WO2007038950A1 - Method for generation of metal surface structures and apparatus therefor - Google Patents

Method for generation of metal surface structures and apparatus therefor Download PDF

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Publication number
WO2007038950A1
WO2007038950A1 PCT/EP2005/010486 EP2005010486W WO2007038950A1 WO 2007038950 A1 WO2007038950 A1 WO 2007038950A1 EP 2005010486 W EP2005010486 W EP 2005010486W WO 2007038950 A1 WO2007038950 A1 WO 2007038950A1
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WO
WIPO (PCT)
Prior art keywords
substrate
metal particles
metal
coating
patterns
Prior art date
Application number
PCT/EP2005/010486
Other languages
French (fr)
Inventor
Jolke Perelaer
Berend Jan De Gans
Ulrich S. Schubert
Original Assignee
Stichting Dutch Polymer Institute
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
Application filed by Stichting Dutch Polymer Institute filed Critical Stichting Dutch Polymer Institute
Priority to PCT/EP2005/010486 priority Critical patent/WO2007038950A1/en
Priority to EP06805928A priority patent/EP1932403A1/en
Priority to US11/992,259 priority patent/US20090191358A1/en
Priority to PCT/EP2006/009437 priority patent/WO2007039227A1/en
Priority to JP2008532675A priority patent/JP2009510747A/en
Publication of WO2007038950A1 publication Critical patent/WO2007038950A1/en

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Classifications

    • 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
    • H05K3/12—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 thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • 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
    • H05K3/12—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 thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1241—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 thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
    • H05K3/125—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 thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
    • 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
    • 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
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
    • 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
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/102—Using microwaves, e.g. for curing ink patterns or adhesive
    • 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
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating

