Patent Publication Number: US-8529738-B2

Title: In situ plating and etching of materials covered with a surface film

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation-in-part of International Application No. PCT/US06/04329, filed Feb. 8, 2006, which claims priority to U.S. provisional patent application Nos. 60/650,870, filed Feb. 8, 2005; 60/675,114, filed Apr. 25, 2005; and 60/700,877, filed Aug. 3, 2005, all of which are incorporated by reference in their entireties herein. Further, this application claims the benefit of U.S. provisional patent application Nos. 60/815,790, filed Jun. 22, 2006 and 60/845,586, filed Sep. 19, 2006, both of which are also incorporated by reference in their entireties herein. 
    
    
     BACKGROUND OF THE INVENTION 
     The present invention relates to systems and methods for metal plating and etching of substrates. More particularly, the invention relates to metal plating and etching of readily oxidizable substrates or other substrates with thin layers that inhibit plating and etching. 
     Metal plating of articles or base substrates is a common industrial practice. A metal layer may be coated or plated on the surface of an article, for example, for decoration, reflection of light, protection against corrosion, or increased wearing quality. Articles or base substrates, which are made of metal or non-metallic material, may be plated with suitable coating metals using techniques such as electroplating, electroless plating, metal spraying, hot dip galvanizing, vacuum metallization or other available processes. Plating by electrolysis, or electroplating, is a commonly used technique for metal plating because it permits the control of the thickness of the plating. Cadmium, zinc, silver, gold, tin, copper, nickel, and chromium are commonly used plating/coating metals. In immersion or electroless plating, some metals are directly precipitated, without electricity, from chemical solutions onto the surface of the substrates. The silvering of mirrors is a type of plating in which silver is precipitated chemically on glass. Any of the common metals and some nonmetals, e.g., plastics, with suitably prepared (e.g., etched) surfaces can be used as the article or base substrate material. 
     However, some metals (e.g., aluminum and refractory metals like tungsten, tantalum and molybdenum), which have desirable physical or structural properties for use as base substrate material, are extremely difficult to plate by simple immersion plating or electroplating techniques. The difficulty in plating these metals may, for example, be related to the propensity of these metals to oxidize in air, as a result of which an interfering metal-oxide or insulating layer forms on any exposed or etched surface of these metals. The interfering metal-oxide or insulating layer hinders reduction of metal ions, which is required to cause metal plating. Therefore, techniques for metal plating readily-oxidizable materials (such as tungsten, tantalum and aluminum) commonly involve a number of expensive and tedious substrate preparation steps, which are designed to avoid or prevent the formation of surface layers which can interfere with the plating processes. For example, a common technique for metal plating onto an aluminum substrate involves first zincating and then gold plating the aluminum substrate prior to plating the aluminum substrate with a metal of choice. For substrates or articles made from refractory metals such as tantalum and tungsten, the substrate preparation steps prior to metal plating often involve cumbersome high temperature processing steps. 
     The interfering surface oxide layers formed on these readily-oxidizable metals also hinders etching of the surface of these metals, which may be necessary prior to any substrate preparation steps themselves. The surface oxide layer coating prevents the dissolution of the metal under conventional etching conditions. Again, a number of fairly harsh steps are required to prepare the substrate surfaces for etching. See e.g., Modern Electroplating (3rd edition), F. Lowenheim, Ed. John Wiley &amp; Sons Inc. (1974), pp. 591-625. Further discussion of electroless plating of common materials that require multistep processing to achieve metal plating due to presence of interfering surface films may, for example, be found, in Electroless Plating: Fundamentals and Applications, Glenn O. Mallory and Juan B. Hajdu, Eds. American Electroplaters and Surface Finishers Society (1990), pp. 193-204. 
     Consideration is now being given to improving metal plating systems and methods. Attention is particularly directed to simplifying techniques for metal plating of substrates on which interfering surface films form, for example, during conventional metal plating processes or steps. Further, attention is directed to substrate preparation techniques (i.e., removal of native or preformed surface oxide layers) prior to plating or etching action. 
     SUMMARY OF THE INVENTION 
     The present invention provides systems and methods for etching and/or metal plating of substrate materials, which are usually coated with thin surface films (e.g., a native oxide film). The systems and methods may employ several in situ techniques for removing the thin surface film, including direct heating and mechanical removal. The systems and methods may alternatively exploit optical energy absorption to remove or inhibit the thin surface films before etching and/or metal plating of substrate materials. An energy beam (e.g., a laser beam), which is generated by a suitable optical source (e.g., a laser), is directed onto the surface of a substrate. Optical absorption of the directed energy beam can lead to localized heating and/or photodecomposition (also known as ablative photodecomposition) of the thin surface film. 
     The removal of the thin surface film material is, in one preferred embodiment, performed “in situ” while the substrate is immersed in plating or etching solution. After the thin surface film material is removed, the plating or etching solution can act on the exposed substrate surfaces before a thin surface film can re-form or reappear. This in situ technique advantageously avoids exposure of clean substrate surfaces to air, preventing surface oxidation. 
     In a variation of the in situ removal technique, the removal of the thin surface film material from the substrate surface is performed prior to immersion of the substrate in the plating/etching bath. The removal of the thin surface film material may be carried out in normal ambient or in a coating-removal enclosure having a specific inert or reducing atmosphere. The enclosure may be in close proximity or attached to the tank, which holds the bath in which the substrate is subsequently immersed for plating or etching. After removal of the thin surface film or coating, the substrate is transferred, for example, from the enclosure into the plating/etching bath, in a short time before any oxide film can reappear or regrow on the substrate surface. This variation of the removal technique advantageously avoids any significant exposure of clean substrate surfaces to air prior to plating or etching action. The transfer also may be carried out in a reducing or inert atmosphere, for example, when the enclosure is attached to the tank, to avoid all exposure to air prior to plating or etching action. 
     In a further variation of the in-situ removal technique, the oxide-coated substrate is placed in contact with a suitable patterning mask. Surface oxide removal is performed through openings in the contact patterning mask to prepare designated surface pattern regions for plating or etching. A suitable patterning mask may be a photoresist pattern layer, which is applied using conventional photolithoprahic techniques (e.g., using contact or non contact photomasks). For some applications that do not require very precise feature definitions, a suitable patterning mask may, for example, be fabricated by applying masking tape (or any other non-conducting material) directly to the substrate surface to cover or mask surface regions that are not to be plated or etched. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       Further features of the invention, its nature, and various advantages will be more apparent from the following detailed description of the preferred embodiments and the accompanying drawings, wherein like reference characters represent like elements throughout, and in which: 
         FIG. 1   a  is a schematic illustration of an exemplary plating/etching cell arrangement, which is configured for removing an interfering insulating surface film by in situ resistive heat treatment just prior to or during the metal plating or etching of a subject substrate, in accordance with the principles of the present invention. The cell is provided with a counter electrode and pump for circulating an electrolyte or etchant. 
