NZ716340B2 - Circuits and substrates fabricated using a method of forming a conductive image on a non-conductive surface - Google Patents

Abstract

Disclosed is a substrate fabricated using a method comprising the steps of: (a) activating at least a portion of a non-conductive substrate surface (10); (b) depositing a metal coordination complex (15) on a part of the activated portion of the surface (10); (c) subjecting the metal coordination complex (15) that is located on the part of the activated portion of the surface (10) to a magnetic field (25) to align molecules of the metal coordination complex (15) with the magnetic field (25) and thereby more deeply injecting the metal coordination complex (15) into the nonconductive substrate (10) than would occur in the step of depositing the metal coordination complex (15); (d) exposing the metal coordination complex (15) to electromagnetic radiation; (e) reducing the metal coordination complex (15) to elemental metal; (f) removing unreduced metal coordination complex (15) from the surface; (g) drying the surface; and (h)depositing a conductive material onto the surface. plex (15) that is located on the part of the activated portion of the surface (10) to a magnetic field (25) to align molecules of the metal coordination complex (15) with the magnetic field (25) and thereby more deeply injecting the metal coordination complex (15) into the nonconductive substrate (10) than would occur in the step of depositing the metal coordination complex (15); (d) exposing the metal coordination complex (15) to electromagnetic radiation; (e) reducing the metal coordination complex (15) to elemental metal; (f) removing unreduced metal coordination complex (15) from the surface; (g) drying the surface; and (h)depositing a conductive material onto the surface.

Description

CIRCUITS AND SUBSTRATES FABRICATED USING A METHOD OF FORMING A CONDUCTIVE IMAGE ON A NON-CONDUCTIVE SURFACE William Wismann CROSS NCE TO RELATED APPLICATIONS This ation is related to and claims the benefit of (1) U.S.

Provisional Patent Application No. 61/525,662, filed in the name of William Wismann on August 19, 2011, (2) U.S. Provisional Patent Application No. 61/568,736, filed in the name of William Wismann on December 9, 2011, and (3) is a continuation of U.S. Patent Application No. ,797, filed in the name of William Wismann on February 23, 2012, all of which are hereby incorporated herein by reference in their entirety. [001a] The t ation has been d out of New Zealand patent application 622408 (NZ 622408). In the description in this present specification reference may be made to subject matter which is not within the scope of the appended claims but relates to subject matter claimed in NZ 622408. That subject matter should be readily fiable by a person skilled in the art and may assist in putting into practice the invention as defined in the presently appended claims.

FIELD This invention relates to the field of electronic device manufacture.

BACKGROUND Conductive images on non-conductive or dielectric surfaces are 8190808_2.docx ubiquitous in today’s technology-driven world. Perhaps the most widely known example of such are the ated 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.

A typical wafer is made out of extremely 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: end-of-line (FEOL) processing and back- end-of-line (BEOL) processing.

FEOL processing refers to the formation of circuits directly in the silicon. The raw wafer is first subjected to epitaxy, 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 tric, traditionally silicon dioxide (SiO2), patterning of the gate, patterning of the source and drain s, and uent implantation or ion of dopants to obtain the desired mentary electrical properties. In dynamic random access memory (DRAM) s, storage capacitors are also fabricated at this time, typically stacked above the access stor.

Once the various semiconductor devices have been created, they must be interconnected to form the desired electrical circuits, which comprise the BEOL portion of the process. BEOL involves creating metal interconnecting wires that are ed by dielectric layers. The insulating material was traditionally a form of silicate glass, SiO2, but other low dielectric constant 8190808_2.docx materials can be used.

The metal interconnecting wires often comprise um. 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 deposited over the exposed wires. The various metal layers are interconnected by etching holes, called vias, in the ting material and depositing tungsten in the holes. This approach is still used in the ation of memory chips such as DRAMs as the number of interconnect levels is small.

More ly, as the number of interconnect levels has increased due to the large number of transistors that now need to be interconnected in a modern microprocessor, the timing delay in the wiring has become significant, prompting a change in wiring al from aluminum to copper and from the silicon dioxides to newer low-K material. 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 tric al 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 trenches 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 simultaneously, 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 r film competes with the available copper wire cross section, formation of the thinnest uous barrier represents one of the greatest g 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 outside the depth of focus of available lithography, interfering with the 8190808_2.docx ability to pattern. CMP (chemical mechanical planarization) is a processing method to achieve such planarization gh dry etch back is still mes employed if the number of interconnect levels is low.

