EP1971704A2 - Couche polymere comprenant de la silicone et au moins un metal a l'etat de trace et procede pour la fabriquer - Google Patents

Couche polymere comprenant de la silicone et au moins un metal a l'etat de trace et procede pour la fabriquer

Info

Publication number
EP1971704A2
EP1971704A2 EP06827730A EP06827730A EP1971704A2 EP 1971704 A2 EP1971704 A2 EP 1971704A2 EP 06827730 A EP06827730 A EP 06827730A EP 06827730 A EP06827730 A EP 06827730A EP 1971704 A2 EP1971704 A2 EP 1971704A2
Authority
EP
European Patent Office
Prior art keywords
polymer
layer
silicone
metal
metal trace
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.)
Withdrawn
Application number
EP06827730A
Other languages
German (de)
English (en)
Inventor
Lucien Laude
Neil Hamilton Talbot
Robert J. Greenberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Doheny Eye Institute of USC
Vivani Medical Inc
Original Assignee
Doheny Eye Institute of USC
Second Sight Medical Products Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US11/270,907 external-priority patent/US8771805B2/en
Application filed by Doheny Eye Institute of USC, Second Sight Medical Products Inc filed Critical Doheny Eye Institute of USC
Publication of EP1971704A2 publication Critical patent/EP1971704A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/265—Selective reaction with inorganic or organometallic reagents after image-wise exposure, e.g. silylation
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
    • C23C18/1868—Radiation, e.g. UV, laser
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/107—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by filling grooves in the support with conductive material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0277—Bendability or stretchability details
    • H05K1/0283—Stretchable printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0286—Programmable, customizable or modifiable circuits
    • H05K1/0287—Programmable, customizable or modifiable circuits having an universal lay-out, e.g. pad or land grid patterns or mesh patterns
    • H05K1/0289—Programmable, customizable or modifiable circuits having an universal lay-out, e.g. pad or land grid patterns or mesh patterns having a matrix lay-out, i.e. having selectively interconnectable sets of X-conductors and Y-conductors in different planes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0133—Elastomeric or compliant polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0162—Silicon containing polymer, e.g. silicone
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0147—Carriers and holders
    • H05K2203/016—Temporary inorganic, non-metallic carrier, e.g. for processing or transferring
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/007—Manufacture or processing of a substrate for a printed circuit board supported by a temporary or sacrificial carrier
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a silicone polymer material comprising at least one metal trace and a process of manufacturing the same.
  • the first step is to coat the substrate part with a precursor composite material layer consisting of a polymer matrix doped with photoreducer material dielectric particles.
  • the second step is to irradiate the surface of the substrate with a light beam emitted by a laser.
  • the third step is to immerse the irradiated part in an autocatalytic bath containing metal ions, with deposition of the metal ions in a layer on the irradiated surface, wherein the dimension of the dielectric particles is less than or equal to 0.5 ⁇ m.
  • the second step consists of immersing the irradiated polymer piece in at least one autocatalytic bath containing metal ions.
  • the immersion induces the deposit of the metal ions onto the irradiated surface area to form a metal film on the surface area, resulting in the selective metallization of the surface area of the polymer piece.
  • the third step consists of thermally processing the metallized polymer piece to induce diffusion of the deposited metal film into the polymer material of the polymer piece.
  • Lucien D. Laude et al. report that excimer lasers are effective tools in engraving ceramics and polymers, changing irreversibly the surface of the irradiated material, and restricting these effects to specific areas of interest. See L. D. Laude, K Kolev, Cl. Dicaraand C. Kus-Bruzek “Laser Metallization for Microelectronics for Bio-applications", Proc. of SPIE Vol. 4977 (2003), pp 578-586.
  • a method of fabricating an electronic apparatus comprising the steps of providing a silicone layer on a matrix, providing a metal layer on said silicone layer, providing a second layer of silicone on said silicone layer, providing at least one electronic unit connected to said metal layer, and removing said electronic apparatus from said matrix wherein said silicone layer and said second layer of a silicone provide a spherical silicone body.
  • One aspect of the present invention is a process for embedding at least one layer of at least one metal trace in a silicone-containing polymer, comprising: a) applying a polymer layer on a substrate; b) thermally treating the polymer; c) irradiating at least one surface area of the polymer with a light beam emitted by an excimer laser; d) immersing the irradiated polymer in at least one autocatalytic bath containing ions of at least one metal, and metallizing the polymer; e) thermally treating the metallized polymer; f) applying a polymer layer covering the thermally treated metallized polymer; and g) thermally treating the metallized covered polymer.
  • Another aspect of the present invention is a polymer layer comprising silicone containing oxide particles Of SiO 2 , TiO 2 , Sb 2 O 3 , SnO 2 , Al 2 O 3 , ZnO, Fe 2 O 3 , Fe 3 O 4 , talc, hydroxyapatite or mixtures thereof and at least one metal trace embedded in said polymer layer.
  • Another aspect of the present invention is a flexible electrode array comprising silicone containing oxide particles of SiO 2 , TiO 2 , Sb 2 O 3 , SnO 2 , Al 2 O 3 , ZnO, Fe 2 O 3 , Fe 3 O 4 , talc, hydroxyl- apatite or mixtures thereof and at least one metal trace embedded in said polymer layer.
  • Fig. 1 depicts a cross-sectional view of a substrate
  • Fig. 2 depicts a cross-sectional view of a substrate and a first polymer layer after curing
  • Fig. 3 depicts a cross-sectional view of a substrate and a cured first polymer layer after laser treatment
  • Fig. 4 depicts a cross-sectional view of a substrate and a cured first polymer layer after metallization whereby metal traces are obtained;
  • Fig. 5 depicts a cross-sectional view of a substrate and a cured first polymer layer after disposing a second polymer layer on top of the first polymer layer and the metal traces;
  • Fig. 6 depicts a cross-sectional view of a substrate and a cured first polymer layer and metal traces after curing the second polymer layer
  • Fig. 7 depicts a perspective view of a cured polymer layer with one embedded series of metal traces as shown in figure 6;
  • Fig. 8 depicts a perspective view of a cured polymer layer with one embedded series of metal traces as shown in figure 6 after a cut out of the polymer;
  • Fig. 9 depicts a top view of a flexible circuit electrode array
  • Fig. 10 depicts a top view of a body comprising a flexible circuit electrode array, a flexible circuit cable and a bond pad before it is folded;
  • Fig. 11 depicts a top view of a body comprising a flexible circuit electrode array, a flexible circuit cable and a bond pad after it is folded;
  • Fig. 12 depicts a flow chart explaining an example of the process.