         FIG. 1   b  schematically illustrates details of exemplary electrical contacts and the electrode support structures for the cell arrangement of  FIG. 1   a , in accordance with the principles of the present invention. 
         FIG. 2  is a schematic illustration of another exemplary plating/etching cell arrangement, which is configured for removal of an interfering insulating surface film by laser light treatment just prior to or during the metal plating or etching of a subject substrate, in accordance with the principles of the present invention. The plating/etching cell arrangement includes a moveable holder for moving the substrate relative to the laser light so that different surface portions of the substrate can be treated sequentially. 
         FIG. 3  is a schematic illustration of yet another exemplary plating/etching cell arrangement, which is configured for in situ removal of an interfering insulating surface film by mechanical treatment during the metal plating or etching of a subject substrate, in accordance with the principles of the present invention. The plating/etching cell arrangement includes a scratching or scraping tool for mechanically removing the interfering insulating film from the substrate while the substrate is at least partially submerged in an electrolyte or other plating/etching fluid. 
         FIG. 4  is a schematic illustration of the plating cell arrangement of  FIG. 3 , which has been additionally configured to apply heat to the substrate facing away from the counter electrode, in accordance with the principles of the present invention. 
         FIG. 5  is a schematic illustration of an exemplary plating/etching cell arrangement, which is configured for removal of an interfering surface film on a wire substrate by in situ mechanical stripping during metal plating or etching of the wire substrate, in accordance with the principles of the present invention. The wire substrate, which may be supplied and picked up in a reel-to-reel arrangement, is passed though a knife-edge die which strips the interfering surface film, while submerged in an electrolyte or other plating/etching fluid. 
         FIG. 6  is a schematic illustration of another exemplary plating/etching cell arrangement, which is configured for in situ mechanical stripping of an interfering film on flat stock substrate during metal plating or etching of the flat stock substrate, in accordance with the principles of the present invention. The flat stock substrate is passed though a knife-edge die, which strips the interfering surface film, while the flat stock substrate is submerged in an electrolyte or other plating/etching fluid. 
         FIG. 7  is a schematic illustration of a metal-plated article made from a refractory metal substrate in which the metal plating layer is bonded directly to the substrate material without any intervening substrate modification or seed layers, in accordance with the principles of the present invention. 
         FIG. 8   a  is a schematic illustration of an exemplary plating/etching cell arrangement including a coating-removal enclosure in which inhibiting surface films are mechanically removed from substrate surfaces prior to immersion in a plating or etching bath, in accordance with the principles of the present invention. The coating-removal enclosure may be supplied with an inert or reducing gas atmosphere, and is compatible with reel-to-reel substrate supply and pick-up arrangements. 
         FIG. 8   b  is a schematic illustration of another exemplary plating/etching cell arrangement including a coating-removal enclosure in which substrates are electrically heated in an inert or reducing ambient to remove inhibiting surface films prior to immersion in a plating or etching bath, in accordance with the principles of the present invention. Like the coating-removal enclosure of  FIG. 8   a , the enclosure of  FIG. 8   b  is compatible with reel-to-reel substrate supply and pick-up arrangements. 
         FIG. 8   c  is a schematic illustration of yet another exemplary plating/etching cell arrangement including a coating-removal enclosure in which a substrate is laser irradiated in an inert or reducing ambient to remove inhibiting surface films prior to immersion in a plating or etching bath, in accordance with the principles of the present invention. Like the coating-removal enclosures of  FIGS. 8   a  and  8   b , the enclosure of  FIG. 8   c  is compatible with reel-to-reel substrate supply and pick-up arrangements. 
         FIG. 8   d  is a schematic illustration of an exemplary plating/etching cell arrangement in which inhibiting surface films are mechanically removed from the substrate surfaces in air prior to immersion in a plating or etching bath, in accordance with the principles of the present invention. The cell arrangement is configured with a reel-to-reel substrate supply and pick-up arrangement. 
         FIG. 9  is a schematic illustration of still another exemplary plating/etching cell arrangement including a coating-removal enclosure in which a substrate may be treated to remove inhibiting surface films prior to immersion in a plating or etching bath, in accordance with the principles of the present invention. The coating removal enclosure is mounted directly above the plating/etching bath and may be configured to treat individual substrate pieces one by one, or to treat a continuous reel-to-reel supply of substrates. 
         FIG. 10  is a schematic illustration of a composite substrate, which may be plated or etched in accordance with the principles of the present invention. The composite substrate has an outer material layer supported on a base substrate. The outer layer is coated with an inhibiting coating film which is removed prior to plating or etching of the composite substrate. 
         FIG. 11  is a schematic illustration of an exemplary plating/etching cell arrangement, which is configured for removal of an interfering insulating surface film by induction heating or microwave irradiation just prior to metal plating or etching of a subject substrate, in accordance with the principles of the present invention. 
         FIG. 12  is a schematic illustration of an exemplary induction heating arrangement, which may be used to remove inhibiting surface films on substrates with trenched surface topography such as silicon substrate wafers, in accordance with the principles of the present invention. 
         FIG. 13  is a schematic illustration of another arrangement, in which an ion beam is used to remove inhibiting surface films on substrates with trenched surface topography such as silicon substrate wafers, in accordance with the principles of the present invention. 
         FIG. 14  is a schematic illustration of an exemplary reel-to-reel plating/etching cell arrangement having a substrate preparation chamber in which induction heating or magnetron radiation is used for removal of interfering surface films, in accordance with the principles of the present invention. 
         FIG. 15  is a schematic illustration of a stamping press, which is used to prepare shaped substrates in an oxide-layer free condition suitable for plating or etching action, in accordance with the principles of the present invention. 
         FIGS. 16 and 17  are schematic illustrations of exemplary plating/etching cell arrangements in which separate tanks are provided for removal of interfering insulating surface films on a substrate and for plating the substrate, in accordance with the principles of the present invention. 
         FIG. 18  is a schematic illustration of another exemplary plating/etching cell arrangement for obtaining electrolytic plating or etching of individual substrates having inhibiting surface films, in accordance with the principles of the present invention. The plating/etching cell is configured so that a high voltage pulse (or a series of pulses) is applied to the substrate to remove the interfering inhibiting surface films and then a low voltage signal, which can be a cw or a modulated cw signal, is applied to activate the desired plating and/or etching processes. 