Definitions

  • This invention relates to the manufacture of surface metal patterns by a simple and efficient method and to an apparatus adapted to carry out this method.
  • Printing techniques such as ink-jet printing, are interesting alternatives for the production of electronic and other structures. Printing has the advantage of low cost, ease of processing, potential for mass production and flexibility. A typical application is ink-jet printing of conductive tracks. Some different strategies were adopted to print such structures. In the scientific literature, the use of inks based on an
  • the precursor is reduced to metal via a post-printing thermal annealing step.
  • the ink used consists of a dispersion of noble metal nanoparticles, usually silver (S. Magdassi et al. in Mater. 2003, 15, 2208, or A. Kamyshny et al. in Macromol. Rapid Commun., 2005, 26, 281-8), though the use of gold nanoparticles is also documented in the scientific literature (4) D. Huang et al. in Electrochem. Soc, 2003, 150, G412).
  • the printed structures need a sintering step to become conductive.
  • the use of nanoparticles reduces the sintering temperature due to the high surface-to-volume ratio, as disclosed in WO-A-2004/005,413.
  • WO-A-00/120,519 discloses preparations containing fine-particulate inorganic particles for ink-jet coating and for generating structured surfaces which are transformed via sintering in reducing atmosphere into electrically conductive surfaces. No ink-jet printing of metallic particles and no microwave sintering of the generated surface patterns is described.
  • WO-A-97/138,810 discloses a method of manufacturing a sintered structure on a substrate by ink-jet printing of surface structure and sintering by laser. By repeating of this method a layer-by-layer structure is generated. Printing of metal nanoparticles and sintering by microwave radiation are not disclosed.
  • US-A-6,508,550 and US-A-6,425,663 describe microwave energy ink drying methods but no printing of metal nanoparticles or sintering by microwave radiation.
  • US-A-2003/10185971 discloses methods for ink-jet printing circuitry including different printing methods for pattern generation including use of metal nanoparticles to form a conductive path. Furthermore, different heating methods are disclosed but no heating by microwave radiation.
  • thermoplastic polymers or paper cannot be used as substrate, as these cannot withstand high temperatures (Kevin Cheng et al. in Macromol. Rapid Commun., 2005, 36, 247-64).
  • Microwave heating of materials is fundamentally different from conventional radiation-conduction-convection heating.
  • microwaves are restricted to materials that absorb microwave radiation, i.e. have a non-zero dielectric loss-factor e" within the frequency range of interest.
  • Microwave sintering of metaloxydes i.e. ceramics
  • Microwave sintering of metals is generally considered as unfeasible, as metals strongly reflect rather adsorb microwaves. Nevertheless, microwave sintering of metals was disclosed in US-A-6, 183,689.
  • the printed structure When using as substrate a material that absorbs microwaves to a lesser extent than the printed structure, i.e. a material with a lower dielectric loss-factor e" within the range of frequencies used, the printed structure is sintered without affecting the substrate.
  • Mircrowave radiation thus allows using substrate materials that are not thermally stable, i.e. would not be able to withstand the high temperatures required for convertional radiation-conduction-convection heating.
  • inkjet inks based on molecules bearing functional groups that polymerise under the influence of microwave radiation without thermally affecting the substrate was disclosed in US-A- 2004/179,076. This patent document discloses novel microwave curable inks for ink-jet printing but neither discloses printing of metal nanoparticles nor their sintering by microwave radiation.
  • the present invention generally relates to a process for the fabrication of metallic structures or metallic patterns onto a substrate.
  • the present invention relates to a process for generating metallic surface patterns on a substrate surface comprising the steps: i) coating a surface of a substrate with a predetermined pattern of metal particles by applying a dispersion containing said metal particles in a liquid onto said surface, ii) optionally drying said coated substrate to cause said liquid to evaporate, and iii) heating said substrate containing a pattern of said metal particles on said surface by means of microwave radiation to effect heating of said metal particles to form conductive metal patterns on said surface.
  • each substrate can be used as long as this absorbs microwave radiation to a smaller extent as the metal particles applied to the surface of said substrate.
  • the selection of substrate and metal is performed to result in a lower dielectric loss factor e" of the material forming the substrate as compared to the dielectric loss factor e" of the metal forming the surface pattern.
  • the dielectric loss factor e" of the substrate is lower than 50 %, preferably lower than
  • the substrate should absorb microwave radiation to a. lesser extent than the metal that constitutes the printed structure, i.e. within the frequency range of interest the dielectric loss factor e" of the metal that constitutes the printed structure should be considerably higher than the dielectric loss factor e" of the substrate material.
  • a large variety of substrates can be chosen for the method of this invention.
  • Non limiting examples are polymers (thermoplastic and duroplastic polymers including elastomers); inorganic materials, such as ceramic materials; semi-conducting substrates, such as silicon or gallium-arsenide, fibrous substrates containing natural and/or man-made fibers, such as paper, textile sheets including non-wovens; film and sheet materials made from polymers and or natural materials, such as leather, wood or thermoplastic sheet or bulk materials including composites, containing said sheet or bulk materials.
  • polymers thermoplastic and duroplastic polymers including elastomers
