kHz and 10 MHz.
Ils ont diverses applications industrielles (filtration, décontamination, nettoyage...) et médicales, parmi lesquels on peut citer le traitement de certaines tumeurs comme le cancer du sein, le fibrome de l'utérus et le carcinome de la prostate.They have various industrial applications (filtration, decontamination, cleaning ...) and medical, among which we can mention the treatment of certain tumors such as breast cancer, fibroid of the uterus and carcinoma of the prostate.
Les applications relativement récentes des ultrasons de puissance à des fins thérapeutiques se sont traduites par le développement d'une génération de transducteurs haute fréquence, désignés HIFU (de l'anglais «High Intensity Focused Uïtrasound »), qui permettent de focaliser les ondes ultrasonores sur une surface bien délimitée, en l'occurrence sur la zone à traiter.The relatively recent applications of power ultrasound for therapeutic purposes have resulted in the development of a generation of high frequency transducers, referred to as HIFUs (High Intensity Focused Utrasound), which focus ultrasound waves on a well-defined surface, in this case on the area to be treated.
L'élaboration par voie anodique de films polymères sur une surface métallique oxydable est perturbée par l'oxydation du matériau. Il se produit en effet une compétition entre l'oxydation du substrat et celle du monomère. Les inventeurs ont constaté que cette compétition est accentuée lors de la réaction de polymérisation sur le substrat oxydable, car les ultrasons provoquent alors une augmentation de la dissolution du matériau. L'utilisation d'électrolytes à base d'ions oxalates ou salicylates, permet d'obtenir la polymérisation en limitant l'oxydation du substrat. La polymérisation est ainsi favorisée en milieu oxalate dans les zones de la surface non irradiées par les ultrasons, alors qu'elle est empêchée dans les zones irradiées.The anodic production of polymer films on an oxidizable metal surface is disturbed by the oxidation of the material. There is in fact a competition between the oxidation of the substrate and that of the monomer. The inventors have found that this competition is accentuated during the polymerization reaction on the oxidizable substrate, since the ultrasound then causes an increase in the dissolution of the material. The use of electrolytes based on oxalate or salicylate ions makes it possible to obtain the polymerization by limiting the oxidation of the substrate. The polymerization is thus favored in oxalate medium in the areas of the non-irradiated surface by ultrasound, while it is prevented in the irradiated areas.
La découverte de ces phénomènes physico-chimiques est à la base de la présente invention.The discovery of these physico-chemical phenomena is the basis of the present invention.
Comme déjà mentionné plus haut, celle-ci est donc un procédé pour épargner au moins une zone donnée de la surface d'un substrat en matériau conducteur et oxydable, au cours d'un processus d'electro-polymensation visant a déposer un film de polymère sur Id surface de ce substratAs already mentioned above, this is therefore a method for saving at least a given area of the surface of a substrate of material conductive and oxidizable, during an electro-polymerization process for depositing a polymer film on the surface of this substrate
Conformément a 1 invention, ce procède consiste a effectuer cette électro-polymérisation en exposant simultanément la zone a masquer a un faisceau focalise d'ultrasons de puissance, ayant une puissance de valeur supérieure a 1 WattAccording to the invention, this process consists of performing this electropolymerization simultaneously exposing the zone to be masked to a focused beam of power ultrasound, having a power of value greater than 1 Watt.
