NZ622408B2 - Method of forming a conductive image on a non-conductive surface - Google Patents

Method of forming a conductive image on a non-conductive surface Download PDF

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Publication number
NZ622408B2
NZ622408B2 NZ622408A NZ62240812A NZ622408B2 NZ 622408 B2 NZ622408 B2 NZ 622408B2 NZ 622408 A NZ622408 A NZ 622408A NZ 62240812 A NZ62240812 A NZ 62240812A NZ 622408 B2 NZ622408 B2 NZ 622408B2
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New Zealand
Prior art keywords
metal
coordination complex
etching
metal coordination
onto
Prior art date
Application number
NZ622408A
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NZ622408A (en
Inventor
William Wismann
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Earthone Circuit Technologies Corporation
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Publication date
Priority claimed from US13/403,797 external-priority patent/US8784952B2/en
Application filed by Earthone Circuit Technologies Corporation filed Critical Earthone Circuit Technologies Corporation
Priority to NZ716340A priority Critical patent/NZ716340B2/en
Publication of NZ622408A publication Critical patent/NZ622408A/en
Publication of NZ622408B2 publication Critical patent/NZ622408B2/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1655Process features
    • C23C18/1664Process features with additional means during the plating process
    • C23C18/1673Magnetic field
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22Roughening, e.g. by etching
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/28Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture 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
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture 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
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801Applying 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 dielectrics, e.g. smoothing
    • H01L21/76802Applying 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 dielectrics, e.g. smoothing by forming openings in dielectrics
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture 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
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838Applying 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture 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
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838Applying 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
    • H01L21/76877Filling of holes, grooves or trenches, e.g. vias, with conductive material
    • H01L21/76879Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/104Using magnetic force, e.g. to align particles or for a temporary connection during processing
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1157Using means for chemical reduction
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus 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
    • H05K3/105Apparatus 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 conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus 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
    • H05K3/18Apparatus 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
    • H05K3/181Apparatus 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
    • H05K3/182Apparatus 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
    • H05K3/185Apparatus 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
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate

Abstract

The present invention relates to a method for forming a raised conductive image on a non-conductive or dielectric surface (15). The method comprising placing a metal coordination complex on a surface of the substrate, exposing the surface (15) to electromagnetic radiation (25), reducing the exposed complex, removing unexposed metal complex leaving an elemental metal image, drying the surface (15) and then plating the resulting elemental metal image with a highly conductive material. complex, removing unexposed metal complex leaving an elemental metal image, drying the surface (15) and then plating the resulting elemental metal image with a highly conductive material.

Description

METHOD OF FORMING A CONDUCTIVE IMAGE ON A NONCONDUCTIVE SURFACE William Wismann CROSS REFERENCE TO D ATIONS This application is related to and claims the benefit of (1) U.S. ional Patent Application No. 61/525,662, filed in the name of William Wismann on August 19, 2011, (2) U.S. Provisional Patent Application No. ,736, filed in the name of William Wismann on December 9, 2011, and (3) is a continuation of U.S. Patent Application No. 13/403,797, filed in the name of William Wismann on February 23, 2012, all of which are hereby incorporated herein by reference in their ty.
FIELD This invention relates to the field of electronic device manufacture.
BACKGROUND tive images on non-conductive or dielectric surfaces are ubiquitous in today’s technology-driven world. Perhaps the most widely known example of such are the integrated circuits found in virtually all electronic devices. Integrated circuits result from a sequence of photographic and chemical processing steps by which the circuits are gradually created on a dielectric substrate such as a silicon wafer. 6252342_4.docx A typical wafer is made out of ely pure silicon that is grown into mono-crystalline cylindrical ingots, called boules, that are up to 300 mm in diameter. The boules are then sliced into wafers about 0.75 mm thick and polished to obtain a very smooth flat surface.
The formation of a circuit on a wafer requires numerous steps that can be categorized into two major parts: front-end-of-line (FEOL) processing and back- end-of-line (BEOL) processing.
FEOL processing refers to the formation of ts directly in the silicon. The raw wafer is first subjected to y, the growth of crystals of ultrapure silicon on the wafer wherein the crystals mimic the orientation of the substrate.
After epitaxy, front-end surface engineering generally consists of the steps of growth of the gate dielectric, traditionally n dioxide (SiO2), patterning of the gate, patterning of the source and drain regions, and subsequent implantation or ion of dopants to obtain the desired complementary electrical properties. In c random access memory (DRAM) devices, storage capacitors are also fabricated at this time, typically d above the access transistor.