The above process, although described ically with regard to n chip manufacture, is fairly generic for most types of printed circuits, printed circuit boards, antennas, solar cells, solar thin films, nductors 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 ctive 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 substrates. The current invention provides such an additive process. [013a] Alternatively or additionally, what is needed is at least a useful choice for the public.

SUMMARY In one aspect the invention comprises an analog circuit fabricated using a method comprising the steps of: activating at least a portion of a non-conductive substrate surface; depositing a metal coordination complex on a part of the activated n of the surface; subjecting the metal coordination complex that is located on the part of the activated portion of the e to a magnetic field to align molecules of the metal coordination x with the magnetic field and 8190808_2.docx thereby more deeply injecting the metal coordination complex into the nonconductive substrate than would occur in the step of depositing the metal coordination x; exposing the metal coordination complex to electromagnetic radiation; reducing the metal coordination x to elemental metal; ng unreduced metal nation complex from the surface; drying the surface; and depositing a conductive material onto the surface. [014a] In another aspect the invention comprises a digital t fabricated using a method comprising the steps of: activating at least a portion of a non-conductive substrate surface; ting a metal coordination complex on a part of the activated portion of the surface; subjecting the metal coordination complex that is located on the part of the activated portion of the surface to a magnetic field to align molecules of the metal coordination x with the magnetic field and thereby more deeply injecting the metal coordination complex into the nonconductive substrate than would occur in the step of depositing the metal coordination exposing the metal coordination complex to electromagnetic radiation; reducing the metal coordination complex to elemental metal; removing unreduced metal nation complex from the surface; drying the surface; and depositing a conductive material onto the surface. [014b] In another aspect the invention comprises a mixed-signal circuit fabricated using a method comprising the steps of: activating at least a portion of a non-conductive substrate surface; depositing a metal nation complex on a part of the activated portion of the surface; subjecting the metal coordination complex that is located on the part of 8190808_2.docx the activated portion of the surface to a magnetic field to align les of the metal nation complex with the magnetic field and thereby more deeply injecting the metal coordination complex into the nonconductive substrate than would occur in the step of depositing the metal coordination complex; exposing the metal coordination complex to electromagnetic ion; reducing the metal coordination complex to elemental metal; removing unreduced metal coordination complex from the surface; drying the surface; and depositing a tive material onto the surface. [014c] In another aspect the invention comprises an RF circuit fabricated using a method comprising the steps of: activating at least a portion of a non-conductive substrate surface; depositing a metal coordination complex on a part of the ted portion of the surface; subjecting the metal coordination x that is located on the part of the activated portion of the surface to a magnetic field to align molecules of the metal coordination complex with the magnetic field and thereby more deeply injecting the metal nation complex into the nonconductive substrate than would occur in the step of depositing the metal coordination complex; exposing the metal coordination complex to electromagnetic radiation; reducing the metal coordination x to elemental metal; removing unreduced metal coordination complex from the surface; drying the surface; and depositing a conductive material onto the e. [014d] In another aspect the ion comprises a substrate fabricated using a method comprising the steps of: activating at least a portion of a non-conductive substrate surface; depositing a metal coordination complex on a part of the activated portion of the surface; subjecting the metal coordination complex that is located on the part of 8190808_2.docx the activated portion of the surface to a ic field to align molecules of the metal coordination complex with the magnetic field and thereby more deeply injecting the metal coordination complex into the nonconductive substrate than would occur in the step of depositing the metal coordination complex; exposing the metal nation 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. [014e] Further aspects are described and d in NZ . [014f] Described herein is a method of forming a conductive layer on a surface, comprising: activating 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 nation complex from the surface; drying the surface; and depositing a conductive material onto the surface.

In an aspect, activating the substrate surface comprises etching the surface.

In an , g the surface comprises chemical etching.

In an aspect, chemical etching comprises acid g, base etching or oxidative etching.

In an aspect, etching the e comprises mechanical etching. 8190808_2.docx In an aspect, etching the surface comprises plasma etching.

In an aspect, etching the surface comprises laser- etching.

In an aspect, plasma or laser etching comprises etching in a predetermined pattern.

In an aspect, the ic field has a magnetic flux density of at least 1000 gauss.