  • inorganic materials such as ceramic materials
  • semi-conducting substrates such as silicon or gallium-arsenide, fibrous substrates containing natural and/or man-made fibers, such as paper, textile sheets including non-wovens
  • film and sheet materials made from polymers and or natural materials, such as leather, wood or thermoplastic sheet or bulk materials including composites, containing said sheet or bulk materials.
  • Suitable substrates can possess a large variety of properties.
  • they can be transparent or non-transparent, or they can be crystalline or non-crystalline or they can contain adjuvants, such as pigments, antistatic agents, fillers, reinforcing materials, lubricants, processing aids and heat and/or light stabilizers.
  • each metal including metal alloys can be chosen.
  • Non limiting examples are noble metals, metals of the platinum group.
  • gold and especially preferred silver or silver alloys are used. Mixtures of different metals can also be used.
  • the metals are applied in the form of particles to the surface.
  • the particle form helps to develop predetermined surface patterns.
  • Typical mean particle diameters are in a range between 1 nm and 10O ⁇ m, preferably 1 nm - 1 ⁇ m, very preferred 1 nm - 100 nm and especially preferred 1 nm - 50 nm.
  • the mean particle diameter is determined by transmission electron microscope (TEM).
  • Very preferably metal nanoparticles are used, which allow the formation of conducting metal surface patterns with minimum amount of microwave energy.
  • the metal particles absorb microwave radiation, i.e. electromagnetic radiation with wavelengths ranging from 1 mm to 1 m in free space corresponding to a frequency between approximately 300 GHz to 300 MHz, respectively. It has been found that the use of microwave processing typically reduces heating time by a factor of 10 or more as compared to conventional heating methods.
  • the surface of the substrate is coated with the metal particles by applying a dispersion containing said metal particles in a liquid onto said surface.
  • Predetermined surface patterns can be layers covering the whole surface or other forms of surface coverage.
  • Preferably surface patterns cover portions of the surface, for example in the form of tracks and/or of isolated spots of metal particles.
  • Several surfaces of the substrate can be coated. For example two surfaces of a sheet material can be coated in the form of tracks which are optionally connected via holes going through the substrate and containing conductive material.
  • coating methods are known in the art of applying surface coatings, such as curtain coating, spin-coating or coating by means of doctor blade.
  • printing methods methods are used, such as offset printing or screen printing and very preferred ink-jet printing.
  • the coating material that forms the patterns on said surface(s) is present as a dispersion of metal particles in a carrier material that renders the coating material pasty or preferably fluid.
  • the pasty coating material is hereafter referred to as
  • the fluid coating material is hereafter referred to as "ink”.
  • the paste of ink is applied to the surface of the substrate to form a pattern after drying by means of a printing technique, more particularty ink-jet printing.
  • the carrier material When applying the paste or ink to the surface of the substrate the carrier material can be removed at the same time, for example by heating the substrate and by chosing a carrier material that evaporates or decomposes at the substrate temperature.
  • the carrier material can be evaporated or decomposed after the formation of the surface pattern in a separate heat treatment step or the carrier material can be evaporated or decomposed during the tretment with microwave radiation.
  • the equipment for performing the method of this invention can be chosen from known devices. Coating devices, heat treatment devices and microwave generators are known in the art and commercially available.
  • the processed substrates containing conductive surface patterns of metal can be compiled to form a layered product with several substrates possessing conductive patterns in the interior and on the surface.
  • the layered products can contain layers of other materials besides the processed substrates containing conductive surface patterns of metal.
  • the invention also relates to a device for performing the above-defined method comprising the combination of
  • the coating device is an ink-jet printer.
  • the invention relates to the use of microwave radiation for the generation of conductive metal patterns on a substrate surface.
  • the process for generating metallic surface patterns on a substrate surface can be used, for example, for the production of printed wiring boards or of integrated circuits, for the production of decorative sheets or for the production of of data recording or of data storing media, for the production of print boards, for the production of radio frequency identification devices (RFID devices) or for the production of electrical devices, like heating elements, resistors, coils or antennas.
  • RFID devices radio frequency identification devices
  • NanopasteTM A dispersion of silver nanoparticles in tetradecane known as NanopasteTM was purchased from Harima Chemical Ltd.
  • a Microdrop Autodrop inkjet printer equipped with a MD-K-140 dispenser system was filled with the aforementioned dispersion.
  • An array of parallel lines with a typical length of 1 cm and a spacing of 5 mm in between was then printed onto the substrate by deposition of droplets with a spacing of 100 ⁇ m.
  • the substrate was heated during printing at 100 0 C.
  • the polyimide foil with printed structure thereon was then sintered during three minutes by microwave radiation using a monomode microwave oven operating at 2.45 GHz and a power of 300 W.
  • the resistance per unit distance of the sintered lines was 4-6 ⁇ *cm '1 .
  • the resistivity of the material as calculated from the resistance and the cross-sectional area of a line is 30 * 10 "8 ⁇ *m.