Once the s semiconductor devices have been created, they must be interconnected to form the desired electrical circuits, which comprise the BEOL n of the s. BEOL involves creating metal interconnecting wires that are isolated by dielectric layers. The insulating material was traditionally a form of silicate glass, SiO2, but other low dielectric constant materials can be used.
The metal interconnecting wires often comprise aluminum. In an approach to wiring called subtractive aluminum, blanket films of aluminum are deposited, patterned and etched to form the wires. A dielectric material is then 6252342_4.docx deposited over the exposed wires. The various metal layers are interconnected by etching holes, called vias, in the insulating material and depositing tungsten in the holes. This approach is still used in the fabrication of memory chips such as DRAMs as the number of interconnect levels is small.
More recently, as the number of interconnect levels has increased due to the large number of transistors that now need to be interconnected in a modern rocessor, the timing delay in the wiring has become icant, ing a change in wiring material from aluminum to copper and from the silicon dioxides to newer low-K al. The result is not only enhanced performance but reduced cost as well in that damascene processing is substituted for subtractive aluminum technology, thereby elimination several steps. In damascene processing, the dielectric material is deposited as a blanket film, which is then patterned and etched leaving holes or trenches. In single damascene processing, copper is then deposited in the holes or es surrounded by a thin barrier film resulting in filled vias or wire lines. In dual damascene technology, both the trench and via are fabricated before the deposition of copper resulting in formation of both vias and wire lines aneously, further reducing the number of processing steps. The thin barrier film, called copper barrier seed (CBS), is necessary to prevent copper diffusion into the dielectric. The ideal barrier film is as thin as possible. As the presence of excessive barrier film competes with the available copper wire cross section, formation of the thinnest continuous barrier represents one of the greatest ongoing challenges in copper processing today.
As the number of interconnect levels increases, planarization of the previous layers is required to ensure a flat surface prior to subsequent lithography. Without it, the levels would become increasingly crooked and extend e the depth of focus of available lithography, interfering with the y to pattern. CMP (chemical mechanical planarization) is a processing method to achieve such planarization although dry etch back is still sometimes employed if the number of onnect levels is low.
The above s, gh described specifically with regard to 6252342_4.docx silicon chip manufacture, is fairly generic for most types of printed circuits, printed circuit boards, antennas, solar cells, solar thin films, semiconductors and the like. As can be seen, the process is subtractive; that is a metal, usually copper, is deposited uniformly over a substrate surface and then unwanted metal, that is, metal that does not comprise some part of the final circuit, is removed. A number of additive processes are known, which resolve some of the problems associated with the subtractive process but which engender problems of their own, a significant one of which involves adherence of a builtup conducting layer to the substrate.
What is needed is an additive process for integrated circuit fabrication that has all of the advantages of other additive processes but which exhibits improved adhesion properties to ates. [013a] Alternatively or additionally, what is needed is at least a useful choice for the public.
SUMMARY In one aspect this ion relates to a method of g a conductive layer on a surface, comprising performing the ing steps in order: activating at least a portion of a non-conductive substrate e; applying a magnetic field to the surface; depositing a metal coordination complex on at least a part of the activated portion of the surface; ng the magnetic field; exposing the metal coordination complex to electromagnetic ion; reducing the metal coordination complex to elemental metal; removing unreduced metal nation complex from the surface; drying the e; and depositing a conductive material onto the surface. [014a] The term ‘comprising’ as used in this specification and claims means ‘consisting at least in part of’. When interpreting statements in this specification and claims which include the term ‘comprising’, other es besides the es prefaced by this term in each statement can also be 6252342_4.docx present. Related terms such as ‘comprise’ and ‘comprised’ are to be interpreted in similar manner.
In an aspect of this ion, activating the substrate surface comprises g the surface.
In an aspect of this invention, etching the surface comprises chemical etching.
In an aspect of this invention, chemical etching comprises acid g, base etching or oxidative etching.
In an aspect of this invention, etching the surface comprises ical g.
In an aspect of this invention, etching the surface comprises plasma etching.
In an aspect of this invention, etching the surface comprises laser- etching.
In an aspect of this invention, plasma or laser etching ses etching in a pre-determined pattern.
In an aspect of this invention, the magnetic field has a magnetic flux density of at least 1000 gauss.
In an aspect of this invention, the ic field is orthogonal to the surface.
In an aspect of this invention, depositing a metal coordination complex on at least a portion of the surface comprises using a mask.