In an aspect, the magnetic field is orthogonal to the surface.

In an aspect, depositing a metal coordination complex on at least a portion of the surface comprises using a mask.

In an aspect, the mask ses an electronic circuit.

In an , the electronic circuit is selected from the group consisting of an analog circuit, a digital circuit, a mixed-signal circuit and an RF circuit.

Described herein is an analog circuit fabricated using the method described herein.

Described herein is a digital circuit fabricated using the method described herein.

Described herein is a mixed-signal t ated using the method described herein. bed herein is an RF circuit fabricated using the method described herein. 8190808_2.docx In an aspect, exposing the metal coordination complex to electromagnetic radiation ses microwave radiation, infrared radiation, visible light radiation, ultraviolet radiation, X-ray radiation or gamma radiation.

In an aspect, reducing the metal coordination complex to a zero oxidation state metal comprises using a combination of metals and/or catalysts.

In an aspect, removing ced metal coordination complex from the surface comprises washing the surface with a solvent.

In an aspect, drying the surface comprises drying at ambient temperature or drying at elevated temperature.

In an aspect, drying the surface at ambient or elevated temperature comprises using a vacuum chamber.

In an aspect, depositing a conductive material onto the surface ses electrolytic deposition of a metal onto the portion of the surface comprising the reduced metal coordination x.

In an aspect, electrolytic deposition of a metal onto the portion of the surface comprising the reduced metal coordination complex comprises: contacting a ve terminal of a direct t power supply with at least the portion of the surface comprising the reduced metal coordination complex; ing 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 ation thereof; contacting a positive terminal of the direct current power supply with the aqueous solution; ting at least the portion of the surface sing the reduced metal coordination complex with the aqueous solution; and turning on the power supply. 8190808_2.docx In an aspect, ting a conductive material onto the surface comprises electroless deposition of a metal onto the portion of the surface sing the d metal nation complex.

In an aspect, electrolessly depositing a metal onto the portion of the surface comprising the reduced metal coordination x comprises contacting at least the portion of the surface comprising the metal coordination complex with a on comprising a salt of the metal, a complexing agent and a reducing agent.

In an aspect, depositing a conductive material onto the surface ses deposition of a non-metallic conductive substance onto the portion of the surface sing the reduced metal coordination complex.

In an aspect, 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, the entire non-conductive substrate surface is activated and the metal coordination complex is deposited onto the entire surface.

In an aspect, the entire non-conductive substrate surface is activated and the metal coordination complex is deposited on a part of the activated surface.

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 ate 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 surface of the substrate. 8190808_2.docx Discussion It is understood that, with regard to this description and the appended claims, reference to any aspect of this invention made in the singular includes the plural and vice versa unless it is expressly stated or unambiguously clear from the context that such is not ed.

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 imation 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 recognize the ed version 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 ise.

As used herein, the use of “preferred,” “preferably,” or “more preferred,” and the like refers to preferences as they d at the time of filing of this patent application.

As used herein, a “conductive layer” refers to an electrically conductive surface, for example, t limitation, a printed circuit.

As used herein, a onductive substrate” refers to a substrate made of an electrically non-conductive material, sometimes referred to as an insulator or a dielectric. Such materials include, without limitation, minerals such as , alumina, magnesia, zirconia and the like, glass and most plastics.

Specific non-limiting examples include FR4, which is the general grade designation for fiberglass reinforced epoxy resin such as, without limitation, 8190808_2.docx 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 portion thereof of, refers to rendering the surface more amenable to interaction with and subsequent physical or chemical g to another material that is disposed onto the surface of the substrate. In an embodiment of this invention, the other al can comprise a metal coordination complex. In addition, altering the surface properties also refers to rendering the surface 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 al means or a combination of the two.

Mechanical means of ng the surface properties of the substrate include, t limitation, simple abrasion of the surface such as with sandpaper or another abrasive al, rasping the surface with a file, g the surface with a sharp object such as, t limitation, a tool bit, and laser etching. ations 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 contour 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 compared to an object molded using a smooth-surfaced mold. These methods of altering a surface property are well-known 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 etching, base etching, oxidative etching and plasma g. 8190808_2.docx Acid etching, as the name implies, refers to the use of a strong acid such as sulfuric acid, hydrochloric acid and nitric acid. A e of hydrochloric acid with nitric acid produces aqua regia, an ely 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 g and involves the use of a basic nce to alter the topology of the surface of a substrate. Many organic polymers are susceptible to chemical ution with basic substances.