Par ailleurs, selon un certain nombre de caractéristiques additionnelles possibles de l'inventionMoreover, according to a number of possible additional features of the invention
- le faisceau focalise d'ondes ultrasonores a une puissance supérieure a 10 Watts ,the focused beam of ultrasonic waves has a power greater than 10 Watts,
- la fréquence des ondes ultrasonores est comprise entre 20 kHz et 10 MHz ,the frequency of the ultrasonic waves is between 20 kHz and 10 MHz,
- le processus d electro-polymeπsation est une electrolyse dans laquelle le substrat constitue 1 anode , - le film polymère dépose est du polypyrrole ou du polythiophene ,the electro-polymeπsation process is an electrolysis in which the substrate constitutes an anode, the deposited polymer film is polypyrrole or polythiophene,
- l'electrolyte mis en œuvre contient des ions oxalates qui favorisent la polymérisation sur les zones de surface non irradiées par les ultrasons,the electrolyte used contains oxalate ions which promote the polymerization on the non-irradiated surface areas by ultrasound,
- le substrat est un métal oxydable, par exemple du cuivre L'invention a aussi pour objet un procède pour revêtir un substrat d'un film polymère et d'au moins un autre élément mince, par exemple un élément monocouche auto-assemble, qui est greffe dans une réservation ménagée dans le film polymèrethe substrate is an oxidizable metal, for example copper. The invention also relates to a method for coating a substrate with a polymer film and at least one other thin element, for example a self-assembled monolayer element, which is a graft in a reservation in the polymer film
Ce procède comprend une première étape qui consiste a masquer la zone du substrat destinée a recevoir ledit élément, ceci de la façon exposée ci- dessus, et une seconde étape qui consiste a appliquer cet élément contre la zone nue, car préalablement masquée, du substratThis method comprises a first step which consists in masking the zone of the substrate intended to receive said element, as in the manner described above, and a second step which consists in applying this element against the bare zone, because previously masked, of the substrate.
Ledit élément est avantageusement applique contre le substrat par trempage dans un liquide II peut consister en un élément métallique ou organique de type monocouche auto-assemble, par exemple d organothiol, qui est greffe sur le substrat par trempage de celui-ci dans une solution alcoolique d' organothiolSaid element is advantageously applied against the substrate by dipping in a liquid II may consist of a self-assembled monolayer metal or organic element, for example an organothiol, which is grafted onto the substrate by soaking it in an alcoholic solution of organothiol
D'autres caractéristiques et avantages de l'invention apparaîtront a la lecture de la description suivante d un mode de réalisation préfère de l'invention Cette description est faite en référence aux dessins annexes dans lesquelsOther characteristics and advantages of the invention will appear on reading the following description of a preferred embodiment of the invention. This description is made with reference to the accompanying drawings in which:
- la figure 1 est un schéma îllustratif du procède de masquage , - la figure 2 représente a plus grande échelle, et partiellement, Ic substrat revêtu d'un film polymère a l'issue de cette opération , - la figure 3 est un schéma qui montre une étape subséquente de trempage du substrat dans un bain en vue de l'application d'un élément monocouche auto-assemblé sur une zone nue de celui-ci ,FIG. 1 is an illustrative diagram of the masking process; FIG. 2 represents on a larger scale, and partially, the substrate coated with a polymer film at the end of this operation, FIG. 3 is a diagram which shows a subsequent step of dipping the substrate in a bath in order to apply a self-assembled monolayer element to a bare zone thereof,
- la figure 4 représente le substrat revêtu du film polymère dans lequel est greffe l'élément monocouche auto-assemblé a l'issue de cette seconde opérationFIG. 4 represents the substrate coated with the polymer film in which the self-assembled monolayer element is grafted at the end of this second operation.