  • Fig. 13 depicts a cross-sectional view of a substrate;
  • Fig. 14 depicts a cross-sectional view of a substrate and a layer of a non adhering agent
  • Fig. 15 depicts a cross-sectional view of a substrate and a layer of a non adhering agent and a first polymer layer after curing
  • Fig. 16 depicts a cross-sectional view of a substrate and a layer of a non adhering agent and a first polymer layer after laser treatment
  • Fig. 17 depicts a cross-sectional view of a substrate and a layer of a non adhering agent and a first polymer layer after metallization whereby metal traces were obtained;
  • Fig. 18 depicts a cross-sectional view of a substrate and a layer of a non adhering agent and a first polymer layer after disposing a second polymer layer on top of the first polymer layer and the metal traces;
  • Fig. 19 depicts a cross-sectional view of a substrate and a layer of a non adhering agent and a first polymer layer and metal traces after curing the second polymer layer;
  • Fig. 20 depicts a cross-sectional view of a polymer layer with one embedded series of metal traces after removing from the rigid substrate;
  • Fig. 21 depicts a perspective view of a polymer layer with one embedded series of metal traces as shown in figure 8;
  • Fig. 22 depicts a perspective view of a polymer layer with one embedded series of metal traces as shown in figure 8 after a cut out of the polymer
  • Fig. 23 depicts a cross-sectional view of a polymer layer with one embedded series of metal traces after opening the traces;
  • Fig. 24 depicts a cross-sectional view of the polymer layer after laser treatment of the second polymer layer
  • Fig. 25 depicts a cross-sectional view of the polymer layer after metallization of the second polymer layer
  • Fig. 26 depicts a cross-sectional view of the polymer layer after applying a third polymer layer and after curing
  • Fig. 27 depicts a cross-sectional view of a polymer layer with two embedded overlapping crossing series of metal traces after removing the layer from the rigid substrate
  • Fig. 28 depicts a perspective view of a polymer layer with two embedded overlapping series of metal traces as shown in figure 27;
  • Fig. 29 depicts a perspective view of a polymer layer with one embedded series of metal traces as shown in figure 28 after a cut out of the polymer;
  • Fig. 30 depicts a cross-sectional view of a polymer layer with two embedded series of metal traces as shown in figure 28 after opening the traces;
  • Fig. 31 depicts a perspective view of a polymer layer with two embedded overlapping crossing series of metal traces
  • Fig. 32 depicts a perspective view of a polymer layer with two embedded series of metal traces as shown in figure 31 after a cut out of the polymer;
  • Fig. 33 depicts a cross-sectional view of a polymer layer with two embedded series of metal traces as shown in figure 31 after opening the traces;
  • Fig. 34 A depicts a perspective view of a first polymer layer with one embedded metal trace;
  • Fig. 34B depicts a perspective view of a first polymer layer after laser drilling through the upper front of the layer to form an opening down to the metal trace;
  • Fig. 34C depicts a perspective view of a first polymer layer after partial metal plating of the laser cut opening
  • Fig. 34D depicts a perspective view of a first polymer layer after laser processing the traces to overlap the opening
  • Fig. 34E depicts a perspective view of a first polymer layer after metallizing of the trace and further metallizing the opening
  • Fig 34F depicts a perspective view of a first polymer layer after disposing a second polymer layer on top of it and form a bi-layer
  • Fig. 34G depicts a perspective view of a polymer layer after removing the layer from the rigid substrate.
  • the present invention relates preferably to the metallization of a polymer, generally Si- based polymers.
  • a more preferred embodiment of the present invention is the metallization of polymers with platinum.
  • the most preferred embodiment is a polymer layer comprising at least one metal trace embedded in the polymer layer.
  • the preferred polymer of the present invention is a silicone containing polymer.
  • Silicone means, in view of the present invention, any and all possible silicone elastomer formulations, silicone craft polymers, silicone copolymers, silicone-silicone copolymers, silicone-hydrocarbon copolymers, silicone block polymers, silicone block copolymers, silicone rubbers or mixtures thereof. Silicone may contain any type and amount of additives.
  • C l- n is an integer > 1.
  • Silicone elastomers have high molecular weight, generally greater than 500,000 g/mol.
  • the production of these types of materials requires di-functional precursors, which form polymer structures.
  • Mono and tri-functional precursors form terminal structures and branched structures respectively.
  • Silicone rubbers contain usually cured additives like peroxides such as benzoyl peroxide,
  • Reinforcing fillers are added to improve the otherwise poor tensile strength of silicones.
  • Silica in the form of silica fume, silica foam, or fumed silica with particle sizes in the range 10 nm - 40 nm is the most preferred filler, although carbon black has been used. Fillers do interact with the vulcanisate, forming a pseudo-vulcanization. This can occur either during mixing and creep hardening or in storage and bin ageing.
  • Fumed silica has unique properties and is commonly added to liquids/coatings and solids to improve various properties. Fumed silica has chain-like particle morphology. In liquids, the chains bond together via weak hydrogen bonds forming a three dimensional network, trapping liquid and effectively increasing the viscosity. The effect of the fumed silica can be negated by the application of a shear force for example mixing, brushing, spraying etc., allowing the liquid to flow, level out and permit the escape of entrapped air.
  • a shear force for example mixing, brushing, spraying etc.
  • HCl can easily be separated as it remains in the gas phase, while SiO 2 is solid in the form of fumed silica.
  • Silicone can be in large variation of shapes and forms, such as thin sheets obtained by spun coating or spray coating, foil obtained by lamination or molding, bloc molded pieces, distributed silicone, silicone mixed with thermoplastic material.