In an aspect of this invention, the mask comprises an electronic circuit. 6252342_4.docx In an aspect of this invention, the onic t is selected from the group consisting of an analog circuit, a digital circuit, a mixed-signal circuit and an RF circuit.
An aspect of this invention is an analog t comprising a conductive layer, the conductive layer being formed on a surface using the method described herein.
An aspect of this invention is a digital circuit comprising a conductive layer, the conductive layer being formed on a surface using the method described herein.
An aspect of this invention is a mixed-signal t comprising a conductive layer, the conductive layer being formed on a surface using the method described herein.
An aspect of this invention is an RF circuit comprising a conductive layer, the conductive layer being formed on a surface using the method described herein.
In an aspect of this invention, exposing the metal coordination complex to omagnetic radiation comprises microwave radiation, infrared radiation, visible light radiation, iolet radiation, X-ray radiation or gamma radiation.
In an aspect of this invention, reducing the metal coordination complex to a zero oxidation state metal comprises using a combination of metals and/or catalysts.
In an aspect of this invention, removing unreduced metal nation complex from the surface comprises washing the e with a solvent. 6252342_4.docx In an aspect of this invention, drying the surface comprises drying at ambient temperature or drying at elevated temperature.
In an aspect of this invention, drying the surface at ambient or ed temperature comprises using a vacuum chamber.
In an aspect of this invention, depositing a conductive al onto the e comprises electrolytic deposition of a metal onto the portion of the surface comprising the d metal coordination complex.
In an aspect of this ion, olytic deposition of a metal onto the portion of the surface comprising the reduced metal coordination complex comprises: contacting a negative terminal of a direct current power supply with at least the portion of the surface comprising the d metal coordination complex; providing an aqueous solution comprising a salt of the metal to be deposited, an electrode made of the metal immersed in the aqueous solution or a combination thereof; contacting a positive terminal of the direct current power supply with the aqueous solution; contacting at least the portion of the e comprising the reduced metal coordination complex with the aqueous solution; and turning on the power supply.
In an aspect of this invention, depositing a conductive al onto the surface comprises electroless deposition of a metal onto the portion of the surface comprising the reduced metal coordination x.
In an aspect of this invention, electrolessly depositing a metal onto the portion of the surface comprising the reduced metal coordination complex comprises ting at least the portion of the surface comprising the metal coordination complex with a solution comprising a salt of the metal, a complexing agent and a reducing agent. 6252342_4.docx In an aspect of this invention, depositing a conductive material onto the surface comprises deposition of a non-metallic conductive substance onto the portion of the surface comprising the reduced metal coordination In an aspect of this invention, the non-metallic conductive material is deposited onto the portion of the surface comprising the reduced metal coordination complex by electrostatic dispersion.
In an aspect of this invention, the entire non-conductive substrate surface is activated and the metal coordination complex is deposited onto the entire surface.
In an aspect of this invention, the entire non-conductive substrate surface is activated and the metal coordination complex is deposited on a part of the activated e.
DETAILED DESCRIPTION Brief description of the figures The figure herein is provided solely to assist in the understanding of the present invention and is not intended nor is it to be construed as limiting the scope of this invention in any manner whatsoever.
Figure 1 shows a substrate to be processed using the method of this invention where the substrate is situated in an magnetic field such that the field is orthogonal to the plane of the e of the ate.
Discussion It is understood that, with regard to this ption and the appended claims, reference to any aspect of this invention made in the singular includes the plural and vice versa unless it is sly stated or guously clear from the t that such is not intended. 6252342_4.docx As used herein, any term of approximation such as, without limitation, near, about, approximately, substantially, essentially and the like, mean that the word or phrase modified by the term of approximation need not be exactly that which is written but may vary from that written description to some extent. The extent to which the description may vary will depend on how great a change can be instituted and have one of ordinary skill in the art ize the modified n as still having the properties, characteristics and capabilities of the word or phrase unmodified by the term of approximation. In general, but with the preceding discussion in mind, a numerical value herein that is modified by a word of approximation may vary from the stated value by ±10%, unless expressly stated otherwise.
As used herein, the use of “preferred,” “preferably,” or “more preferred,” and the like refers to preferences as they existed at the time of filing of this patent application.
As used herein, a ctive layer” refers to an electrically conductive surface, for example, without limitation, a d circuit.
As used herein, a “non-conductive ate” refers to a substrate made of an electrically non-conductive material, sometimes referred to as an insulator or a dielectric. Such als include, without limitation, minerals such as , alumina, magnesia, zirconia and the like, glass and most plastics.