For instance, without limitation, potassium hydroxide will react with ters, polyimides and oxides to alter their e properties. Other materials tible to base etching will be known those skilled in the art. All such materials are within the scope of this invention.

Oxidative 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 g refers to the process of impacting the surface of a substrate with a high-speed stream of a glow discharge 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 further description for the purposes of this invention.

Laser etching is well-known in the art. Briefly, a laser beam is ed at a surface 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 8190808_2.docx surface, the material of the surface is, generally, vaporized thus g 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 involves exposing the surface of the substrate to a fluid that is know of found to soften the e, often with concomitant swelling of the surface. When a 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 tightly bound to the surface, in particular when the coated substrate is dried.

As used herein, "applying an magnetic field" to a substrate surface involves placing a surface of the substrate on or near a source of a magnetic field. The magnetic field may be ted by either a permanent magnet, an electromagnet or a combination thereof. A single magnet or plurality of magnets may be used. The e of the ate 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 " refers to the ted surface of the substrate and "below" refers to the surface opposite the ted surface. If the magnetic field is generated using a permanent , 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 presently preferred permanent magnet is a neodymium magnet. It is also preferred that a permanent 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 surface 15. Permanent magnet 20 is ed 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. 8190808_2.docx 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 complexes 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. Without 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 into the e 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 d magnetic field, the source of the magnetic field is removed.

The metal coordination complex coated substrate is then d to electromagnetic radiation to activate the metal coordination x toward a reducing agent. As used herein, electromagnetic radiation includes virtually the entire spectrum of such, i.e., microwave, infrared, e, iolet, 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 electromagnetic spectrum or, if desired, sensitizer(s) may be added to the complex when it is disposed on the substrate to render the complex ensitive or, if the complex is inherently photosensitive, to render it even more so. As used here, "photosensitive" has its dictionary definition: ive or responsive to light or other radiant energy, which would include each of the types of radiation mentioned above.

Exposure to ion renders a portion of the metal coordination complex susceptible to reduction. The reducing agent will reduce the metal 8190808_2.docx coordination complex to elemental metal. The reducing agent can be any metal- inclusive salt wherein the metal has a reduction ial that is greater, i.e., conventionally has a more negative reduction potential than the metal of the coordination complex. The following chart shows the reduction ial of a number of common substances. Substances higher on the list are capable of reduction of those beneath it. 8190808_2.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 ion step is, of course, insoluble in most ts. Thus, g the surface of the substrate with an appropriate t, which is determined by the composition of the initial metal coordination complex, will remove unexposed complex leaving the metal.

The metal may be evenly dispersed over the surface of the substrate if the surface of the substrate was generally exposed or the metal may form a te pattern if the substrate surface was d through a mask. A mask is simply a material 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 radiation 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 8190808_2.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 ate can be accomplished, without tion, by ting the surface with a solution of a salt of a metal to be deposited in the presence of a complexing agent to keep the metal ions in solution and to stabilize the solution generally. The e with the complexed metal salt in contact with it or at least near the surface is simultaneously or consecutively contacted with an s solution of a reducing 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 concurrently sprayed onto the patterned substrate either from te spray units, the spray streams being directed so as to intersect at or near the substrate surface, or from a single spray unit having separate reservoirs and spray tip orifices, the two streams being mixed as they emerge from the spray tip and impinge on the substrate surface.

The electrodeposition s contemplated herein is well-known in the art and need not be extensively described. In brief, the tal metal image is connected to the negative terminal (cathode) of a direct current power source, which may simply be a y but, more commonly, is a rectifier. The 8190808_2.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 contact with a spray of the solution.

The electrolyte on contains dissolved metal salts of the metal to be plated as well as other ions that render the olyte 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 e, 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 invention, a solution of cations of the metal to be deposited can be prepared and the solution can be sprayed onto the metalized uct.