  • the present invention provides a cured silicone layer which has a preferred thickness of 10 ⁇ m to 80 ⁇ m, preferably 20 ⁇ m to 40 ⁇ m. This layer contains laser-drawn traces up to 10 ⁇ m to 20 ⁇ m traces or pads with a dimension of 100 ⁇ m to 200 ⁇ m which are filled with metallized deposit.
  • the present invention further provides a silicone layer which has a preferred thickness of
  • This layer contains laser-drawn traces having a width of to 10 ⁇ m to 20 ⁇ m which are filled with metallized deposit, preferably with Pt.
  • This layer contains further a second 15 ⁇ m to 25 ⁇ m thick silicone layer covering the once metallized first silicone layer. After curing that second silicone layer an optimum silicone-to-silicone adhesion of the second silicone layer provides a fully protected cover to the metallized silicone layer. A full silicone- encapsulation of the once produced metal traces is thereby obtained.
  • silicones have a formulation that contains generally a variable amount of fumed silica (silica foam) that serves to strengthen the polymeric structure in various ways. It also favors the electroless-metallization process and improves substantially the mechanical behavior of metallized silicone.
  • the final silicone cover remains unmetallized and serves solely for the purpose of protecting and insulating the underlying metallized silicone layers. That silicone cover may be formed with a silicone that is different from the silicone that has been used for the underlying layers. In particular, it may not contain silica foam at all and may then be more readily applied even to very small layer thickness. Therefore, a silicone cover of 15 ⁇ m to 20 ⁇ m is formed on the metallized silicone layer. That silicone cover is formed with a silica foam free silicone that is spun onto the metallized silicone before curing as above.
  • a non-organic powder is dispersed in any given polymer, for example polyamide.
  • the non-organic powder is for example at least one oxide of antimony, aluminum, iron, zinc or tin.
  • the oxide particles have variable particle sizes, preferably smaller than about 50 ⁇ m.
  • the concentration of the oxide particles in the polymer exceeds about 1 VoL- % or 1 wt.-%.
  • the surface of the polymer material is irradiated with the light beam emitted by a laser.
  • the light is emitted preferably in the ultraviolet wavelength range, during a very short duration or pulse and repeated if necessary at regular time intervals.
  • the pulsed emission has preferably high energy, for example, between 0.05 J and 1.0 J.
  • the desired emission may be obtained from an excimer laser source emitted during about 10 ns, at a wavelength of about 248 nm which corresponds to photon energy of 5.0 eV.
  • the laser beam may be passed through a mask having a specific geometry, and projected upon focalization onto the surface of the material to be treated.
  • a desired processing is obtained beyond a given energy density of about 0.5J/cm 2 , or fluence, and as a function of the material optical properties and the laser photon energy.
  • UV laser irradiation may produce two effects that depend on both fluence and photon energy.
  • the silicone undergoes partial decomposition by breaking the Si-C bonds. This results in ablation of the C-radicals but leaves unaffected the Si-O bonds of the polymer backbone.
  • the silicone undergoes total decomposition by breaking both Si-C and Si-O bonds. This results in a full ablation of silicone, typically at a rate of some 0.5 ⁇ m per pulse at 0.5mJ/cm 2 , and irrespective of the silicone formulation.
  • silicone treated with the 248 nm laser is immersed in an autocatalytic bath that contains metal ions, for example Ni 2+ , Cu 2+ , or Pt 2+ . These ions are selectively driven to deposit and react on the partially decomposed silicone structure regardless if the treated silicone contains an additive, for example silica foam, or not.
  • irradiating silicone at 193 nm provides a very efficient way to fully and exclusively ablate silicone, containing silica foam or not.
  • irradiating silicone at 193 nm allows opening clean and well defined cuts, grooves, blind holes or vias through it.
  • Silicone parts engraved by 193 nm do not metallize by immersing in an autocatalytic bath. During immersion of the laser processed surface into the autocatalytic bath, metallization is restricted to the actual laser treated surface. The incubation time measures the period of time which is necessary to form a continuous metal film on the composite surface.
  • the metal deposition which is usually 10 ⁇ m to 20 ⁇ m per hour for Ni, may develop perpendicularly to the surface in a most efficient manner.
  • the advantages of the process of the present invention result directly from the use of an intense and pulsed ultraviolet light beam, as for instance the one emitted by an excimer laser source working at a wavelength equal or inferior to 308 nm. All other light sources working in the visible or infrared range, in pulsed or continuous regime are inactive on silicone.
  • the preferred irradiation source according to this invention is an excimer laser.
  • the preferred excimer laser performs engraving at about 248 nm with partial decomposition of silicone and allows metallization.
  • the laser pulse duration is in the range of 1 ns to 40 ns by steady or scanning irradiation. In comparison engraving below about 200 nm performs full ablation but no metallization can follow after the ablation.
  • a silicone layer is spun on a clean glass plate and cured in an oven.
  • the layer may have a near constant thickness at about 40 ⁇ m across the glass substrate. The thickness depends on spinning conditions and the content of additives. The higher the content of additives is the more difficult is the spinning.
  • This layer is then scanned with a focused 248 nm excimer laser beam working at a sufficient fluence that allows partial decomposition of the silicone material down to some 10 ⁇ m to 15 ⁇ m into the layer.
  • the laser processed silicone layer, on its glass substrate, is further immersed in an electroless bath containing metal ions. Subsequently, the latter ions condense solely on the laser-processed areas of the silicone layer where they contribute to form metallized deposits precisely in the laser-drawn areas and remain embedded in the silicone layer without touching the glass substrate underneath.
  • Silicones have a formulation that contains generally a variable amount of silica foam additive that serves to strengthen the polymeric structure in various ways. This additive or other form of silica for example fiber also favors the electroless-metallization process and improves substantially the mechanical behavior of metallized silicone.
  • the final silicone cover remains un-metallized and serves solely the purpose of protecting the underlying metallized layers.