Sur la figure 1 est représentée une cuve d'électrolyse 1 contenant un électrolyte 3 a l'intérieur duquel est plongé et immobilisé - au moyen d'organes de montage appropriés, non représentés- un substrat 2 en forme de plaquette ainsi qu'une contre électrode 40, par exemple de forme annulaireFIG. 1 shows an electrolysis tank 1 containing an electrolyte 3 inside which is immersed and immobilized - by means of suitable mounting members, not shown - a substrate 2 in the form of a plate and a counter electrode 40, for example of annular shape
La contre électrode 40 et le substrat 2 sont tous deux en matériau électriquement conducteur, par exemple métallique , le substrat 2 est de plus en matériau oxydableThe counter electrode 40 and the substrate 2 are both made of electrically conductive material, for example metal, the substrate 2 is also made of oxidizable material
Un générateur de courant électrique est connecte par son pôle négatif a la contre électrode 40 -qui fait donc office de cathode- et par son pôle positif au substrat 2 -qui fait donc office d' anode- Dans une mise en œuvre possible de l'invention, la plaquette constitutive du substrat 2 est en cuivre, et on souhaite déposer un film mince de polypyrrole sur l'une 2a de ses faces , son autre face est éventuellement, mais non obligatoirement, protégée par une couche 2b en matériau approprié, pouvant être amovible L'électrolyte 3 est du genre habituellement utilise pour réaliser Pélectro- polymensation du pyrrole sur un métal oxydable, par exemple une solution aqueuse d'oxalate de sodium ou de potassium ayant un pH de 5An electric current generator is connected by its negative pole to the counter electrode 40 - which therefore serves as a cathode - and by its positive pole to the substrate 2 - which therefore acts as anode - in a possible implementation of the invention, the constituent wafer of the substrate 2 is made of copper, and it is desired to deposit a thin film of polypyrrole on one of its faces, its other face is optionally, but not necessarily, protected by a layer 2b of suitable material, which can The electrolyte 3 is of the kind usually used to carry out the electropensation of pyrrole on an oxidizable metal, for example an aqueous solution of sodium or potassium oxalate having a pH of 5.
A titre indicatif, la densité de courant mise en œuvre est comprise entre 1 mA/cm2 et 100 mA/cm2 As an indication, the current density used is between 1 mA / cm 2 and 100 mA / cm 2
On souhaite recouvrir la face supérieure du substrat 2 de manière incomplète, en préservant une zone 7 de dimensions réduites, et de contour bien défini, par exemple circulaire d'un diamètre de 3 mmIt is desired to cover the upper face of the substrate 2 incompletely, preserving a zone 7 of reduced dimensions, and of well-defined contour, for example circular with a diameter of 3 mm
A cet effet, on fait usage d'un transducteur piézoélectrique HIFU 5 Celui-ci est adapte pour générer des ondes ultrasonores 6 selon un faisceau focalise 60 qui converge (en traversant l'ouverture centrale de la contre électrode annulaire 40) vers la face 2a de la plaquette de substrat immergée 2, et qui est conforme et réglé pour irradier précisément la zone 7, et uniquement cette zoneFor this purpose, a piezoelectric transducer HIFU 5 is used. This transducer is adapted to generate ultrasonic waves 6 according to a focused beam 60 which converges (through the central opening of the annular counter-electrode 40) towards the face 2a. of the submerged substrate wafer 2, and which is compliant and adjusted to accurately irradiate the zone 7, and only this zone
Selon une variante de réalisation non représentée sur les figures, il serait également possible d'adapter l'installation de façon que le faisceau d'ondes ultrasonores soit focalisé en plusieurs points différents, afin d'irradier plusieurs zones de la plaquette de substrat 2.According to an alternative embodiment not shown in the figures, it would also be possible to adapt the installation so that the wave beam ultrasound is focused at several different points to irradiate several areas of the substrate wafer 2.
La fréquence et la puissance mises en œuvre sont par exemple respectivement de 750 kHz et de 10 W pour un transducteur ayant un diamètre de 5 cm.The frequency and power used are, for example, respectively 750 kHz and 10 W for a transducer having a diameter of 5 cm.
L'irradiation aux ultrasons et l'électrolyse sont menées simultanément. Cette irradiation empêche le dépôt du polymère sur la zone 7, conformément au but recherché.Ultrasonic irradiation and electrolysis are conducted simultaneously. This irradiation prevents the deposition of the polymer on the zone 7, according to the desired purpose.
A titre indicatif la durée de l'opération est de quelques secondes. A l'issue du traitement, comme illustré sur la figure 2, la plaquetteAs an indication, the duration of the operation is a few seconds. At the end of the treatment, as illustrated in FIG. 2, the wafer
2 possède une face revêtue d'un film mince de polymère 8, en l'occurrence de polypyrrole, tandis que la zone 7 est parfaitement nue.2 has a side coated with a thin film of polymer 8, in this case polypyrrole, while the zone 7 is perfectly bare.