The conductive material to be coated on the elemental metal image may also comprise a non-metallic conductive substance such as, without limitation, carbon or a tive polymer. Such materials may be deposited on the metal image by techniques such as, without limitation, electrostatic powder g and electrostatic dispersion coating, which may be conducted as a wet (from solvent) or dry s. 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 charged with the opposite charge to that applied to the metal image. In addition, to further ensure that only the metal image is coated, the non- conductive substrate may be grounded to eliminate any possibility of an tive charge developing on the substrate or the substrate may be charged with the same polarity charge as the substance to be ted such that the substance is repelled by the substrate. 8190808_2.docx EXAMPLES Example 1 1. DuPont Kapton PV9103 ide, in small sheets is chemically etched using a mixture of 0.1 N KOH (5.6 grams potassium hydroxide per 1 liter of deionized water (DI)) with a 60% by weight solution of isopropanol alcohol, for 2 to 4 minutes 2. The etched polyimide sheet is rinsed with DI water and dried for 30 minutes in an oven at 100 ºC. 3. 10 grams of ferric um 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 m 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 8190808_2.docx . The masked surface of the polyimide sheet was exposed to an ASC365 iolet light source at full strength for no less than 3 minutes 11. The light source was removed, the mask was separated from the substrate surface and the surface was rinsed for 5 minutes with DI water and then placed in a ethylenediamine tetraacetic acid (EDTA) bath comprising 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 minutes 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 ally etched with Electro-Brits E-prep 102, approximately 5% by volume (40 grams per liter of sodium ide) 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% on of ic acid for 10 seconds and rinsed. 8190808_2.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 nitrate 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 s 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 d 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 minutes. 13. The LCP sheet was then rinsed with DI for 10 minutes and put it into an oven at 40 ºC for 5 s or until dry. 14. The LCP sheet was then placed in a bath comprising Shipley Electroless t 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 removed from the bath, rinsed for 10 8190808_2.docx s 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 darkroom) 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 addition of DI water.

. The mixture was filtered and bottled when cool. 6. 6 drops of the ammonium 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 nated complex solution was sponge brushed thinly on the surface of the sheet (in the darkroom). 8. The FR4 sheet was then place in an oven at 40 ºC for 10 s or until dry. 9. A pull test ed mask was then placed on the treated surface of the FR4 sheet. 8190808_2.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 minutes 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 s 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. 8190808_2.docx CLAUSES 1. A method of forming a tive layer on a surface, sing: activating 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 tive al onto the e. 2. The method of clause 1, wherein activating the substrate surface comprises etching the surface. 3. The method of clause 2, wherein etching the surface comprises chemical etching. 4. The method of clause 3, wherein chemical g comprises acid g, base etching or oxidative etching.

. The method of clause 2, wherein etching the surface ses mechanical etching. 6. The method of clause 2, wherein etching the surface comprises plasma etching. 7. The method of clause 2, wherein etching the surface comprises laseretching. 8. The method of clause 6, wherein plasma or laser etching comprises etching in a pre-determined pattern. 8190808_2.docx 9. The method of clause 1, where the magnetic field has a magnetic flux density of at least 1000 gauss.

. The method of clause 9, wherein the magnetic field is onal to the surface. 11. The method of clause 1, where depositing a metal nation complex on at least a n of the surface comprises using a mask. 12. The method of clause 10, wherein the mask comprises an electronic circuit. 13. The method of clause 12, wherein the electronic circuit is selected from the group consisting of an analog t, a digital circuit, a signal circuit and an RF circuit. 14. An analog circuit fabricated using the method of clause 1.

. A digital circuit fabricated using the method of clause 1. 16. A mixed-signal circuit fabricated using the method of clause 1. 17. An RF circuit fabricated using the method of clause 1. 18. The method of clause 1, wherein exposing the metal coordination complex to electromagnetic radiation comprises ave radiation, infrared radiation, visible light radiation, ultraviolet radiation, X-ray radiation or gamma radiation. 19. The method of clause 1, where reducing the metal coordination complex to a zero oxidation state metal comprises using a combination of metals and/or catalysts.

. The method of clause 1, wherein removing unreduced metal 8190808_2.docx coordination complex from the e comprises washing the surface with a solvent. 21. The method of clause 1, wherein drying the surface comprises drying at ambient temperature or drying at elevated temperature. 22. The method of clause 21, wherein drying the surface at ambient or elevated temperature comprises using a vacuum chamber. 23. The method of clause 1, wherein depositing a conductive material onto the surface comprises electrolytic deposition of a metal onto the portion of the surface comprising the reduced metal nation complex. 24. The method of clause 23, wherein electrolytic deposition of a metal onto the portion of the e comprising the reduced metal coordination complex: contacting a negative terminal of a direct current power supply with at least the portion of the e comprising the reduced metal coordination complex; providing an aqueous solution comprising a salt of the metal to be deposited, an ode 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 complex with the aqueous solution; and turning on the power .