  • That silicone cover may be formed with a silicone that is different from the one silicone that has been used for the other underlying layers. In particular, it may not contain silica at all and may then be more readily spun, even to very small layer thickness. Therefore, a silicone cover of 20 ⁇ m is formed on the last metallized silicone layer. That silicone cover is formed with a silica-free silicone that is spun onto the metallized silicone before curing as above.
  • the electroless Pt-metallization proceeds via forming a thin so-called black metal film and then goes on a second step of Pt-deposit that thickens the metal layer. That second step is extremely slow being impaired in particular with the formation of H-bubbles on a quite uneven metallizing surface; bubbles that tend to obliterate the surface and limit its direct contacting to the electroless bath. Accelerating this second metallization step may be performed as follows.
  • the silicone layer on its substrate is removed from the bath and its surface is blown for a few seconds with a hot air jet as produced by a standard air gun.
  • the jet cleans up the surface and heats up the metal deposit.
  • the layer is then returned to the bath for a period of 5 min to 10 min before being removed again from the bath, re-blown as before and re-immersed in the bath.
  • the process is repeated regularly (and automated eventually) at 5 min to 10 min intervals until the necessary metal thickness has been attained. With this transient heat procedure, time reduction from 2 h to 3 h to 30 min in the process of Pt- metallizing is substantial and the metal deposit may attain a large thickness that may not be accessible without it.
  • Figure 1 depicts a cross-sectional view of a substrate (1).
  • the substrate (1) is a rigid supporting substrate preferably made of glass, molded silicone, ceramic, semiconductor, at least one metal, or at least one metal alloy.
  • Figure 2 depicts a cross-sectional view of the substrate (1) and a first silicone layer (3 a) after curing.
  • the silicone is preferably applied and distributed by spun coating. Then the sample is heat treated to perform curing of the silicone layer (3a).
  • the silicone layer (3a) is about 20 ⁇ m thick.
  • Figure 3 depicts a cross-sectional view of a substrate (1) and a cured first silicone layer (3 a) after laser treatment.
  • the desired emission may be obtained from an excimer laser source emitting during about 10 ns, at a wavelength of about 248 nm which corresponds to photon energy of 5 eV.
  • the threshold energy density may be obtained by focalizing the laser beam on the irradiated surface and is usually at about 0.5 J/cm 2 .
  • the laser beam cuts traces (4) with a preferable trace width of 5 ⁇ m to 15 ⁇ m.
  • Figure 4 depicts a cross-sectional view of a substrate (1) and a cured first silicone layer (3 a) after metallization of the engraved traces (4) whereby Pt traces (5) are obtained.
  • the silicone layer (3 a) is immersed in a Pt autocatalytic bath whereby deposition of Pt is induced on.
  • Figure 5 depicts a cross-sectional view of a substrate (1) and a cured first silicone layer (3 a) after disposing a second silicone layer (3 b) on top of the first silicone layer (3 a) and the Pt traces (5).
  • the second silicone layer (3b) is of 15 ⁇ m to 20 ⁇ m thick.
  • the used silicones have a formulation that contains generally a variable amount of silica foam additive that serves to strengthen the polymeric structure in various ways. It also favors the electroless-metallization process and improves substantially the mechanical behavior of metallized silicone.
  • the final silicone cover can remain un-metallized and serves solely to the purpose of protecting from ambient of the underlying metallized layers. That silicone cover may be formed with a silicone that is different from the one silicone that has been used for the other underlying layers. In particular, it may not contain silica at all and may then be more readily spun, even to very small layer thickness. Therefore, the silicone cover can be formed with a silica-free silicone that is spun onto the multi-layered metallized silicone before curing as above.
  • Figure 6 depicts a cross-sectional view of a substrate (1) and a cured first silicone layer (3a) and Pt traces (5) after curing the second silicone layer (3b).
  • Figure 7 depicts a spherical view of a substrate (1) and a cured silicone polymer layer (3) with one embedded series of Pt traces (5).
  • the first silicone layer (3a) and the second silicone layer (3b) become one silicone layer (3) after curing as shown in figure 6.
  • Figure 8 depicts a spherical view of a cured silicone polymer layer (3) with one embedded series of Pt traces (5) after a cut out of the silicone as performed by laser irradiating at about 193 nm to enable connection of the Pt traces (5) to external electrodes or other devices.
  • Figure 9 depicts an enlarged top view of a flexible circuit electrode array (6) which is a part of the body (10) as shown for example in figures 10 and 11.
  • the preferred positions of the electrodes (7) and the preferred wiring by the trace metal (5) both embedded in the polymer (3) are shown in figure 9.
  • the trace metal contains preferably platinum.
  • the electrodes (7) contain preferably platinum.
  • the preferred flexible electrode array (6) of the present invention comprises silicone polymer (3) containing SiO 2 in which platinum trace metals (5) are embedded and which contains platinum electrodes (7).
  • Figures 10 and 11 depict a body (10) containing the flexible circuit electrode array (6), a flexible circuit cable (12) and the interconnection pad (14). At one end of the flexible circuit cable (12) is an interconnection pad (14).
  • the flexible circuit electrode array (6) At the other end of the flexible circuit cable (12) is the flexible circuit electrode array (6). Further, an attachment point (16) is provided near the flexible circuit electrode array (6). A retina tack (not shown) is placed through the attachment point (16) to hold the flexible circuit electrode array (6) to the retina. A stress relief (18) is provided surrounding the attachment point (16). The stress relief (18) may be made of a softer polymer than the flexible circuit, or it may include cutouts or thinning of the polymer to reduce the stress transmitted from the retina tack to the flexible circuit electrode array (6).
  • Figure 10 depicts that the flexible circuit cable (12) is formed in a dog led pattern so then when it is folded at fold (20) it effectively forms a straight flexible circuit cable (12) with a narrower portion at the fold (20) for passing through the scleratomy.
  • Figure 11 depicts the flexible circuit electrode array (6) after the flexible circuit cable (12) is folded.
  • Figure 12 depicts a flow chart which is an example for the manufacturing of a flexible electrode array containing a polymer comprising silicone, SiO 2 , and platinum traces and electrodes.
  • the present invention provides a multi-layer metallized silicone.
  • the second and last layer is laser irradiated and metallized as previously.