Abstract

Disclosed is a method for generating conductive surface patterns on a substrate by coating the substrate with metal particles and heating the coated substrate by means of microwave radiation. The process is easy to implement and can be used to generate metal pattern at low cost.

Description

Disclosure
Method for generation of metal surface structures and apparatus therefor
This invention relates to the manufacture of surface metal patterns by a simple and efficient method and to an apparatus adapted to carry out this method.
Printing techniques, such as ink-jet printing, are interesting alternatives for the production of electronic and other structures. Printing has the advantage of low cost, ease of processing, potential for mass production and flexibility. A typical application is ink-jet printing of conductive tracks. Some different strategies were adopted to print such structures. In the scientific literature, the use of inks based on an
(in)organic silver or copper precursor is described (A. L. Dearden et al. in Macromol. Rapid Commun. 2005, 26, 315-8 or Z. Liu et al. in Thin Solid Films 2005, 478, 275-9 or J. B. Szczech et al. in IEEE Trans, on Electronics Packaging Manuf., 2002, 25, 26-33 or C. M. Hong et al. in IEEE Electron Device Letters, 2000, 21 , 384-6 or T. Cuk et al. in Appl. Phys. Lett. 2000, 77, 2063-5).
The precursor is reduced to metal via a post-printing thermal annealing step. In most cases, however, the ink used consists of a dispersion of noble metal nanoparticles, usually silver (S. Magdassi et al. in Mater. 2003, 15, 2208, or A. Kamyshny et al. in Macromol. Rapid Commun., 2005, 26, 281-8), though the use of gold nanoparticles is also documented in the scientific literature (4) D. Huang et al. in Electrochem. Soc, 2003, 150, G412). The printed structures need a sintering step to become conductive. The use of nanoparticles reduces the sintering temperature due to the high surface-to-volume ratio, as disclosed in WO-A-2004/005,413.
In the past two different techniques were used to sinter printed nanoparticle structures, conventional radiation-conduction-convection heating being the most common method. To obtain sufficient conductivity temperatures required are typically above 200° C, whereas the sintering times are typically 60 minutes or more. The long sintering times required imply that the technique is not feasible for fast industrial production.
Examples for use of ink-jet printing for generating surface patterns are given in several patent documents.
WO-A-00/120,519 discloses preparations containing fine-particulate inorganic particles for ink-jet coating and for generating structured surfaces which are transformed via sintering in reducing atmosphere into electrically conductive surfaces. No ink-jet printing of metallic particles and no microwave sintering of the generated surface patterns is described.
WO-A-97/138,810 discloses a method of manufacturing a sintered structure on a substrate by ink-jet printing of surface structure and sintering by laser. By repeating of this method a layer-by-layer structure is generated. Printing of metal nanoparticles and sintering by microwave radiation are not disclosed.
US-A-6,508,550 and US-A-6,425,663 describe microwave energy ink drying methods but no printing of metal nanoparticles or sintering by microwave radiation.
US-A-2003/10185971 discloses methods for ink-jet printing circuitry including different printing methods for pattern generation including use of metal nanoparticles to form a conductive path. Furthermore, different heating methods are disclosed but no heating by microwave radiation.
With heating methods disclosed in the prior art many potentially interesting materials, such as thermoplastic polymers or paper cannot be used as substrate, as these cannot withstand high temperatures (Kevin Cheng et al. in Macromol. Rapid Commun., 2005, 36, 247-64).
As an alternative a laser sintering method was developed (Nicole R. Bieri et al. in Superlattices and Microstructures 2004, 35., 437-44; or Tae Y. Clioi et al. in Appl. Phys. Lett. 2004, 85, 13-5; or Jaewon Chung et al. in Appl. Phys. Lett., 2004, 84, 801-3; or Nicole R. Bieri et al. in Appl. Phys. Lett., 2003, 82, 3529-31 ). The laser follows the conductive tracks and sinters these selectively, without affecting the substrate. This method however, is costly and complex from a technical point of view.
Thus, it is an objective of the present invention to provide a fast, simple and thus cost-efficient technique that allows sintering or melting of printed structures by selective heating of the printed structure only.
Microwave heating of materials is fundamentally different from conventional radiation-conduction-convection heating.
The use of microwaves is restricted to materials that absorb microwave radiation, i.e. have a non-zero dielectric loss-factor e" within the frequency range of interest.
Microwave sintering of metaloxydes, i.e. ceramics, was disclosed in a large number of patent documents. Microwave sintering of metals is generally considered as unfeasible, as metals strongly reflect rather adsorb microwaves. Nevertheless, microwave sintering of metals was disclosed in US-A-6, 183,689.