         FIG. 19  is a schematic illustration of yet another exemplary plating/etching cell arrangement for obtaining electrolytic plating or etching of long wire or flat sheet stock substrates having inhibiting surface films, in accordance with the principles of the present invention. The plating/etching cell arrangement includes a reel-to-reel material handling system. Like the plating/etching cell arrangement of  FIG. 18 , the plating/etching cell is configured so that a high voltage pulse can be applied to the substrate to remove the interfering or inhibiting surface films, and then a low voltage signal can be applied to activate the desired plating and/or etching processes. 
         FIGS. 20 and 21  are schematic illustrations of the alternating high voltage and low voltage pulses that can be used in electroplating or etching processes in the cell arrangements of  FIGS. 18 and 19 , respectively. 
         FIG. 22  is a schematic illustration of still another exemplary plating/etching cell arrangement for obtaining electrolytic plating or etching of substrates having inhibiting surface films, in accordance with the principles of the present invention. The plating/etching cell arrangement employs an electrolyte jet to co-linearly guide a high intensity laser beam for removal of the inhibiting surface films. 
         FIG. 23  is a schematic illustration of a further exemplary plating/etching cell arrangement for obtaining electrolytic plating or etching of substrates having inhibiting surface films, in accordance with the principles of the present invention. The plating/etching cell arrangement uses a high intensity laser beam for removal of the inhibiting surface films for substrate surface portions under a defined volume of electrolyte. 
         FIG. 24  is a schematic illustration of a sample which a contact patterning mask disposed thereon. The contact mask may be a positive or negative photo resist photo resist layer which patterned using photolithography. Plating and/or etching of the substrate occurs in the pattern openings from which inhibiting surface coatings are removed by the in-situ removal techniques of the present invention. 
         FIG. 25   a  is a schematic illustration of the voltage pulse applied between the counter electrode and the substrate of  FIG. 24  while the latter is immersed in an electrolyte cell ( FIG. 25   b ) in order to remove inhibiting surface coatings from the substrate surface in the pattern opening regions, in accordance with the principles of the present invention. 
         FIG. 26  is a schematic illustration of the electrolyte cell of  FIG. 25   b  now used to apply a small voltage for the purpose of plating or etching the substrate surface in the pattern opening regions from which inhibiting oxide layers have been removed by application of the voltage pulse of  FIG. 25   a.    
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention provides systems and methods for metal plating and etching of substrates that are covered by interfering surface films. The plating and etching methods involve in situ removal of the interfering surface films or surface preparation in such a way that plating/etching becomes possible. The in situ removal of the interfering surface films may be obtained by in situ application of heat, laser light, or mechanical abrasion, or by similar ex situ methods including, for example, placing the substrate in a reducing gas atmosphere. Accordingly, various plating/etching cell arrangements are provided for in situ application of resistive heating, laser light, mechanical abrasion, or reducing gas to the subject substrate just prior to or even as the subject substrate is undergoing etching or plating processes. 
     The invention enables convenient manufacture of metal-plated articles that are made from structurally desirable substrate materials, which are readily oxidizable (e.g., aluminum, and refractory metals). For these metal-plated articles, the metal plating is deposited on or bonded directly to the underlying substrate material dispensing with the need for intermediate substrate modification or seed layers. The invention, for example, enables manufacture of metal-plated aluminum articles in which the metal coating (e.g., nickel) is deposited directly on the aluminum substrate without any intervening zinc or gold seed layers. 
     It is well known that many materials, particularly metals develop an oxide coating or may have some other form of a thin surface layer, which may act as a protective coating. For those cases, it is necessary to remove the oxide or coating in some manner prior to subjecting the material to plating or etching. The removal of such surface layers is necessary for electroplating, electroless plating, immersion plating, electro etching and chemical etching of the material. The various plating/etching systems or arrangements described herein are designed to remove the protective coatings either while or just before the materials are submerged in the electrolyte, which is used for carrying out the desired plating/etching processes. These plating/etching systems or arrangements allow removal of interfering coatings or surface films on a substrate (e.g., where the coating or surface film is a naturally grown oxide) without requiring any subsequent exposure, or at least any significant subsequent exposure, of the substrate to air prior to placing it in a plating/etching cell. Some of the plating/etching systems are designed so that suitable preprocessing or coating removal steps are carried out in close proximity to the plating/etching bath, either in air or in a controlled atmosphere enclosure. Further, the plating/cell systems are designed to reduce and simplify the number of processing steps common in conventional metal plating/etching processes that are performed in separate baths, tanks or ovens, and in particular to avoid the cumbersome high temperature processing steps. 
     All metallization/etching process steps can take place in situ or immediately after oxide removal so that there is no significant exposure of the substrate to air between the oxide removal and the plating/etching process steps. The inventive processes avoid conventional expensive and somewhat cumbersome coating removal steps such as are presently required in plating onto, for example, an aluminum substrate. 
     Conventional procedures for metal plating aluminum substrates involve a number of steps to overcome the deleterious effects of aluminum oxide coatings that form on exposed aluminum surfaces. These steps may include zincating followed by gold plating before the metal of choice can be plated onto the aluminum substrate. By application of the present invention, interfering aluminum oxide materials can be readily removed in situ by any of the several techniques described herein, which avoid exposing the substrate material to air (or oxygen) or limit such exposure to less than a few seconds. Short exposures to air of about 1 to 10 seconds have been shown to be benign with respect to plating and etching quality. Thus, plating and etching steps may be initiated immediately or within 1-10 seconds after the interfering coating materials on the aluminum substrate are removed. This in situ processing also may be similarly advantageous for metal plating or etching of refractory metal substrates such as tungsten, tantalum, titanium, molybdenum and rhenium. 
     An exemplary plating/cell arrangement or system, which is designed for in situ processing of difficult substrates (i.e., substrates whose outer surfaces are coated by an interfering film that makes direct plating or etching difficult or impossible), may include a fluid-holding tank which can hold a fluid electrolyte (e.g., copper sulfate, nickel sulfate or other chemical solutions), an electroless plating solution (e.g., electroless gold) or a chemical etchant (e.g., hydrogen fluoride, sodium hydroxide or the like). The tank may be suitably sized so that the subject substrate (which is preferably electrically conductive) can be fully submerged or partially submerged in the fluid. This exemplary plating/cell arrangement or system may be modified to include an enclosure in close proximity or attached to the fluid-holding tank. This enclosure may be used for substrate preprocessing steps including coating removal steps prior to submerging the substrate in the fluid tank. 