  • the new metallized traces in that second layer remain within the engraved part of that layer down to 5 ⁇ m to 10 ⁇ m.
  • the traces are still separated from the underlying metallized traces in the first layer by some 10 ⁇ m. Any undesired interconnects in between the two sets of metallized traces are avoided.
  • the two-layer silicone structure is then covered with a final, cured virgin silicone layer.
  • a silicone-encapsulated 3-D structure that contains two sets of independent metallized Pt-traces is obtained.
  • the present invention provides interconnection in multi-layered silicone 3-D structure.
  • irradiation with the same excimer laser source working at 248nm is performed onto the cover at an area that overlaps a section of an underlying Pt-trace.
  • Decomposition of silicone is performed at the site and maintained upon repeated pulsed- irradiation.
  • the procedure drives silicone out of that area and cuts the layer until reaching the underlying Pt-trace to open a window to the embedded Pt-circuit.
  • the window is filled with Pt after metallization down to the underlying trace.
  • a new laser-irradiation of that second silicone layer that is now equipped with the metallized window is performed along a path that crosses the metallized window.
  • a further immersion in the autocatalytic bath results in the metallization of the path while bringing additional metal to the window. In that way, a direct interconnect is obtained between the upper lying trace in the second silicone layer and the lower lying trace in the first one.
  • silicones have a formulation that contains generally a variable amount of fumed silica (silica foam) that serves to strengthen the polymeric structure in various ways. It also favors the electroless-metallization process and improves substantially the mechanical behavior of metallized silicone.
  • the final silicone cover remains un-metallized and serves solely for the purpose of protecting the underlying metallized layers from ambient. That silicone cover may be formed with a silicone that is different from the one silicone that has been used for the other underlying layers. In particular, it may not contain silica foam at all and may then be more readily applied even to very small layer thickness.
  • a silicone cover of 15 ⁇ m to 20 ⁇ m is formed on the last metallized silicone layer. That silicone cover is formed with a silica foam free silicone that is spun onto the multi-layered metallized silicone before curing as above.
  • the present invention provides silicone with a spherical geometry. The cured silicone surface with spherical geometry is scanned with an excimer laser and followed by a subsequent platinum-metallization of the resulting laser-produced trace. A second silicone layer is further spun on this metallized silicone surface and cured in an oven. That silicone structure is not planar but curved.
  • the present invention provides metallized spherical, silicone molded substrates. Silicone rubber is injected in an hemispherical moid.
  • the present invention provides the metallizing of an expanded silicone layer for enhanced metal imbedding.
  • a silicone is applied on a glass cylinder.
  • the silicone layer on the glass cylinder is brought in an electro less Pt bath for metallization of the traces.
  • the metallized silicone layer is detached from the glass cylinder and recovers its original planar geometry.
  • the expanded Pt-traces contract enclosing the metal parts into silicone and providing an enhanced integration of these traces into the silicone layer.
  • the present invention relates to an improved process for positive metallization of a polymer surface.
  • a non-organic powder is dispersed in any given polymer, for example polyamide.
  • the non-organic powder is for example at least one oxide of antimony, aluminum, iron, zinc or tin.
  • the oxide grains have variable grain sizes, preferably smaller than 50 ⁇ m.
  • the concentration of the oxide grains in the polymer exceeds about 1 VoI.- % or 1 wt.-%.
  • the surface of the polymer material or composite is irradiated with the light beam emitted by a laser.
  • the light is emitted preferably in the ultraviolet area, during a very short duration or pulse and repeated if necessary at regular time intervals.
  • the pulsed emission has preferably high energy, for example, between 0.05 J and 0.2 J. It contains a very large number of photons. It may also operate at a wavelength below or equal to 350 nm which corresponds to photon energy approximately equal to or larger than 3.5 eV.
  • the desired emission may be obtained from an excimer laser source emitting during 20 nanoseconds, at a wavelength of 248 nm which corresponds to photon energy of 5 eV.
  • the threshold energy density may be obtained by focalizing the laser beam on the irradiated surface and is usually at about 0.5 J/cm 2 .
  • the process of radiation has two effects if the above given energy density, threshold energy, and the value which depends on the nature and concentration of the oxide grains in the composite are applied: a) the base material itself, for example the polymer, undergoes a superficial ablation of some 0.2 micrometer per pulse; and b) depending on the choice of the incorporated granular substance, the same radiation creates at the surface of the oxide grains a high concentration of polarized defects.
  • the defects are a consequence of breaking some of the interatomic bonds at the surface of the surface grains. They result from the combined actions of the electronic excitations which take place within these bonds following the absorption of the laser photons by the grains themselves.
  • the actual concentration of such defects at the surface of the oxide grains is proportional to the laser energy density as resulting from the laser beam focalization at the surface of the composite.
  • the laser- treated material is directly immersed in an autocatalytic bath containing metal ions for example Pt .
  • the metal contained in the bath is then selectively driven to deposit on those sections of the polymer surface which have been previously irradiated by the laser beam and which contain the polarized defects produced by the same irradiation.
  • the present invention does not have to apply any substances containing Palladium to control the Pt 2+ polymer surface metallization due to the defects on the oxide grains.
  • the metallization is directly induced by the superficial defects which are laser-created on the oxide grains present at the composite surface.
  • the duration of the incubation time decreases when the laser energy density increases.
  • the thickness of the Pt deposition of 20 or 5 micrometers per hour in a Pt bath after the incubation is approximately proportional to the actual immersion duration.
  • the interface between the composite and the metal film is rough as a result from the partial ablation of the polymer surface.
  • the interstitial coupling, either by covalent or ionic strong bonds, of the metal ions from the autocatalytic bath onto the superficial grain defects of that roughened surface is selective and strong.
  • the adhesion of the metal deposition onto the polymer is remarkably high.
  • the adhesion of the metal film onto the polymer surface is performed by the superficially metallized oxide grains which are present at the composite surface.
  • the resulting metal adhesion attains then some 10 MPa.
  • the adhesion of the metal film to the polymer surface may be further increased by letting the metal diffusing towards the inner part of the polymer.