When using as substrate a material that absorbs microwaves to a lesser extent than the printed structure, i.e. a material with a lower dielectric loss-factor e" within the range of frequencies used, the printed structure is sintered without affecting the substrate. Mircrowave radiation thus allows using substrate materials that are not thermally stable, i.e. would not be able to withstand the high temperatures required for convertional radiation-conduction-convection heating. The use of inkjet inks based on molecules bearing functional groups that polymerise under the influence of microwave radiation without thermally affecting the substrate was disclosed in US-A- 2004/179,076. This patent document discloses novel microwave curable inks for ink-jet printing but neither discloses printing of metal nanoparticles nor their sintering by microwave radiation. The present invention generally relates to a process for the fabrication of metallic structures or metallic patterns onto a substrate.
The present invention relates to a process for generating metallic surface patterns on a substrate surface comprising the steps: i) coating a surface of a substrate with a predetermined pattern of metal particles by applying a dispersion containing said metal particles in a liquid onto said surface, ii) optionally drying said coated substrate to cause said liquid to evaporate, and iii) heating said substrate containing a pattern of said metal particles on said surface by means of microwave radiation to effect heating of said metal particles to form conductive metal patterns on said surface.
In the process of this invention generally each substrate can be used as long as this absorbs microwave radiation to a smaller extent as the metal particles applied to the surface of said substrate. The selection of substrate and metal is performed to result in a lower dielectric loss factor e" of the material forming the substrate as compared to the dielectric loss factor e" of the metal forming the surface pattern. In general the dielectric loss factor e" of the substrate is lower than 50 %, preferably lower than
10 % of the dielectric loss factor e" of the metal forming the surface pattern. This causes the microwaves to couple predominantly with the material with the highest dielectric loss factor, resulting in selective heating of the printed structure, which in turn results in an improvement of desirable properties, such as conductivity or mechanical strength.
More particularly, the substrate should absorb microwave radiation to a. lesser extent than the metal that constitutes the printed structure, i.e. within the frequency range of interest the dielectric loss factor e" of the metal that constitutes the printed structure should be considerably higher than the dielectric loss factor e" of the substrate material.
A large variety of substrates can be chosen for the method of this invention. Non limiting examples are polymers (thermoplastic and duroplastic polymers including elastomers); inorganic materials, such as ceramic materials; semi-conducting substrates, such as silicon or gallium-arsenide, fibrous substrates containing natural and/or man-made fibers, such as paper, textile sheets including non-wovens; film and sheet materials made from polymers and or natural materials, such as leather, wood or thermoplastic sheet or bulk materials including composites, containing said sheet or bulk materials.
Suitable substrates can possess a large variety of properties. For example, they can be transparent or non-transparent, or they can be crystalline or non-crystalline or they can contain adjuvants, such as pigments, antistatic agents, fillers, reinforcing materials, lubricants, processing aids and heat and/or light stabilizers.
As material forming the surface pattern in general each metal including metal alloys (hereinafter together called ,,metals") can be chosen. Non limiting examples are noble metals, metals of the platinum group. Preferably gold and especially preferred silver or silver alloys are used. Mixtures of different metals can also be used.
The metals are applied in the form of particles to the surface. The particle form helps to develop predetermined surface patterns. In addition it has been found that with smaller particle diameters and thus larger surface to volume ratios of the particles the heat generation and development of conductive patterns is promoted.
Typical mean particle diameters are in a range between 1 nm and 10Oμm, preferably 1 nm - 1 μm, very preferred 1 nm - 100 nm and especially preferred 1 nm - 50 nm.
The mean particle diameter is determined by transmission electron microscope (TEM).
Very preferably metal nanoparticles are used, which allow the formation of conducting metal surface patterns with minimum amount of microwave energy.
The metal particles absorb microwave radiation, i.e. electromagnetic radiation with wavelengths ranging from 1 mm to 1 m in free space corresponding to a frequency between approximately 300 GHz to 300 MHz, respectively. It has been found that the use of microwave processing typically reduces heating time by a factor of 10 or more as compared to conventional heating methods.
The surface of the substrate is coated with the metal particles by applying a dispersion containing said metal particles in a liquid onto said surface.