     In one version of plating/etching cell arrangement, heat is applied to the substrate while submerged in the plating/etching solution to remove the offending film or coating from the surfaces of the substrate. The heat may be applied as resistive heat, which is locally generated by passing a high current through the substrate. The high current flow may be intermittent. A first voltage/current source, whose leads are connected to opposite ends of the substrate, is provided for this purpose. The voltage/current source may be any suitable pulser or pulsed voltage source that can produce a high current. Suitable pulsers produce pulses that are that are greater than 100 ps wide. The resistive or Joule heating due to the passage of current within the substrate serve to heat the substrate, whereby this heat can lead to dissolution or disintegration of the offending coating. The offending coating may be removed possibly by ablation, melting, or cracking due to differential thermal expansion. Once the coating has been removed and the pulser is no longer operating, the substrate may remain free of coating in the plating or etching fluid free of coating for at least about 0.1 second, but often for a much longer time on the order of minutes. 
     In a variation of the inventive processes, coating removal steps, which may be similar to the heat, mechanical or other coating removal steps described above, may be performed before submerging the substrate in the fluid tank. For such processes, the plating/etching cell system or arrangement may be provided with a separate enclosure in close proximity or attached to the fluid tank. The separate enclosure may have a controlled atmosphere, which can be beneficial to the coating removal process. For example, a reducing gas (e.g., HF gas) atmosphere may be used to remove an offending substrate coating (e.g., an oxide coating) by chemical reduction of the coating. Further, for example, an inert gas atmosphere may be used to hinder oxide regrowth during heat or mechanical coating removal steps. In some instances when mechanical removal of the coating can be successfully achieved in an air ambient, the provision of a separate coating removal enclosure in the plating/etching cell arrangement may be unnecessary. 
     In any of the plating/etching cell systems or arrangements including arrangements in which resistive Joule heating is utilized for removing a coating while the substrate is submerged in the fluid tank, a coating-free substrate can act as a working electrode while submerged in the fluid. A suitably positioned counter electrode may be submerged in the tank fluid for conducting electrolytic metal plating or etching. A second voltage/current source may be connected between the counter electrode and the substrate to provide current for electrolytic action. In the case where the fluid is an electrolyte, the second voltage/current source may be activated at suitable times to cause electrolytic plating or etching of the substrate when the substrate surface is free of the offending coating. Thus steady (continuous wave) or pulse plating and etching can be accomplished. 
     In a typical electroplating/electroetching process using the present invention in which both the coating removal process and the plating/etching process occur within the plating bath, the second source of voltage may be applied immediately after the current pulse applied by the first voltage source (used for resistive Joule heating) is terminated. Alternatively, the second voltage/current source may be activated even before or during the application of the current pulse to remove the substrate coating. In instances where the fluid in the tank is an electrolyte, it also may be possible to obtain exchange plating (e.g., immersion plating) without the use of the second voltage source for certain electrolyte and substrate combinations. If the electrolyte fluid contains a more noble metal than the substrate material then, once the offending coating is removed from the substrate surface, the more noble metal atom will plate or deposit on the surface by replacing an exposed substrate surface atom. 
     The plating/etching cell arrangement also may be used for an electroless plating (using a fluid which is an electroless plating solution). In such application, a catalyst in the electroless solution leads to plating without any applied voltage to the substrate electrode. Accordingly, it is not necessary to use the counter electrode and second voltage source to produce plating. Similarly, when a chemical etchant is used as the tank fluid, etching of the substrate may readily occur without the use of the counter electrode or second voltage source once the surface coating is removed by heat or mechanical treatment. 
     In yet another version of the in situ plating/etching cell arrangement, the first voltage/current source, which is used to heat the substrate for in situ removal of the offending coating layers, may be replaced as a heat energy source by any suitable energy beam that can penetrate the fluid or the gas in the enclosure of the alternate embodiment to reach the substrate surface. The energy beam (e.g., a laser beam) may be generated by a laser. The laser beam may be directed onto the substrate surface through an optical fiber or an optical wave-guide (e.g., a light pipe). Alternatively, the laser beam may, in certain instances, be directed onto the substrate through the electrolyte without the use of a light pipe or optical fiber. 
     Similar localized surface heating may occur with the use of either the voltage source or the laser beam as the heat or photoablative energy source for removing the substrate coating while the substrate is submerged or is in the preprocessing enclosure. The plating/etching cell arrangement may be configured with a suitable fluid stirring mechanism to mitigate any local boiling of the fluid or bubble formation in contact with the substrate. For example, a circulating flow system using pump may be used as a fluid stirring mechanism. The circulating flow system may be pressurized by way of the pump and use gravity flow to form a complete closed system for agitating the fluid. Alternatively or additionally, a mechanical magnetic stirrer may be placed within the fluid containing tank to maintain fluid agitation as is well known to those skilled in the art. 
     In an alternate version of the plating/etching cell arrangement, a movable scraping or abrasion tool is provided to remove the offending coating by applying mechanical force to the substrate. The scraping or abrasion tool may be scanned across the substrate to remove the substrate&#39;s coating. Mechanical removal of the offending coating may be in addition or as an alternate to the heat-based removal (i.e., using the first voltage source or the energy source to remove the coating of the substrate in situ). 
     An exemplary scraping or abrasion tool may be a mechanical scribe with a sharpened end, which is placed in intimate contact with the substrate surface. In operation, the scribe mechanically penetrates the coating. The mechanical scribe may be driven by a motorized moveable arm, which is preferably computer controlled. As the scribe traverses the areal dimensions of the substrate, the coating is removed from the substrate surface. Removal of the coating allows plating and etching of the substrate surface to occur immediately thereafter, while the scribe and the substrate are submerged in the plating/etching solution or, alternatively, while the scribe and substrate are positioned in the preprocessing enclosure. 
     In some versions of the plating/etching cell arrangement in which the offending coating is removed within the plating/etching bath, the mechanical scribe may be used in conjunction with the first voltage source to remove a coating by application of both resistive (Joule) heating and mechanical force to the substrate surface. In such versions, the mechanical scribe may be made from conducting material, which allows localized current to flow from the scribe to the substrate. In a preferred embodiment of such a version of the plating/etching cell arrangement, the mechanical scribe is disposed to make contact with the back of the substrate (which may be sheet or flat stock). In this configuration, current that is supplied from the first voltage source flows through the substrate and heats the front of the substrate to remove the coating on the front surface of the substrate to be plated or etched (i.e. the surface facing the counter electrode). 