  • This step can be performed by selectively heating the metal film during a short period of time for example in a microwave oven. During that period, the polymer and the other non-metallic components of the complex formed by the polymer and the metal film are not affected by the waves emitted in the oven and, therefore do not heat. The emitted waves selectively heat the metal which may then diffuse in part into the polymer.
  • the modifications which are produced at the polymer surface by the ultraviolet light beam are restricted to those areas which have been irradiated.
  • the precise definition of the limits to those areas is further proportioned to the actual wavelength which is preferably chosen to be lesser than 350 nm.
  • the surface sensitivity to the laser radiation depends for every polymer formulation on the incident laser energy density.
  • metallization is at first restricted to the actual surface of the oxide grains which emerge from the composite. Then, metallization proceeds at random from those grain sites and covers progressively the whole of the laser processed surface area of the composite.
  • the incubation time measures the period of time which is necessary to form a continuous metal film on the composite surface. After that time, the metal deposition, which is usually 20 micrometers per hour for Ni, may develop perpendicularly to the surface in a most efficient manner.
  • the actual thickness of the metal film increases homogeneously all over the laser processed polymer surface whatever the polymer formulation and the initial laser processing is applied.
  • the laser energy density which is utilized for irradiation can be very for a given polymer.
  • the areas which are irradiated at high energy density have an incubation time at the time of immersion in the autocatalytic bath of some 10 minutes.
  • the areas which are irradiated at lower energy density have an incubation time of about 50 minutes.
  • the process of the present invention allows producing metal films with varied thicknesses on the same polymer surface during one single immersion of the irradiated polymer in an autocatalytic bath.
  • the preferred irradiation source according to this invention is an excimer laser.
  • the preferred excimer laser performs engraving at 248 nm with partial decomposition and allows metallization. In comparison engraving below 200 nm performs full ablation but no metallization can follow after the ablation.
  • the laser pulse duration is in the range of Ins to 40ns by steady or scanning irradiation.
  • the preferred metallization includes the following steps a) PMMA coating prior irradiation b) standard electroless process with platinum salt c) multi-bath procedure at 50 0 C d) intercalated transient heat treatment e) dissolving PMMA after metallization
  • the overall process of metallizing silicone involves the following preferred process steps.
  • a silicone layer is spun on a clean glass plate and cured in an oven.
  • the layer has a near constant thickness at 40 ⁇ m across the glass substrate.
  • This layer is then scanned with a focused 248 nm excimer laser beam working at a sufficient fluence that allows partial decomposition of the silicone material down to some 10 ⁇ m - 15 ⁇ m into the layer.
  • the laser processed silicone layer, on its glass substrate, is further immerged in an electroless bath containing Pt ions. Subsequently, the latter ions condense solely on the laser-processed areas of the silicone layer where they contribute to form metallized deposits that precisely decorate the laser-drawn areas and remain embedded in the silicone layer without touching the glass substrate underneath.
  • a glass plate is coated on one of its faces with a anti adherent layer (2) like CaF 2 or MgF 2 film as shown in Figures 13 and 14.
  • a silicone layer is then spun on the coated face of the glass plate and form a 10 ⁇ m - 30 ⁇ m thick layer. That layer is cured in oven before being further scanned with a focused 248nm excimer laser beam.
  • the laser beam induces partial decomposition of the silicone material and engraves it to 10 ⁇ m - 15 ⁇ m depth.
  • Immersion in a Pt autocatalytic bath induces deposition of Pt on these engraved traces as in Example 1 above.
  • the metallized silicone layer is further pulled from the MgF 2 coated glass plate and made free as shown in Figs. 13 - 20.
  • the second and last layer is laser irradiated and metallized as previously.
  • the new metallized traces in that second layer remain within the engraved part of that layer down to approx. 5 ⁇ m - 15 ⁇ m, i.e. still separated from the underlying metallized traces in the first layer by some 5 ⁇ m - 15 ⁇ m and, thus, avoiding eventual and undesired interconnects in between the two sets of metallized traces.
  • the 2-layer silicone structure is then covered with a final, cured virgin silicone layer.
  • the resulting 3-layer structure is further pulled from the MgF 2 coated glass substrate, materializing a silicone- encapsulated 3-D structure that contains two sets of independent metallized Pt-traces as shown in Figs. 24 - 27.
  • a first silicone layer is spun on a MgF 2 covered glass substrate.
  • the outer surface of that first layer is further excimer laser processed and Pt-metallized.
  • a second silicone layer is spun on the metallized silicone surface to form a cover to the first layer.
  • irradiation with the same excimer laser source working at 248nm is performed onto the cover at an area that overlaps a section of an underlying Pt-trace.
  • Decomposition of silicone is performed at the site and maintained upon repeated pulsed- irradiation. The procedure drives silicone out of that area and bores the layer until reaching the underlying Pt-trace.
  • the silicone structure on its glass substrate is immersed in a Pt-autocatalytic bath that drives the metallization into the window, down to the underlying trace and ultimately fills the window space with Pt.
  • a new laser- irradiation of that second silicone layer that is now equipped with the metallized window is performed along a path that crosses the metallized window.
  • a further immersion in the autocatalytic bath results in the metallization of the path while bringing additional metal to the window. In that way, a direct interconnect is obtained between the upper lying trace in the second silicone layer and the lower lying trace in the first one.
  • the excimer laser source is here operated at 193 nm, 6.2 eV photon energy, when opening the windows to the second silicone layer.
  • full decomposition of silicone is achieved in contrast with the partial decomposition resulting from the 248 nm irradiation.
  • decomposition and emission of matter is i) far more efficient (i.e. rapid) than at 248 nm and ii) leaves a clean and smooth opening down to the underlying trace.
  • silicones have a formulation that contains generally a variable amount of silica foam additive that serves to strengthen the polymeric structure in various ways. It also favors the electroless-metallization process and improves substantially the mechanical behavior of metallized silicone.