. The method of clause 1, wherein depositing a conductive material onto the surface ses electroless deposition of a metal onto the portion of the surface comprising the reduced metal coordination complex. 26. The method of clause 25, wherein olessly ting a metal onto the portion of the surface comprising the reduced metal coordination complex 8190808_2.docx ses contacting at least the portion of the surface sing the metal nation complex with a solution comprising a salt of the metal, a complexing agent and a reducing agent. 27. The method of clause 1, wherein depositing a conductive material onto the surface comprises deposition of a non-metallic conductive substance onto the portion of the surface comprising the d metal coordination complex. 28. The method of clause 27, wherein the tallic conductive material is deposited onto the portion of the surface comprising the reduced metal coordination complex by electrostatic dispersion. 29. The method of clause 1, wherein the entire non-conductive substrate surface is activated and the metal coordination complex is deposited onto the entire surface.

. The method of clause 1, wherein the entire non-conductive substrate surface is activated and the metal coordination complex is deposited on a part of the activated surface. 8190808_2.docx

Claims (20)

What is claimed:

1. A substrate fabricated using a method comprising the steps of: activating at least a portion of a non-conductive substrate surface; depositing a metal coordination complex on a part of the activated portion of the surface; ting the metal coordination x that is located on the part of the ted portion of the e to a magnetic field to align molecules of the metal coordination complex with the magnetic field and thereby more deeply injecting the metal coordination complex into the nonconductive substrate than would occur in the step of depositing the metal coordination complex; exposing the metal coordination complex to electromagnetic radiation; reducing the metal coordination x to elemental metal; removing unreduced metal coordination complex from the surface; drying the surface; and depositing a conductive material onto the surface.

2. An analog circuit comprising the substrate ing to claim 1.

3. A digital circuit comprising the substrate according to claim 1.

4. A mixed-signal circuit comprising the substrate according to claim 1.

5. An RF t comprising the substrate according to claim 1.

6. The analog circuit according to claim 2, wherein the method further ses the step of: applying the magnetic field during the step of depositing the metal coordination complex.

7. The digital circuit according to claim 3, wherein the method further comprises the step of: applying the magnetic field during the step of depositing the metal coordination complex.

8. The mixed-signal circuit according to claim 4, n the method 8190808_2.docx further comprises the step of: applying the magnetic field during the step of depositing the metal nation complex.

9. The RF circuit according to claim 5, n the method further comprises the step of: applying the magnetic field during the step of depositing the metal coordination complex.

10. The analog circuit according to claim 2, wherein in the step of subjecting the metal nation complex to the magnetic field, ligands of the metal coordination complex are aligned with the magnetic field.

11. The digital circuit according to claim 3, wherein in the step of the subjecting the metal coordination complex to the magnetic field, ligands of the metal coordination complex are aligned with the magnetic field.

12. The mixed-signal t according to claim 4, wherein in the step of subjecting the metal nation complex to the magnetic field, ligands of the metal coordination complex are d with the magnetic field.

13. The RE circuit according to claim 5, wherein in the step of ting the metal coordination complex to the magnetic field, ligands of the metal coordination complex are aligned with the magnetic field.

14. The substrate according to claim 1, wherein the method further comprises the step of: applying the magnetic field during the step of ting the metal coordination complex.

15. The substrate according to claim 1, wherein in the step of subjecting the metal coordination complex to the magnetic field, ligands of the metal nation complex are aligned with the magnetic field.

16. The analog circuit of claim 2, the method being substantially as hereinbefore described with reference to the accompanying drawing and/or Examples. 8190808_2.docx

17. The digital circuit of claim 3, the method being substantially as hereinbefore described with reference to the accompanying drawing and/or Examples.

18. The mixed-signal circuit of claim 4, the method being substantially as hereinbefore described with reference to the accompanying drawing and/or Examples.

19. The RF circuit of claim 5, the method being substantially as hereinbefore described with nce to the accompanying drawing and/or es.

20. The substrate of claim 1, the method being substantially as before described with reference to the accompanying drawing and/or Examples. 8190808_2.docx . _ . 1 , . . . _ . .