     The in situ plating/etching cell arrangements may be configured to operate with reel-to-reel material handling systems that are commonly used in industrial processing of long lengths of wire or sheet flat stock. In these reel-to reel material handling systems, the unprocessed substrates (i.e., long length of wire or sheet flat stock) are wound on a donor reel and fed into the processing fluid (tank fluid) by a series of support wheels. Processed substrates are similarly picked up by a series of wheels and wound on a mechanically driven take-up reel. The inventive in situ plating/etching cell arrangements may be provided with suitable scrapers for mechanically removing the offending coating on the substrate surface in situ in the processing fluid or in a small preprocessing enclosure in close proximity to the fluid. For example, the substrates may be driven or pulled through a die that removes the coating by way of a sharpened inner peripheral die surface (i.e. a knife edge). The substrate feed rate may be adjusted by suitably setting the speed of the reels. The substrate feed rate for the plating/etching processes may be selected so that the wire or flat stock substrates remain submerged in the plating/etching tank fluid for at least 0.1 s, as the substrates are pulled through the die using the mechanically driven take-up reel. The shape of the die (e.g., circular or rectangular) may be designed in consideration of the shape of the substrate material (e.g., wire or flat stock). 
     In some versions of the plating/etching cell arrangements, the die structures may be used in conjunction with the first source of voltage to apply heat to wire or flat stock substrates as they pass through the die. For example, opposite ends of a die may be used to pass current and to cause heating as the wire or flat stock passes through the die. This heating mechanism may be used as an alternate or an additional mechanism for removal of surface coatings. In another embodiment, heat may be generated directly in the wire or flat stock by contacting a voltage source by means of sliding contacts to the wire/flat stock directly, thereby using the resistance of the wire/flat stock in conjunction with current flow to generate the necessary heat to remove the coating. 
     After removal of surface coatings using the die, a second voltage can be applied to the wire or flat stock substrate across from a counter electrode to cause electroplating or electroetching. 
     Examples of plating/etching processes and cell arrangements are further described herein with reference to  FIGS. 1   a ,  1   b ,  2 - 6 ,  8   a - 8   d ,  9 , and  11 - 17 . 
       FIG. 1   a  shows an exemplary plating/etching cell arrangement  100  for in situ removal of interfering surface coating during plating/etching of substrates  103  in a plating tank or vessel  101 . Tank  101  contains an electrolyte  102 , which can be either plating or etching bath. The substrate material to be plated or etched (i.e. substrate  103 ) is submerged in electrolyte  102 . 
     In general, a plating bath may be an electroless, electroplating or immersion plating or other chemical solution. For etching, the bath may be a chemical etchant such as sodium hydroxide or any other etchant known to those skilled in the art. For electroetching, the etchant may, for example, be a copper sulfate solution. Plating/etching cell arrangement  100  may be provided with an optional counter electrode  104 , which is used only for those applications that utilize either electroplating or electroetching. For immersion plating and electroless plating as well as for chemical etching, use of this electrode is unnecessary. A galvanostat  105  may provide the required electrolytic current for electroplating and electroetching. A simple voltage/current supply may also be used in its place. It will be understood that for electroless and immersion plating as well as for chemical etching, galvanostat  105  and counter electrode  104  need not be used. 
     As an initial step in the plating/etching process, a high current pulse is passed through substrate  103  using a first source of current/voltage (i.e. pulse generator  109 ). Pulse generator  109 , which may be connected across opposite ends of substrate  103  by wires  110  and  111 , supplies current pulses through substrate  103 . Pulse generator  109  may be any suitable current source capable of generating current pulses, which, for example, have spans ranging from tens of pico seconds to continuous wave (CW). The current pulses may be designed to heat substrate  103  or its surfaces while it is immersed in  102 . Substrates  103  or its surfaces may be heated sufficiently by the current pulses so that the interfering surface coating is removed. For electroplating and electroetching, a second source of voltage/current is provided by source  113 . Source  113  may be utilized prior to the heating current pulse applied by pulse generator  109 , concurrently, or at any time thereafter. 
     A fluid circulation system may be set up to agitate the fluid contained in tank  101  to avoid or prevent boiling or bubbling in the fluid at the surfaces of substrate  103 , which may be induced by localized heating caused by passage of the current pulse. The circulation system may include a pump  106  with an input  107  to tank  101 , and a drain  108 . 
       FIG. 1   b  shows a more detailed view an exemplary fixture assembly designed to hold substrate  103  in tank  101 . The fixture assembly includes a pair of metallic posts  1001 , each of which is made from two separate metal sections  1003  and  1004 . Metal sections  1003  and  1004  may be rectangular in shape and may be held together by mechanically (e.g., by bolts  1002  with  1003  clamped between sections  1003  and  1004 ). Metallic posts  1001  may be fastened to a base plate (not shown) that allows posts  1001  to rest on the bottom of tank  101 . Pulser  109  may be electrically connected to substrate  103  by a pair of connecting wires  110  and  111  running along substrate support posts  1001 . A similar fixture assembly may be used to hold counter electrode  104  when such an electrode is used. The dimensions of metal sections  1003  and  1004  may be selected so that their widths  1005  are small compared to the distance between them. Posts  1001  may have any suitable thickness (e.g., of the order of 1-5 mm). Posts  1001  may be made of material, which preferably has high electrical conductivity (e.g., copper posts for copper plating/etching). An insulating sleeve may enclose portions of post  1001  below substrate  103  to avoid plating or etching of post  1001  itself. It will be understood that the fixture assembly shown in  FIG. 1   b  is exemplary, and that one skilled in the art can readily design alternative fixture assemblies. 
       FIG. 2  shows another exemplary plating/etching cell arrangement  200 , in which a laser  207  is exploited to irradiate substrate  203  to be etched or plated. In plating/etching cell arrangement  200 , substrate  203  may be at least partially submerged in an electrolyte or other plating/etching solution  202  contained within a tank  201 . A counter electrode  204  for electroplating and electroetching is also submerged in solution  202  in tank  201 . A galvanostat or other voltage/current supply  205  may be connected via wires  209  and  210  to impose an electric potential difference between counter electrode  204  and substrate  203 . Counter electrode  204  and galvanostat  205  are not used when plating/etching cell arrangement  200  is used for electroless, immersion plating or chemical etching of substrate  203 . 