Specific non-limiting examples e FR4, which is the general grade designation for fiberglass reinforced epoxy resin such as, without limitation, DuPont Kapton® PV9103 polyimide and ULTRALAM® liquid crystal polymer (Rogers Corporation, Chandler AZ).
As used herein, to “activate a non-conductive substrate surface,” or a n thereof of, refers to rendering the surface more amenable to interaction with and subsequent physical or chemical bonding to r material that is disposed onto the surface of the ate. In an embodiment of this invention, the other material can comprise a metal coordination complex. In 6252342_4.docx addition, altering the surface properties also refers to rendering the e more diffusive toward incident electromagnetic radiation. Altering the surface properties can be accomplished by altering the aphy or the permeability of the surface or a combination of the two. The topography of the surface can be altered by mechanical or chemical means or a ation of the two.
Mechanical means of altering the surface properties of the substrate include, without limitation, simple on of the surface such as with sandpaper or another abrasive al, rasping the surface with a file, scoring the e with a sharp object such as, without limitation, a tool bit, and laser etching. Combinations of these and any other methods that result in an abraded surface are within the scope of this invention.
In some embodiments, the surface may be prepared ab initio using a mold that includes an abraded surface r and forming the substrate with altered surface properties by disposing a molten polymer into the mold. When removed, the molded object will have an altered surface as ed to an object molded using a -surfaced mold. These methods of altering a surface property are nown to those skilled in the art and require no further description, Chemical means of altering the surface properties of a substrate include, without limitation, acid g, base etching, oxidative etching and plasma etching.
Acid etching, as the name implies, refers to the use of a strong acid such as sulfuric acid, hydrochloric acid and nitric acid. A mixture of hydrochloric acid with nitric acid produces aqua regia, an extremely strong acid which can be used to alter the surface properties of a substrate. Most commonly, however, the surface to be acid etched is a glass and the acid use to etch the glass is hydrofluoric acid. This, and other acid etching technologies are well-known in the art and likewise require no detailed explanation.
Base etching is the converse of acid etching and involves the use 6252342_4.docx of a basic nce to alter the topology of the surface of a substrate. Many organic polymers are susceptible to chemical dissolution with basic substances.
For instance, without limitation, potassium hydroxide will react with polyesters, polyimides and polyepoxides to alter their surface ties. Other materials susceptible to base etching will be known those skilled in the art. All such als are within the scope of this invention. ive etching refers to the alteration of the surface properties of a substrate by contacting the surface with a strong oxidant which as, without limitation, potassium permanganate.
Plasma etching refers to the process of impacting the e of a substrate with a peed stream of a glow rge of an appropriate gas.
The etching species may comprise charged ions or neutral atoms and radicals.
During the etch process, elements of the material being etched can chemically react with the reactive species generated by the plasma. In addition, atoms of the plasma- generating substance may imbed themselves at or just below the surface of the substrate, further altering the properties of the surface. As with the other methods of altering the properties of a surface, plasma etching is wellknown in the art and needs no r description for the purposes of this invention.
Laser etching is well-known in the art. Briefly, a laser beam is ed at a e that is within the laser's focal plane. The laser's movement is controlled by a computer. As the laser focal point is moved across the surface, the material of the surface is, generally, vaporized thus leaving the image being traced by the laser on the surface. With regard to this invention, the laser may be used to impart an overall pattern on the surface of a substrate or it may be used to trace the actual image to eventually be rendered conductive onto the substrate.
Another means of altering the surface properties of a substrate es exposing the surface of the substrate to a fluid that is know of found to soften the surface, often with concomitant swelling of the e. When a 6252342_4.docx coating material is applied to the swollen surface, the material can physically ct at the boundary between it and the swollen surface, which can result the material being more y bound to the e, in particular when the coated ate is dried.
As used herein, "applying an magnetic field" to a substrate surface es placing a surface of the substrate on or near a source of a magnetic field. The magnetic field may be generated by either a permanent magnet, an electromagnet or a combination thereof. A single magnet or plurality of magnets may be used. The surface of the substrate that is in contact with or near the magnet may be the surface opposite to that surface onto which a metal coordination complex is to be deposited or it may be the surface onto which a metal coordination complex is to be deposited. That is, the source of the magnetic field may be above or below the substrate wherein "above" refers to the activated surface of the substrate and "below" refers to the surface opposite the activated surface. If the magnetic field is generated using a permanent magnet, any type of magnet may be used so long as the field strength is at least 1000 gauss, more preferably at least 2000 gauss. A tly preferred permanent magnet is a neodymium magnet. It is also preferred that a ent magnet have dimensions such that close to or all of the activated surface of the substrate is contained within the dimensions of the magnet. Such an arrangement is shown in Fig. 1. In Fig. 1, substrate 10 has an ted e 15. Permanent magnet 20 is disposed below substrate 10 and positioned such that the magnetic field generated by the magnet is orthogonal to activated surface 15, which is a presently preferred configuration.