Different coating methods can be used as long as these allow the coating of a surface by creation of a predetermined surface pattern. Predetermined surface patterns can be layers covering the whole surface or other forms of surface coverage. Preferably surface patterns cover portions of the surface, for example in the form of tracks and/or of isolated spots of metal particles. Several surfaces of the substrate can be coated. For example two surfaces of a sheet material can be coated in the form of tracks which are optionally connected via holes going through the substrate and containing conductive material.
Examples of coating methods are known in the art of applying surface coatings, such as curtain coating, spin-coating or coating by means of doctor blade.
Preferably printing methods methods are used, such as offset printing or screen printing and very preferred ink-jet printing.
Initially, the coating material that forms the patterns on said surface(s) is present as a dispersion of metal particles in a carrier material that renders the coating material pasty or preferably fluid. The pasty coating material is hereafter referred to as
"paste". The fluid coating material is hereafter referred to as "ink".
The paste of ink is applied to the surface of the substrate to form a pattern after drying by means of a printing technique, more particularty ink-jet printing.
When applying the paste or ink to the surface of the substrate the carrier material can be removed at the same time, for example by heating the substrate and by chosing a carrier material that evaporates or decomposes at the substrate temperature. In an alternative or an additional step the carrier material can be evaporated or decomposed after the formation of the surface pattern in a separate heat treatment step or the carrier material can be evaporated or decomposed during the tretment with microwave radiation.
After a predetermined pattern of metal particles has been formed on the substrate surface(s) this is then exposed to microwave radiation.
As the microwaves couple predominantly with the metal particles forming the material with the highest dielectric loss factor e" this results in selective heating of the printed structure. Most of the heat generated by absorption of the microwave radiation develops in the metal particles and causes these to melt and/or to sinter, which in turn results in an improvement of desirable properties, such as conductivity or mechanical strength.
The equipment for performing the method of this invention can be chosen from known devices. Coating devices, heat treatment devices and microwave generators are known in the art and commercially available.
But the combination of these devices has not been used yet and is also subject of this invention.
The processed substrates containing conductive surface patterns of metal can be compiled to form a layered product with several substrates possessing conductive patterns in the interior and on the surface. The layered products can contain layers of other materials besides the processed substrates containing conductive surface patterns of metal.
The invention also relates to a device for performing the above-defined method comprising the combination of
A) a coating device for surface coating of a substrate with a predetermined pattern of metal particles, optionally
B) a heating device for heating the coated substrate, and C) a microwave generator for treating the coated substrate to generate conductive metal patterns from the patterns of metal particles on the surface of said substrate.
Preferably the coating device is an ink-jet printer.
Furthermore, the invention relates to the use of microwave radiation for the generation of conductive metal patterns on a substrate surface.
The process for generating metallic surface patterns on a substrate surface can be used, for example, for the production of printed wiring boards or of integrated circuits, for the production of decorative sheets or for the production of of data recording or of data storing media, for the production of print boards, for the production of radio frequency identification devices (RFID devices) or for the production of electrical devices, like heating elements, resistors, coils or antennas.
These uses are also subject of the present invention.
The following Example illustrates the invention without any limitation.
Example
Printing and sintering of silver tracks on polyimide
A dispersion of silver nanoparticles in tetradecane known as Nanopaste™ was purchased from Harima Chemical Ltd. A polyimide foil with a thickness of 100 μm and known as Kapton HN was used as substrate.
A Microdrop Autodrop inkjet printer, equipped with a MD-K-140 dispenser system was filled with the aforementioned dispersion. An array of parallel lines with a typical length of 1 cm and a spacing of 5 mm in between was then printed onto the substrate by deposition of droplets with a spacing of 100 μm. To avoid bleeding of the ink the substrate was heated during printing at 100 0C. The polyimide foil with printed structure thereon was then sintered during three minutes by microwave radiation using a monomode microwave oven operating at 2.45 GHz and a power of 300 W.
The resistance per unit distance of the sintered lines was 4-6 Ω*cm'1. The resistivity of the material as calculated from the resistance and the cross-sectional area of a line is 30 * 10"8 Ω*m.