     Laser  207 , which is disposed external to tank  201 , may be configured so that its output light is directed into a light pipe or light fiber  206  extending into tank  201 . Light fiber  206  may be suitably oriented so that the laser light output is incident on substrate  203 . Laser  207  may be suitably pulsed to generate light pulses with pulse widths (e.g., ranging from a few ps to hundreds of microseconds). For some applications longer pulses extending to cw operation may be used. A laser voltage control unit  208  may be used to set the pulse width and pulse intensity of laser  207 . Laser  207  may have a laser wavelength in the range of about 0.1-10 micrometers. Laser  207  may, for example, be a near infrared or infrared laser emitting radiation at wavelengths that are suitable for absorption in and heating of the substrates. The intensity and duration of the laser light incident on substrate  203  may be theoretically or empirically designed to remove coatings from the surface of substrate  203  by heating. The coatings/substrate may be sufficiently heated to bring about coating removal by ablation, differential expansion of the coating and the substrate leading to cracking of the coating, melting or any by other mechanism. Alternatively, laser  207  may be an ultraviolet laser emitting radiation at wavelengths that are suitable for photoablative decomposition and removal of the inhibiting layer without substantial heating of the substrates. 
     Substrate  203  may be mounted on a moveable arm  211  assembly, which may be operated by a computer (not shown) to move substrate  203 , for example, in vertical and horizontal directions. By coordinating the pulsing of laser  207  with the movement of substrate  203 , patterned coating-removal, plating or etching of substrate  203  can be obtained. The degree of etching or plating of substrate  203  may be controlled by varying the intensity of laser  207 , for example, by using voltage control unit  208  after the coating has been removed. Additional contrast in the pattern on substrate  203  may be achieved by making counter electrode  204  comparable in diameter to that of light fiber  206  to limit the region of plating as a function of position of substrate  203 . Suitable contrast in the electroplating/etching patterns on substrate  203  also may be obtained by controlling the voltage between counter electrode  204  and substrate  203  as arm  211  is set into motion. For this purpose, galvanostat  205  may be programmed using any suitable computer or microprocessor (not shown). Laser light from laser  207  may also be aimed directly at the substrate  203  without the use of fiber  206 . 
       FIG. 3  shows another exemplary plating/etching cell arrangement  300 , in which a sharp probe or pointed scribe  306  is used to remove the surface coatings on substrate  303 , while the latter is submerged in the plating/etching solution  302  in tank  301 . Solution  302  may be an electrolyte or a process liquid used to cause plating or etching for cases where no external voltage need be supplied to a counter electrode. In tank  301 , electrolyte (or process liquid)  302  at least partially covers substrate  303 . Sharp probe or pointed scribe  306  may be mounted on moveable arm  307 , which can be set in motion by a translation motor and computer (not shown). Sharp probe or pointed scribe  306  may be spring loaded or biased so that it is in mechanical contact with substrate  303 . The contact pressures may be suitably set so that movement of scribe  306  across the surface of substrate  303  by arm  307  results in removal of coating or oxide layers on substrate  303 . 
     In plating/etching cell arrangement  300 , an optional counter electrode  304  is attached to a galvanostat or voltage/current supply  305 . For electroplating or electroetching of substrate  303 , a voltage can be applied between counter electrode  304  and substrate  303  before, during, or after moving scribe  306  along the surface of the substrate  303 . It will be understood that for electroless, immersion plating and chemical etching processes, galvanostat  305  and counter electrode  304  are not needed or activated. 
       FIG. 4  shows another plating/etching cell arrangement  400 , in which a sharp probe or pointed scribe  410  is used to deliver an electrical current generated by a high current pulser  405  for passage through substrate  403  (and its surface coatings), while the latter is submerged in the plating/etching solution  402  in tank  401 . The electrical current pulses may be designed to dissipate and resistively heat the surface coatings on substrate  403  to induce their removal. 
     In plating/etching cell arrangement  400 , pointed scribe  410  is spring loaded and may rest on either the front or back surface of substrate  403 . In the example shown, pointed scribe  410  rests on the back surface of substrate  403 . Further, pointed scribe  410  may be mounted on moveable arm  406  so that it can be moved along the surface of substrate  403  in a controlled manner (using, for example, a controller and computer (not shown)). An optional insulation material  407  may cover portions of moveable arm  406  to isolate those portions electrically or chemically. As arm  406  together with spring loaded scribe  410  is moved along the back of substrate  403 , a pulser  405  can deliver a pulse of current or a cw current (depending on the settings of pulser  405 ) through scribe  410 . For this purpose, current pulser  405  may be connected to pointed scribe  410  and to substrate  403 , by connecting wires  411  and  412 , respectively. The current transmission through the point of contact of scribe  410  on the back of substrate  403  results in localized heating to remove localized regions of coating on both the front and back surface of  403 . 
     Counter electrode  404 , which faces the front surface of substrate  403 , may be operated in conjunction with galvanostat or voltage source  408  at any time during the coating removal process to cause plating or etching of front surface regions of substrate  403 . These front surface regions correspond to regions of the back of substrate  403  where scribe  410  has delivered current. It will be understood that for electroless, immersion plating and chemical etching, galvanostat  408  and counter electrode  404  are not needed or activated. 
     The plating/etching cell arrangements may be adapted for use with common industrial material handling systems (e.g., reel-to-reel systems for wire and flat stock substrates).  FIG. 5  shows a plating/etching cell arrangement  500 , which is configured for processing wire substrates  513 . Plating/etching cell arrangement  500  includes a tank  501  for holding electrolyte or other plating/etching chemical solutions  502 . A die with a sharp inner edge  503  rests on a die support post  505  within tank  501 . Coated or partially coated (e.g., oxidized) wire substrate  513 , which is used as raw material, is wound on a donor reel  506 . From reel  506 , wire  513  is guided by a set of guide wheels  511  into tank  501  containing processing fluids or solutions (e.g., electrolyte  502 ). Wire  513  is pulled or drawn through a die  503  having knife-edges for stripping or scraping undesirable coating material from the wire substrate surface. An exemplary annular design of die  503  is shown in the inset in  FIG. 5 . Exemplary die  503  may have split annular rings  509 , which are clamped (e.g., with one or more screws  510 ) around wire substrate  513 . Wire substrate  513 , which is passed through die  503 , also may be passed through a similar hole or opening in counter electrode  504  (for applications involving electroplating or electroetching) to facilitate continuous movement of wire substrate  513  through tank  501 . Additional guide wheels  511  may direct processed wire substrates  513  out of tank  501  onto a take-up reel  507 . Die  503  may have a sharp inner circumferential portion (e.g. a knife edge  514 ) designed to scrape the surface of passing wire substrate  513  to remove any surface coatings so that unhindered plating or etching of the wire substrate material can take place. The rate at which wire substrate  513  is processed through plating/etching cell arrangement  500  may depend in part on the rotation speeds of reels  506  and  507 . The rotation speeds of reels  506  and  507  may be controlled, for example, by a computer-controlled drive motor (not shown) or by any other suitable conventional mechanical mechanisms. For electroplating and electroetching processes conducted in plating/etching cell arrangement  500 , a galvanostat  508  (or any other suitable current/voltage source) may be connected to the die  513  and a counter electrode  504  using connecting wires  514  and  512 , respectively. 