As used herein, a "paramagnetic or ferromagnetic metal coordination complex" is understood to have the meaning that would be ascribed to these classes of metal xes by those skilled in the art. The metal coordination complex must be ferro- or para- magnetic so that, when disposed on the surface of the substrate, it is affected by the orthogonal magnetic field. t being held to any particular theory, it is ed that the complex, under the influence of the magnetic field, will either be drawn in toto toward the source of the magnetic field and thereby be more deeply injected 6252342_4.docx into the surface of the substrate or the field may cause the ligands of the complex to align with the magnetic field thereby drawing the ligands further into the substrate. A combination of the two processes may also occur. The result in any case would be more tightly bound complex than that which would be obtained without the influence of the magnetic field.
After the metal coordination complex is applied to the surface of the substrate under the influence of the applied magnetic field, the source of the magnetic field is removed.
The metal coordination complex coated substrate is then exposed to omagnetic radiation to activate the metal nation complex toward a ng agent. As used herein, electromagnetic radiation includes virtually the entire spectrum of such, i.e., microwave, infrared, visible, ultraviolet, X-ray and gamma ray radiation. The composition of the metal coordination complex can be manipulated to render it sensitive to a particular range with the omagnetic um or, if desired, sensitizer(s) may be added to the complex when it is disposed on the substrate to render the complex photosensitive or, if the complex is inherently photosensitive, to render it even more so. As used here, "photosensitive" has its dictionary definition: sensitive or responsive to light or other radiant energy, which would include each of the types of radiation mentioned above. re to ion renders a portion of the metal coordination complex susceptible to reduction. The reducing agent will reduce the metal coordination complex to tal metal. The reducing agent can be any metal- inclusive salt wherein the metal has a reduction potential that is greater, i.e., conventionally has a more negative reduction potential than the metal of the nation complex. The following chart shows the reduction ial of a number of common substances. Substances higher on the list are e of reduction of those beneath it. 6252342_4.docx Reducing agent Reduction potential (V) Li −3.04 Na −2.71 Mg −2.38 Al −1.66 H2(g) + 2OH − −0.83 Cr −0.74 Fe −0.44 H2 0.00 Sn2+ +0.15 Cu+ +0.16 Ag +0.80 2Br− +1.07 2Cl− +1.36 Mn2+ + 4H2O +1.49 The elemental metal resulting from the reduction step is, of course, insoluble in most solvents. Thus, washing the surface of the substrate with an appropriate solvent, which is determined by the composition of the initial metal nation complex, will remove unexposed complex leaving the metal.
The metal may be evenly dispersed over the e of the substrate if the surface of the substrate was generally d or the metal may form a discrete pattern if the substrate surface was exposed through a mask. A mask is simply a al that is placed between the source of the electromagnetic radiation and the surface of the substrate and which includes an image is to be transferred to the surface of the substrate. The image may be a negative image in which case the portions of the substrate surface that receive ion corresponds to those portions of the mask that are transparent to the particular radiation or the image may be a positive image in which case the portions of the substrate surface that receive radiation correspond to those portions outside the 6252342_4.docx image areas of the mask.
Once the unexposed metal coordination complex is removed, the substrate with is dried to complete formation of the metal image.
The metal image can be used as is, plated with another metal or coated with a non-metallic conductive material.
If the metal image is to be plated with another metal, such can be accomplished electrolytically or electrolessly. In this manner a conductive metal layer is formed only on the regions of the image comprising the metal image, the result being a raised conductive surface.
Electroless plating of the metal image portions of the surface of the substrate can be accomplished, without limitation, by contacting the surface with a solution of a salt of a metal to be deposited in the presence of a xing agent to keep the metal ions in solution and to stabilize the solution generally. The surface with the complexed metal salt in contact with it or at least near the surface is simultaneously or consecutively contacted with an aqueous solution of a ng agent. The metal complex is reduced to afford elemental metal which adheres to the metal image already on the surface of the substrate; i.e., an electrolessly deposited layer of metal on metal results.