  • the final silicone cover remains un-metallized and serve solely the purpose of protecting from ambient the underlying metallized layers. That silicone cover may be formed with a silicone that is different from the one silicone that has been used for the other underlying layers. In particular, it may not contain silica at all and may then be more readily spun, even to very small layer thickness Therefore, following from Examples 3 and 4 above, a silicone cover of 20 ⁇ m is formed on the last metallized silicone layer. That silicone cover is formed with a silica-free silicone that is spun onto the multi-layered metallized silicone before curing as above.
  • a plano-convex lens is coated on its convex surface with a MgF 2 film. Then, the lens is positioned and fixed solidly on a turntable having i) its planar, uncoated surface directly in contact with the turntable surface and ii) its axis precisely along the turntable rotation axis. A given amount of silicone is then positioned about the center of the convex surface of the lens and the turntable let to rotate.
  • Silicone rubber is injected in an hemispherical mold. After un-molding the resulting silicone piece and like in all preceding examples, a laser beam is scanned on its molded hemispherical surface and the resulting laser-processed traces brought to further Pt-metallize. Similarly to Example 8, a silicone layer is further spun on the hemispherical metallized silicone surface.
  • Silicone is spun on a planar, MgF 2 -coated glass substrate, oven-cured and pealed off its substrate.
  • the pealed-off layer is then mounted to adhere gently but uniformly onto the surface of a MgF 2 -coated glass cylinder, in such a way that the actual cylinder diameter does allow the silicone layer to run all around the cylinder without overlapping on itself.
  • the silicone-covered cylinder is then mounted on a motorized rotation axel and that motorized axel positioned on an x-y table that may move the motorized axel in a plan parallel to the axel axis.
  • Laser processing the silicone layer is further performed with the laser axis being perpendicular to the cylinder axis while displacing it along with the x-y table.
  • the silicone layer on its glass cylinder is brought in an electroless Pt bath for metallization of the traces. This being done, the metallized silicone layer is detached from the glass cylinder and recovers its original planar geometry. In so doing, the once- expanded Pt-traces (at time of their production) contract, enclosing the metal parts into silicone and providing an enhanced integration of these traces into the silicone layer. Accelerating Pt-Metallization of Silicone
  • the electroless Pt-metallization proceeds via forming a thin so-called black Pt film and then goes on a second step of Pt-deposit that thickens the metal layer. That second step is extremely slow being impaired in particular with the formation of H-bubbles on a quite uneven metallizing surface, bubbles that tend to obliterate the surface and limit its direct contacting to the electroless bath. Accelerating this second metallization step is performed as follows.
  • the silicone layer on its substrate is pulled out of the bath and its surface is blown for a few seconds with a hot air jet as produced by a standard air-gun.
  • the jet cleans up the surface and heats up the metal deposit.
  • the layer is then returned to the bath for a period of 5 to 10 minutes before being pulled again from the bath, re-blown as before and re-immersed in the bath.
  • the process is repeated regularly (and automated eventually) at 5-10 minutes intervals until the necessary metal thickness has been attained. With this transient heat procedure, time reduction in the process of Pt-metallizing is substantial (from 2-3 hours to 30 minutes) and the metal deposit may attain a large thickness that may not be accessible without it.
  • Figs. 21 to 23 show a polymer layer preferably silicone layer (3) containing metal traces
  • Fig. 21 shows the polymer layer (3) after being removed from the substrate (1).
  • Fig. 22 shows the polymer layer (3) shaped as a circle.
  • Fig. 23 shows the polymer layer (3) after applying openings to the metal traces (5).
  • Figs. 28 to 30 and Figs. 31 to 33 show similar to Figs. 21 to 23 a polymer layer lift off a substrate (Figs. 28 and 31), shaped as a circle (Figs. 29 and 32) and after applying openings to the traces (Figs. 30 and 33).
  • Figs 28 to 30 show two layers of metal traces (5) and (5A) stacked parallelly in the polymer layer (3).
  • Figs. 31 to 33 show metal traces (5) and (5B) stacked perpendicularly in the polymer layer (5).
  • Figs. 34A to 34G show the sequence for producing an interconnection between traces crossing each other like traces of platinum (5) and (5B).
  • Fig. 34A depicts a perspective view of a polymer layer (3A) and (3B) layer with one embedded metal trace (5) in (3A).
  • Fig. 34B depicts a perspective view of a polymer layer (3 A and (3B) after laser drilling through the upper font (3B) of the layer to form an opening (6) down to the metal tract (5).
  • Fig. 34C depicts a perspective view of a polymer layer (3A) and (3B) after partial metal plating (7) of the laser cut opening (6).
  • Fig. 34D depicts a perspective view of a polymer layer after laser processing traces (8) into the upper layer (3B) to overlap the opening (6).
  • Fig. 34E depicts a perspective view of a polymer layer after metallizing (5B) of the tract (8) and further metallizing (7) the opening (6).
  • Fig. 34F depicts a perspective view of a polymer layer after disposing a second polymer (3C) layer on top of it and form a bi-layer.
  • Fig. 34G depicts a perspective view of a polymer layer (3 A-3C) after removing the layer from the rigid substrate (1).
  • the platinum metallization of silicone is a process of several steps which are explained below in Example 1 and Example 2.
  • a silicone sheet (NuSiI MED 4950 from NUSIL TECHNOLOGY LLC 5 Carpinteria, California) having a thickness of 80 ⁇ m was spray-coated with a 2 ⁇ m thick PMMA layer.
  • the silicone sheet was immersed for five minutes in an ultrasonic bath at 40 °C, containing a low acidity 1.5% HCl solution.
  • the silicone sheet was than two times rinsed with distilled water.
  • the silicone sheet was Pt-metallized for 6 hours in two successive platinization baths.
  • the silicone sheet was immersed in 100 ml plating solution containing 0.6 g of potassium (II) tetra-nitro-platinate, 20 ml of ammonium hydroxide 28 %, and 0.2 g of complexing agent.
  • the silicone sheet was then rinsed with distilled water.
  • Silicone sheet was mounted on a glass cylinder.
  • the glass with the silicone sheet was immersed in the same metallizing solution being in a thermo stated vessel for 3 hours to 5 hours. From time to time (e.g. every 10 minutes), H 2 bubbles are eliminated from sheeting by vibrating the cylinder or by heat flashing the silicone sheet.