Claims

What is claimed is:
1. A process for generating metallic surface patterns on a substrate surface comprising the steps: i) coating a surface of a substrate with a predetermined pattern of metal particles by applying a dispersion containing said metal particles in a liquid onto said surface, ii) optionally drying said coated substrate to cause said liquid to evaporate, and iii) heating said substrate containing a pattern of said metal particles on said surface by means of microwave radiation to effect heating of said metal particles to form conductive metal patterns on said surface.
2. A process as claimed in claim 1 , wherein the substrate is selected from the group consisting of polymers, inorganic materials, semi-conducting substrates, fibrous substrates containing natural and/or man-made fibers, film and sheet materials made from polymers and/or natural materials.
3. A process as claimed in claim 1 , wherein the substrate is a thermoplastic or duroplastic polymer, an elastomer, a ceramic materials, silicon or gallium- arsenide, paper, leather, wood, thermoplastic sheet or bulk material or a composite containing said sheet or bulk material.
4. A process as claimed in claim 1 , wherein the metal is gold and/or silver or silver alloys
5. A process as claimed in claim 4, wherein the metal is silver.
6. A process as claimed in claim 1 , wherein the metal particles possess a mean particle diameter between 1 nm and 100μm, especially preferred between 1 nm and 50 nm.
7. A process as claimed in claim 1 , wherein the predetermined surface pattern covers a portion of the surface in the form of tracks and/or of isolated spots of metal particles.
8. A process as claimed in claim 7, wherein as a coating method a printing method is used.
9. A process as claimed in claim 8, wherein the printing method is ink-jet printing.
10. A process as claimed in claim 1 , wherein the dispersion of metal particles is in the form of a paste or preferably in the form of an ink.
11.A process as claimed in claim 1 , wherein the substrate is heated during the coating of the surface with the dispersion of metal particles.
12. A device for performing the method according to claim 1 comprising the combination of
A) a coating device for surface coating of a substrate with a predetermined pattern of metal particles, optionally
B) a heating device for heating the coated substrate, and C) a microwave generator for treating the coated substrate to generate conductive metal patterns from the patterns of metal particles on the surface of said substrate.
13. A device according to claim 12, wherein the coating device is an ink-jet printer.
14. Use of microwave radiation for the generation of conductive metal patterns on a substrate surface.
15. Use of the process according to claim 1 for the production of printed wiring boards or of integrated circuits, for the production of decorative sheets, for the production of of data recording or of data storing media, for the production of print boards, for the production of radio frequency identification devices (RFID devices) or for the production of electrical devices.
16. Use according to claim 15, wherein the electrical device is a heating element, a resistor, a coil or an antenna.
PCT/EP2005/010486 2005-09-28 2005-09-28 Method for generation of metal surface structures and apparatus therefor WO2007038950A1 (en)

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PCT/EP2005/010486 WO2007038950A1 (en) 2005-09-28 2005-09-28 Method for generation of metal surface structures and apparatus therefor
EP06805928A EP1932403A1 (en) 2005-09-28 2006-09-28 Method for generation of metal surface structures and apparatus therefor
US11/992,259 US20090191358A1 (en) 2005-09-28 2006-09-28 Method for Generation of Metal Surface Structures and Apparatus Therefor
PCT/EP2006/009437 WO2007039227A1 (en) 2005-09-28 2006-09-28 Method for generation of metal surface structures and apparatus therefor
JP2008532675A JP2009510747A (en) 2005-09-28 2006-09-28 Method for generating metal surface structure and apparatus therefor

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