The metal complex solution and the reducing solution can be rently sprayed onto the patterned substrate either from separate spray units, the spray streams being directed so as to ect at or near the substrate surface, or from a single spray unit having separate reservoirs and spray tip orifices, the two s being mixed as they emerge from the spray tip and impinge on the substrate e.
The electrodeposition process contemplated herein is well-known in the art and need not be extensively bed. In brief, the elemental metal image is connected to the negative terminal (cathode) of a direct t power source, which may simply be a y but, more commonly, is a rectifier. The 6252342_4.docx anode, which constitutes the second metal to be deposited onto the first metal image, is connected to the positive terminal (anode) of the power source. The anode and cathode are electrically connected by means of an electrolyte on in which the imaged metal surface is submersed or bathed as by t with a spray of the solution.
The electrolyte solution contains dissolved metal salts of the metal to be plated as well as other ions that render the electrolyte conductive.
When power is applied to the system, the metallic anode is oxidized to produce cations of the metal to be deposited and the positively charged cations migrate to the cathode, i.e., the metal image on the substrate surface, where they are reduced to the zero valence state metal and are deposited on the surface.
In an embodiment of this ion, a solution of cations of the metal to be deposited can be ed and the solution can be sprayed onto the metalized construct.
The conductive material to be coated on the elemental metal image may also comprise a non-metallic conductive substance such as, without tion, carbon or a conductive polymer. Such materials may be deposited on the metal image by techniques such as, without limitation, electrostatic powder coating and electrostatic dispersion g, which may be conducted as a wet (from solvent) or dry process. The process may be carried out by electrostatically charging the metal image and then contacting the image with nano- or micro- sized particles that have been electrostatically d with the opposite charge to that applied to the metal image. In addition, to r ensure that only the metal image is coated, the non- conductive ate may be grounded to eliminate any possibility of an attractive charge developing on the substrate or the substrate may be charged with the same polarity charge as the substance to be deposited such that the substance is repelled by the substrate. 6252342_4.docx EXAMPLES Example 1 1. DuPont Kapton PV9103 polyimide, in small sheets is chemically etched using a mixture of 0.1 N KOH (5.6 grams ium hydroxide per 1 liter of deionized water (DI)) with a 60% by weight on of isopropanol alcohol, for 2 to 4 minutes 2. The etched ide sheet is rinsed with DI water and dried for 30 minutes in an oven at 100 ºC. 3. 10 grams of ferric ammonium oxalate are suspended in 25ml of DI water (in the darkroom) (Solution 1). 4. 10 grams of ferric ammonium oxalate are mixed with 1.0 gram of potassium chlorate and 25 ml of DI water (also in the darkroom) (Solution 2). . 2.3 grams of ammonium tetrachloroplatinate(II) are mixes with 1.7 grams of lithium chloride and 2ml of DI water (Solution 3). 6. ons 1, 2, and 3 are mixed together in equal amounts. 7. The etched polyimide sheet is placed on a 2000 gauss magnet that has dimensions larger than those of the polyimide sheet and the mixture of Step 6 is applied thinly over the surface of the sheet (in the darkroom) with a sponge brush. 8. The coated polyimide sheet was air dried for 30 minutes (alternatively the coated sheet may be placed an oven at 40 ºC for about 5 minutes or until dry). 9. A mask comprising the desired pull tab image was placed on top of the coating 6252342_4.docx . The masked surface of the ide sheet was exposed to an ASC365 ultraviolet light source at full strength for no less than 3 minutes 11. The light source was d, the mask was separated from the substrate surface and the surface was rinsed for 5 s with DI water and then placed in a ethylenediamine tetraacetic acid (EDTA) bath sing 15 grams of EDTA per 1000ml of DI water 10 minutes. 12. The rinsed substrate was placed in an oven at 40 ºC for 5 minutes or until dry. 13. The substrate was placed in a bath comprising Shipley Electroless Cuposit 328 with 27.5% 328 (A-12.5%, L-12.5%, C-2.5%) and 72.5% DI 25 ºC for 5 minute intervals to record plating. 14. The resulting copper-plated polymide was rinsed with DI water for 10 s and air dried for 30 minutes (or can be placed in an oven at 40 ºC for 5 minutes or until dry).