A titre indicatif, l'épaisseur du film 8 est de quelques micromètres.As an indication, the thickness of the film 8 is a few microns.
On notera que le procédé est très simple et très rapide. Le masquage de la zone 7 est obtenu sans contact d'un masque matériel (tel que ruban ou résine) avec le substrat 2 ou l'électrolyte 3, de sorte que tout risque de pollution ou de dépôt d'impuretés est éliminé, sans nécessité de nettoyage ultérieur.Note that the process is very simple and very fast. The masking of the zone 7 is obtained without contact of a material mask (such as ribbon or resin) with the substrate 2 or the electrolyte 3, so that any risk of pollution or deposition of impurities is eliminated, without need subsequent cleaning.
La figure 3 montre une étape subséquente servant à insérer un élément monocouche auto-assemblé sur le substrat, contre la zone nue 7.FIG. 3 shows a subsequent step for inserting a self-assembled monolayer element on the substrate, against the bare zone 7.
Un tel élément est usuellement désigné par SAM, de l'anglais « Self Assembled Monolayer ».Such an element is usually designated by SAM, from the English "Self Assembled Monolayer".
Selon le mode d'exécution mis en œuvre ici, il s'agit d'une SAM d'organothiol. Pour cela l'ensemble 20 composé du substrat 2 et du film 8 est plongé dans une solution alcoolique d'organothiol contenue dans un bac 10.According to the embodiment implemented here, it is an organothiol SAM. For this, the assembly 20 consisting of the substrate 2 and the film 8 is immersed in an alcoholic solution of organothiol contained in a tank 10.
Ceci a pour résultat que l'élément monocouche auto-assemblé se greffe chimiquement à la surface 2a dans la zone nue 7, et dans cette zone uniquement. A l'issue de l'opération, après enlèvement éventuel de la sous- couche protectrice 2b, on obtient une plaquette de cuivre 2 recouverte d'un film de polypyrrole dans lequel est greffée la SAM d'organothiol 9, comme cela est illustré sur la figure 4.As a result, the self-assembled monolayer is chemically bonded to the surface 2a in the bare area 7, and in this area only. At the end of the operation, after optional removal of the protective underlayer 2b, a copper wafer 2 covered with a polypyrrole film into which is grafted the organothiolan SAM 9, as illustrated on Figure 4.
La notion de monocouche SAM peut s'appliquer à diverses molécules aptes à se greffer sur une pièce métallique, parmi lesquelles outre l'organothiol on citera, à titre, d'exemple l'organosilane, ou d'une manière plus générale tout autre élément métallique ou organique.SAM monolayer concept can be applied to various molecules capable of grafting onto a metal part, among which the organothiol is, by way of example, the organosilane, or more generally any other metallic or organic element.
On peut bien évidemment masquer plusieurs zones d'un même substrat en faisant simultanément usage de plusieurs faisceaux d'ondes sonores focalisées au cours du processus d'électro polymérisation.It is of course possible to mask several zones of the same substrate by simultaneously making use of several beams of focused sound waves during the electro-polymerization process.
Comme autres métaux susceptibles de convenir pour le substrat, on peut citer à titre d'exemples, le fer, le zinc, le nickel ou l'aluminium, sans que cet énoncé soit limitatif.Other metals that may be suitable for the substrate include, for example, iron, zinc, nickel or aluminum, without this statement being limiting.