       FIG. 6  shows a plating/etching cell arrangement  600 , which is configured for processing flat stock substrate  615 . Plating/etching cell arrangement  600  includes a tank  601  for holding electrolyte or other plating/etching fluid  602 . A die with a sharp inner edge  603  rests on a die support post  605  within tank  601 . Coated or partially coated (oxidized) flat stock substrate  615  may be fed from a donor reel  605  over a set of guide rollers  606  into tank  601 . In tank  601 , flat stock substrate  615  is pulled or driven through a die  608  with a rectangular opening. Die  608  may be mounted on support  621  disposed on the bottom of tank  601 . Die  608  may have knife-edges or blades disposed in the rectangular opening for stripping or scraping undesirable coating material from the flat stock substrate surface. For electrolytic plating or etching processes, the cell arrangement  600  may be provided with a slotted counter electrode  604  to facilitate passage of processed flat stock substrate  615  through tank  601  onto take-up reel  607 . A galvanostat (voltage/current source)  603  may be connected to die  608  and counter electrode  604  by suitable wires  611  and  612 , respectively. 
     An exemplary design of die  608  is shown in the inset in  FIG. 6 . Die  608  may be assembled from two split sections  609  and  610  that are held together by bolts  611 . The dimensions of the rectangular opening in die  608  may be selected so that scraping blade  620  acts against the surface of flat stock substrate  615  passing through the opening and mechanically removes coating or oxide materials, which may be present on the surface. 
     In some applications, die  503  and die  608  in plating/etching cell arrangements  500  and  600 , respectively, may additionally or alternatively be employed as heaters to provide energy pulses for heat removal of the coating or oxides on the in-process wire or flat stock substrates. In such applications, the dies may be suitably modified and connected to a voltage/current source to deliver current pulses to the substrate, for example, in a manner similar to the one previously described with reference to plating/etching cell arrangement  100  ( FIG. 1   a ). 
       FIG. 7  shows in partial cross-section the layered structure of a metal-plated article  700 , which may be fabricated using, for example, plating/arrangement  600 . Metal-plated article  700  includes a flat stock substrate core  710  made of readily oxidizing material (e.g., aluminum or a refractory metal). A metal plated layer  720  is disposed directly on the surfaces of core  710 , any inhibiting or interfering surface coating having been removed. Metal plated layer  720  may be any desired plating material (e.g. nickel, silver, gold, copper, cadmium, etc.). 
     It will be understood that metal plated layer  720  may be formed by exchange plating from the chemical solution, which can take place after in-situ removal of inhibiting or interfering surface coatings by application of heat pulses or abrading action ( FIGS. 1-7 ). Additional electroplating using a voltage supply or potentiostat may not be required when the usually very thin coatings obtained by exchange plating are sufficient, for example, by design of metal-plated article  700 . 
       FIGS. 8   a - 8   d  and  9  show plating/etching cell arrangements  800  and  900 , in which coating removal steps are performed before the substrates are immersed in plating/etching baths  801  and  901 , respectively. These arrangements may include controlled atmosphere enclosures  803  or  903  in which the coating removal steps and/or other substrate preprocessing steps may be performed. The enclosures may be in close physical proximity to the plating/etching baths (e.g., enclosure  803   FIGS. 8   a - 8   c ) or mounted directly on the plating/etching baths (enclosure  904 ,  FIG. 9 ).  FIG. 8   d  shows a plating/etching cell arrangement  800  in which a mechanical coating removal step can be performed in ambient air just prior to immersion of the substrate in the plating/etching bath  800 . 
     With reference to  FIG. 8   a , plating/cell arrangement  800 , which includes a plating/etching bath tank  801  holding an electrolyte  8001  and a controlled atmosphere enclosure  803 , is configured for operation with a reel-to-reel substrate material handling system. The material handling system may include supply and pick-up reels  805  and  809 , respectively. Raw wire or flat stock  806  unwound from supply reel  805  is passed through enclosure  803  before being processed in plating/etching bath tank  801  and being rewound on pick-up reel  809 . The walls of enclosure  803  may be provided with slots or openings of suitable dimensions (not shown) to accommodate the passage of raw wire or flat stock  806  through enclosure  803 . A mechanical abrasion die  804  may be located in enclosure  803  to provide the necessary mechanical contact with wire or flat stock  806  to remove the unwanted coating from the surfaces of stock  806 , for example, by friction. The atmosphere in enclosure  803  may be controlled during the coating removal processes. Inert or non-oxidizing atmospheres made of gases such as nitrogen, helium, or argon may be desirable to prevent or hinder reoxidation of cleaned substrate surfaces. The suitable specific gas or gases may be supplied from a gas source  802  connected to enclosure  803 . In operation, undesired coatings are stripped from the surface of wire or flat feed stock  806  in enclosure  803  by mechanical die  804  so that stock  806 , which passes into plating/etching bath  801 , has a clean surface. 
     Mechanical abrasion die  804  also may serve as an electrical contact to wire or flat stock  806 . A voltage source or potentiostat  807  connected to abrasion die  804  may be used to apply an electrical voltage to wire or flat stock  806  across from counter electrode  808  to obtain electroplating or etching action as coating-free wire or flat stock  806  passes through electrolyte  8001 . Processed wire or flat stock  806  is drawn out of electrolyte  8001  and wound on pick-up reel  809 . 
       FIG. 8   b  shows a variation of the plating/etching cell arrangements  800  in which mechanical abrasion die  804  is replaced by a heating arrangement  8041 . Heating arrangement  8041  is configured to make a pair of electrical contacts  8042  with wire or flat stock  806  as the stock passes through enclosure  803 . A voltage applied across the pair of electrical contacts  8042  by heating arrangement  8041  causes an electrical current to flow through the intervening section of stock  806 . The magnitude of the electrical current may be suitably selected to cause sufficient resistive or Joule heating to remove the unwanted coating/film from the surfaces of stock  806 . The heating process may be conducted in an inert gas atmosphere, which is supplied from gas tank  802 , to minimize surface oxidation or reoxidation. 