Example 2 1. A Rogers ULTRALAM 3000 liquid crystal polymer (LCP) sheet was chemically etched with Electro-Brits E-prep 102, approximately 5% by volume (40 grams per liter of sodium hydroxide) 2. The sheet was static rinsed followed by a double cascade rinse. 3. The rinsed etched sheet was then processed with E-Neutralizer and then rinsed again. 4. The sheet was then dipped in a 10% solution of sulfuric acid for 10 seconds and rinsed. 6252342_4.docx . 10 grams of silver nitrate were dissolved in 25 ml of DI water (in the darkroom). 6. 5 grams of potassium chromate were mixed with 5 ml of DI water (in the darkroom) 7. Drops of silver e were added to the potassium chromate solution until a red precipitate formed. The mixture was allowed to stand for 24 hours and then was filtered and diluted to 100 ml with DI water (in the darkroom) 8. The sheet was then placed on a 2000 gauss magnet and the silver chromate mixture was thinly applied to it (in the darkroom) with a sponge brush. 9. The coated sheet was placed in an oven at 40 ºC for 10 minutes or until dry.
. A pull test designed mask was placed on the coated surface of the LCP sheet. 11. The masked LPC sheet was then exposed to ultraviolet light from an ASC365 ultraviolet light source for 5 minutes. 12. The UV light source was removed, the LCP sheet was separated from the mask and rinsed for 5 minutes with DI water and then placed in an EDTA bath (15 grams of EDTA, per 1000ml of DI water) for 10 s. 13. The LCP sheet was then rinsed with DI for 10 s and put it into an oven at 40 ºC for 5 minutes or until dry. 14. The LCP sheet was then placed in a bath comprising Shipley Electroless Cuposit 328 with 27.5% 328 (1-12.5%, L-12.5%, C-2.5%) and 72.5% deionized water at 25 ºC for 5 minute intervals to record plating.
. The copper-plated LCP sheet was d from the bath, rinsed for 10 6252342_4.docx minutes and then placed in an oven at 40 ºC for 5 minutes until dry.
Example 3 1. A thin sheet (0.15" thickness) of FR4 was chemically etched with a 10% solution of sulfuric acid for 3 minutes and then with a 6% solution of potassium hydroxide. 2. The sheet was then rinsed with DI water. 3. 30 grams of ammonium ferric citrate (the green form, 7.5% ammonia, % iron and 77.5% hydrated citric acid) was mixed with 35 ml of warm (50 ºC) DI water (in the om) and then made up to a final volume of 50 ml with DI water in an amber bottle (in the darkroom). 4. 1.8 grams of ammonium chloride in 20 ml of hot (70-80 ºC) DI water was mixed with stirring with 3 grams of palladium(II) chloride until dissolved, and then made up to 25 ml by on of DI water.
. The mixture was filtered and bottled when cool. 6. 6 drops of the um ferric citrate was added to 1 drop of palladium chloride solution in a beaker until 20 ml of solution is obtained (in the darkroom). 7. The FR4 sheet was placed on a 2000 gauss magnet with dimensions larger than those of the FR4 sheet and the coordinated complex solution was sponge brushed thinly on the surface of the sheet (in the om). 8. The FR4 sheet was then place in an oven at 40 ºC for 10 minutes or until dry. 9. A pull test designed mask was then placed on the treated surface of the FR4 sheet. 6252342_4.docx . The masked FR4 sheet was then exposed to UV light from an ASC365 ultraviolet emitter for 6 minutes. 11. The UV light source was removed, the mask separated from the FR4 sheet, the sheet was rinsed for 5 s with DI water and then was placed in an EDTA bath (15 grams of EDTA, per 1000ml of DI water) 10 minutes. 12. The FR4 sheet was removed from the EDTA bath, rinsed with DI water for 10 minutes and then placed in an oven at 40 ºC for 5 minutes or until dry. 13. The FR4 sheet was placed in a bath of Shipley Electroless Cuposit 328 with 27.5% 328 (A-12.5%, L-12.5%, C-2.5%) and 72.5% zed water at 25 ºC for 5 minute intervals to record plating. 14. The copper plated FR4 sheet was then rinsed for 10 minutes and put it into an oven at 40 ºC for 5 minutes until dry. 6252342_4.docx

Claims (28)

What is claimed:
1. A method of forming a conductive layer on a surface, comprising performing the following steps in order: ting at least a portion of a non-conductive substrate surface; applying a magnetic field to the surface; depositing a metal coordination complex on at least a part of the activated portion of the surface; removing the magnetic field; exposing the metal coordination complex to electromagnetic radiation; reducing the metal coordination complex to elemental metal; removing unreduced metal coordination complex from the surface; drying the surface; and depositing a conductive material onto the surface.