  • the silicone sheet was rinsed in distilled water at the end of the procedure.
  • PMMA coating allowed removal of irradiation residues that were generated during irradiation and could sediment laterally to the irradiated areas. It should be operated at constant pressure of the PMMA suspension, scanning the sheeting at fixed distance and constant speed, and in a clean environment (either grey room or glove box under Argon atmosphere).
  • Step-two glass cylinder and thermo stated vessel both were specifically designed for this purpose.
  • the present invention provides the metallizing of an expanded silicone layer for enhanced metal imbedding.
  • a silicone is applied on a glass cylinder.
  • the silicone layer on the glass cylinder is brought in an electroless Pt bath for metallization of the traces.
  • the metallized silicone layer is detached from the glass cylinder and recovers its original planar geometry.
  • the expanded Pt- traces contract enclosing the metal parts into silicone and providing an enhanced integration of these traces into the silicone layer.
  • a silicone sheet (NuSiI MED 4950 from NUSIL TECHNOLOGY LLC, Carpinteria, California) having a thickness of 80 ⁇ m was spray-coated with a 2 ⁇ m thick PMMA layer.
  • the silicone sheet was immersed for five minutes in an ultrasonic bath at 40 °C, containing a low acidity 1.5% HCl solution.
  • the silicone sheet was than two times rinsed with distilled water.
  • the silicone sheet was Pt-metallized for 6 hours in two successive platinization baths.
  • the silicone sheet was immersed in 100 ml plating solution containing 0.6 g of potassium (II) tetra-nitro-platinate, 20 ml of ammonium hydroxide 28 %, and 0.2 g of complexing agent.
  • the silicone sheet was then rinsed with distilled water.
  • the silicone sheet was immersed in two successive and fresh ultrasonic baths for five minutes each containing CHCl 3 that dissolved the PMMA protection layer.
  • the silicone sheet was two times rinsed for 5 minutes to 10 minutes in ultrasonic distilled water bath and dried.
  • Silicone sheet was mounted on a glass cylinder.
  • the glass with the silicone sheet was immersed in the same metallizing solution being in a thermo stated vessel for 3 hours to 5 hours. From time to time (e.g. every 10 minutes), H 2 bubbles are eliminated from sheeting by vibrating the cylinder or by heat flashing the silicone sheet.
  • the silicone sheet was rinsed in distilled water at the end of the procedure.
  • PMMA coating allowed removal of irradiation residues that were generated during irradiation and could sediment laterally to the irradiated areas. It should be operated at constant pressure of the PMMA suspension, scanning the sheeting at fixed distance and constant speed, and in a clean environment (either grey room or glove box under Argon atmosphere).
  • Step-two glass cylinder and thermo stated vessel both were specifically designed for this purpose.
  • the present invention provides the metallizing of an expanded silicone layer for enhanced metal imbedding.
  • a silicone is applied on a glass cylinder.
  • the silicone layer on the glass cylinder is brought in an electroless Pt bath for metallization of the traces.
  • the metallized silicone layer is detached from the glass cylinder and recovers its original planar geometry.
  • the expanded Pt- traces contract enclosing the metal parts into silicone and providing an enhanced integration of these traces into the silicone layer.
  • the once-expanded Pt-traces at time of their production contract and enclose the metal parts in the silicone providing an enhanced integration of these traces into the silicone layer.

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Abstract

La présente invention concerne un procédé visant à incorporer au moins une couche d’au moins un métal à l’état de trace dans un polymère contenant de la silicone, ledit procédé comprenant les étapes consistant à : a) appliquer un agent anti-adhésif sur un substrat ; b) appliquer une couche polymère sur l’agent anti-adhésif ; c) irradier au moins une zone superficielle dudit polymère à l’aide d’un faisceau lumineux émis par un laser à excimère ; d) immerger ledit polymère irradié dans au moins un bain autocatalytique contenant des ions métalliques d’au moins un métal et métalliser le polymère ; e) traiter thermiquement ledit polymère métallisé ; f) appliquer une couche polymère sur ledit polymère métallisé traité thermiquement ; et g) traiter thermiquement ledit polymère métallisé.
EP06827730A 2005-11-10 2006-11-10 Couche polymere comprenant de la silicone et au moins un metal a l'etat de trace et procede pour la fabriquer Withdrawn EP1971704A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11/270,907 US8771805B2 (en) 2005-11-10 2005-11-10 Polymer layer comprising silicone and at least one metal trace and a process of manufacturing the same
US81168306P 2006-06-07 2006-06-07
PCT/US2006/043863 WO2007058975A2 (fr) 2005-11-10 2006-11-10 Couche polymere comprenant de la silicone et au moins un metal a l’etat de trace et procede pour la fabriquer

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EP1971704A2 true EP1971704A2 (fr) 2008-09-24

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EP06827730A Withdrawn EP1971704A2 (fr) 2005-11-10 2006-11-10 Couche polymere comprenant de la silicone et au moins un metal a l'etat de trace et procede pour la fabriquer

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EP (1) EP1971704A2 (fr)
WO (1) WO2007058975A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007149465A2 (fr) * 2006-06-19 2007-12-27 Second Sight Medical Products, Inc. Électrode à stabilité augmentée et son procédé de fabrication

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
US5108819A (en) * 1990-02-14 1992-04-28 Eli Lilly And Company Thin film electrical component
US5817550A (en) * 1996-03-05 1998-10-06 Regents Of The University Of California Method for formation of thin film transistors on plastic substrates
JP3399434B2 (ja) * 2001-03-02 2003-04-21 オムロン株式会社 高分子成形材のメッキ形成方法と回路形成部品とこの回路形成部品の製造方法
US6596569B1 (en) * 2002-03-15 2003-07-22 Lucent Technologies Inc. Thin film transistors

Non-Patent Citations (1)

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Title
See references of WO2007058975A3 *

Also Published As

Publication number Publication date
WO2007058975A2 (fr) 2007-05-24
WO2007058975A3 (fr) 2008-01-24

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