S'agissant d'obtenir un film polymère, on peut citer, comme molécules monomères pouvant être mises en œuvre pour l'électro polymérisation, outre le pyrrole, l'aniline ou le thiophène par exemple. As regards obtaining a polymer film, there may be mentioned, as monomeric molecules that can be used for electropolymerization, in addition to pyrrole, aniline or thiophene, for example.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0858814A FR2940324B1 (en) | 2008-12-19 | 2008-12-19 | METHOD OF SELECTIVELY MASKING A SUBSTRATE DURING AN ELECTRO POLYMERIZATION PROCESS |
| FR0858814 | 2008-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010070127A1 true WO2010070127A1 (en) | 2010-06-24 |
Family
ID=40790799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2009/067588 Ceased WO2010070127A1 (en) | 2008-12-19 | 2009-12-18 | Method for selectively masking a substrate during an electropolymerisation process |
Country Status (2)
| Country | Link |
|---|---|
| FR (1) | FR2940324B1 (en) |
| WO (1) | WO2010070127A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2111530A (en) * | 1981-12-08 | 1983-07-06 | Standard Telephones Cables Ltd | Selective electro plating or etching process |
-
2008
- 2008-12-19 FR FR0858814A patent/FR2940324B1/en active Active
-
2009
- 2009-12-18 WO PCT/EP2009/067588 patent/WO2010070127A1/en not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2111530A (en) * | 1981-12-08 | 1983-07-06 | Standard Telephones Cables Ltd | Selective electro plating or etching process |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2940324B1 (en) | 2012-04-27 |
| FR2940324A1 (en) | 2010-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100454501C (en) | Surface-coating method, production of microelectronic interconnections using said method and integrated circuits | |
| BE1004844A7 (en) | Metallisation methods surface using metal powder. | |
| JP7237000B2 (en) | Apparatus and method for controlled electrochemical surface modification | |
| FR2944982A1 (en) | PROCESS FOR PREPARING A METALLIZED SUBSTRATE, ANDTHE SUBSTRATE AND USES THEREOF | |
| EP1872116B1 (en) | Method using an electrochemical sensor and electrodes forming said sensor | |
| Ghilane et al. | Oxidative and stepwise grafting of dopamine inner-sphere redox couple onto electrode material: Electron transfer activation of dopamine | |
| CN103364243A (en) | Preparation method of titanium alloy surface passivation film transmission observation sample | |
| EP2922987A1 (en) | Method for coating the surface of an organic or metal material with particular organic compounds by means of a pulsed-current electrochemical reduction of the diazonium ions of said organic compounds | |
| Bai et al. | Ultraminiaturized Microfluidic Electrochemical Surface‐Enhanced Raman Scattering Chip for Analysis of Neurotransmitters Fabricated by Ship‐in‐a‐Bottle Integration | |
| WO2010070127A1 (en) | Method for selectively masking a substrate during an electropolymerisation process | |
| CN115305535B (en) | A surface-enhanced Raman substrate with high membrane-base binding force and preparation method thereof | |
| US6867134B2 (en) | Adherent all-gold electrode structure for lithium niobate based devices and the method of fabrication | |
| EP0500415B1 (en) | Contact of an electric connector protected by a polymer film and method for its fabrication | |
| CA2210961A1 (en) | Resonating electrolytic plating anode | |
| Taouil et al. | Electropolymerization of pyrrole on oxidizable metal under high frequency ultrasound irradiation. Application of focused beam to a selective masking technique | |
| KR100960005B1 (en) | Plating method of RF equipment and RF equipment manufactured thereby | |
| Meinderink et al. | Electrodeposition of poly (acrylic acid) on stainless steel with enhanced adhesion properties | |
| Olson et al. | Electrodeposition of gold particles on aluminum substrates containing copper | |
| JP5379117B2 (en) | Gold surface treatment method | |
| Xu et al. | Study on the preparation mechanism and property analysis of a localized Au coating by laser-induced cyanide-free electroplating | |
| Song et al. | Fabrication of gold microelectrodes on a glass substrate by femtosecond-laser-assisted electroless plating | |
| JP6819416B2 (en) | Through Silicon Via Substrate and Its Manufacturing Method | |
| Banks et al. | Sonovoltammetric Elucidation of Electron Transfer Rates: The Oxidation of Dimethyl‐p‐phenylenediamine in Aqueous Solution | |
| EP2676740A1 (en) | Method for the covalent grafting of a polyarylene film on an electrically conductive or semi-conductive surface | |
| EP2262866B1 (en) | Method for localised electro-grafting on conducting or semiconducting substrates in the presence of a microelectrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09795773 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 09795773 Country of ref document: EP Kind code of ref document: A1 |