2. The method of claim 1, wherein activating the substrate surface comprises etching the e.
3. The method of claim 2, n etching the surface comprises chemical etching.
4. The method of claim 3, wherein chemical etching ses acid etching, base etching or oxidative etching.
5. The method of claim 2, wherein etching the surface comprises ical etching.
6. The method of claim 2, n etching the surface ses plasma etching.
7. The method of claim 2, wherein etching the surface comprises tching.
8. The method of claim 6, wherein plasma etching comprises etching in a 6252342_4.docx pre-determined pattern.
9. The method of claim 1, where the magnetic field has a ic flux density of at least 1000 gauss.
10. The method of claim 9, n the magnetic field is onal to the surface.
11. The method of claim 1, where depositing a metal coordination complex on at least a portion of the surface comprises using a mask.
12. The method of claim 11, wherein the mask comprises an electronic circuit.
13. The method of claim 12, wherein the electronic circuit is selected from the group consisting of an analog circuit, a digital circuit, a mixed-signal circuit and an RF circuit.
14. The method of claim 1, wherein exposing the metal coordination complex to electromagnetic radiation comprises microwave radiation, ed radiation, visible light radiation, ultraviolet radiation, X-ray radiation or gamma radiation.
15. The method of claim 1, where reducing the metal coordination complex to a zero oxidation state metal comprises using a combination of metals and/or catalysts.
16. The method of claim 1, wherein ng unreduced metal coordination complex from the surface comprises washing the surface with a solvent.
17. The method of claim 1, n drying the surface comprises drying at ambient temperature or drying at elevated temperature.
18. The method of claim 17, wherein drying the surface at ambient or 6252342_4.docx elevated temperature comprises using a vacuum chamber.
19. The method of claim 1, wherein ting a tive material onto the surface ses electrolytic deposition of a metal onto the n of the surface comprising the reduced metal nation complex.
20. The method of claim 19, wherein electrolytic deposition of a metal onto the portion of the surface comprising the reduced metal coordination complex comprises: contacting a negative al of a direct current power supply with at least the n of the surface comprising the reduced metal coordination complex; providing an aqueous solution comprising a salt of the metal to be deposited, an electrode made of the metal immersed in the aqueous solution or a combination thereof; contacting a positive terminal of the direct current power supply with the aqueous solution; contacting at least the portion of the surface comprising the reduced metal coordination x with the aqueous solution; and turning on the power supply.
21. The method of claim 1, wherein depositing a conductive material onto the surface comprises electroless deposition of a metal onto the portion of the surface sing the reduced metal coordination complex.
22. The method of claim 21, wherein electrolessly depositing a metal onto the portion of the surface comprising the reduced metal coordination complex comprises contacting at least the portion of the surface comprising the metal coordination complex with a solution comprising a salt of the metal, a complexing agent and a reducing agent.
23. The method of claim 1, wherein ting a conductive material onto the surface comprises deposition of a non-metallic conductive substance onto the portion of the surface comprising the reduced metal coordination complex. 6252342_4.docx
24. The method of claim 23, wherein the non-metallic tive material is deposited onto the portion of the surface comprising the reduced metal coordination complex by electrostatic dispersion.
25. The method of claim 1, wherein the entire non-conductive ate surface is activated and the metal coordination complex is deposited onto the entire surface.
26. The method of claim 1, wherein the entire non-conductive substrate surface is activated and the metal coordination complex is deposited on a part of the activated surface.
27. The method of claim 7, wherein laser g comprises etching in a pre-determined pattern.
28. A method of forming a conductive layer on a surface, the method being substantially as hereinbefore described with nce to the accompanying drawing and/or Examples. 6252342_4.docx W0 28473 SUBSTITUTE SHEET (RULE 26)
NZ622408A 2011-08-19 2012-08-16 Method of forming a conductive image on a non-conductive surface NZ622408B2 (en)

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US201161525662P 2011-08-19 2011-08-19
US61/525,662 2011-08-19
US201161568736P 2011-12-09 2011-12-09
US61/568,736 2011-12-09
US13/403,797 US8784952B2 (en) 2011-08-19 2012-02-23 Method of forming a conductive image on a non-conductive surface
US13/403,797 2012-02-23
PCT/US2012/051193 WO2013028473A1 (en) 2011-08-19 2012-08-16 Method of forming a conductive image on a non-conductive surface

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