       FIG. 8   c  shows another variation of plating/etching cell arrangement  800  in which laser heating is employed instead of mechanical abrasion or Joule heating to remove unwanted coatings from the surface of wire or flat stock  806  passing through enclosure  803 . A laser  8042  may be deployed to direct light onto wire or flat stock  806  passing through enclosure  803 . Laser  8042  may be selected to have a light wavelength suitable for absorption in and consequent heating of the stock material or absorption in the inhibiting film itself giving rise to photoablation of the inhibiting film. In operation, laser  8042  may be operated at a power sufficient to heat wire or flat stock  806  so that unwanted surface coatings are removed as wire or flat stock  806  moves through enclosure  803 . Voltage source or potentiostat  807  may be configured to make a sliding electrical contact  8044  with wire or flat stock  806  as the stock passes through enclosure  803 . Voltage source or potentiostat  807  may be used to apply an electrical voltage to wire or flat stock  806  across from sliding contact  8044  and counter electrode  808  to obtain electro plating or etching action as coating-free wire or flat stock  806  passes through electrolyte  8001 . 
     In another implementation of plating/etching cell arrangement  800 , removal of unwanted surface coatings may be accomplished by chemical action. In such an implementation, enclosure  803  may be configured to hold a reducing gas atmosphere (e.g., hydrogen) to treat the surfaces of passing wire or flat stock  806  to remove unwanted coatings. 
     It will be understood that in  FIGS. 8   a - 8   c , enclosure  803  is shown as separated from tank  801  by an arbitrary distance, which is selected only for visual clarity in illustration. In practical implementations of plating/etching cell arrangements  800 , enclosure  803  may be separated from tank  801  by a distance selected in consideration of the tolerable transit time of cleaned stock  806  through air prior to plating or etching action. In some implementations, enclosure  803  may be attached to tank  801  so that cleaned wire or flat stock  806  can exit directly into tank  801 . Such implementations minimize the time cleaned wire or flat stock  806  is exposed to air before submerging in electrolyte  8001 . 
     Conversely, for certain applications in which air exposure times are not a significant issue (e.g., the plating or etching of cleaned aluminum), enclosure  803  may be completely dispensed with.  FIG. 8   d  shows a plating/etching cell arrangement  800 , which is configured for processing materials such as aluminum. In this configuration, surface coatings may be adequately removed from aluminum wire or flat stock  806  by mechanical die  804  in air without the benefit of a controlled atmosphere of enclosure  803 . It will be understood that mechanical die  804  is placed in close proximity to tank  801 . 
       FIG. 9  shows another plating/etching cell arrangement  900 , which is adapted for processing substrates that are not conveniently supplied by reel-to-reel material handling systems. The substrates may be discrete individual parts or parts having non-flat geometrical shapes. Plating/etching cell arrangement  900  is designed so that unwanted surface coatings can be removed from substrate  906  having any arbitrary shape prior to etching and plating. Plating/etching cell arrangement  900  includes a tank  901  which can hold an electrolyte  902 . An enclosure  904 , which has a substrate loading door  9004 , is disposed directly atop tank  901 . Enclosure  904  is provided with ports  903  and  912  that may be used to flow gases through the enclosure. A sliding access door  905  may be provided between enclosure  904  and tank  901 . Substrate  906  may be loaded through loading door  9004  and attached by fastener  908  to substrate holding rod  907 , which may be adapted for controlled vertical motion to position loaded substrate  906  in either enclosure  904  or tank  901 . Rod  907  is also connected to a terminal of voltage supply or potentiostat  910  by way of a wire lead  909 . 
     In preparation for plating or etching in tank  901 , substrate  906  is first suspended in enclosure  901 . A reducing gas (e.g., hydrogen) may be passed over substrate  906  through ports  903  and  912  to chemically reduce and remove unwanted surface coatings. After removal of the unwanted surface coatings, substrate  906  may be lowered through sliding door  905  into electrolyte  902  for plating or etching action on cleaned substrate surfaces. The intimate proximity of enclosure  904  and electrolyte  902  prevents re-oxidation of substrate  906  between the coating removal and initiation of plating or etching action. For plating or etching action by electrolyte  902 , a potential difference may be established between substrate  906  and a counter electrode  911  by connecting electrode  911  to the opposite polarity terminal of supply  910 . 
       FIG. 10  shows an exemplary composite substrate  1000 , which may be plated or etched using the inventive systems and methods. Substrate  1000  may, for example, include a silicon, or glass base  1001  on whose surface a film  1002  is deposited. An inhibiting film  1003  may reside on top of film  1002 . Removal of film  1003  (and/or film  1002 ) may be necessary for successful plating or etching of composite substrate  1000 . Such removal may be effected using the systems and methods described herein. 
     The present invention also provides additional techniques and arrangements for in situ removal of inhibiting or interfering surface films to prepare substrates for plating and/or etching. These additional techniques include induction heating, microwave heating and mechanical stamping processes. The additional techniques may be individually used to prepare substrates for plating and/or etching. Alternatively, the techniques may be used in any suitable combination (e.g., abrading and stamping, stamping and microwave heating, etc.) to prepare substrates for plating and/or etching. 
     Induction heating is a well known method for providing fast, consistent heat to a metallic object. Induction heating is used in many manufacturing applications, including, for example, bonding, annealing, metal working and the like. In common induction heating arrangements, an ac coil (i.e., induction coil) is placed in close proximity to a work piece or substrate. The ac coil radiates a time-varying electromagnetic field, which induces eddy currents in a surface layer (“skin depth”) of the metal or metallic work piece/substrate. These eddy currents dissipate energy in the skin depth causing the temperature of the work piece/substrate to rise. The thickness of the “skin depth” of the metal or metallic work piece/substrate depends on the frequency of the ac current driving the induction coil and on the intrinsic electric conductivity of the metal or metallic work piece/substrate. The overall work piece/substrate heating is also a function of the thermal conductivity, geometry and the immediate environment of the work piece/substrate. 
     In the present invention related to metal plating and etching, substrates are subjected to induction heating to remove inhibiting surface films or regrowth. The substrates may be inductively heated when they are either (1) submerged in a plating/etching solution bath or (2) contained within an inert atmosphere in a preparation chamber in close proximity to the plating/etching bath. 
       FIG. 11  shows such a preparation chamber, which may be used to prepare substrates for plating/etching. The substrates may be inductively heated in an inert atmosphere to remove inhibiting oxide or other films. Immediately after the inductive heating step, the substrates can be subjected to etching or plating action.  FIG. 11  shows an arrangement in which the preparation chamber is separated from the plating/etching tank by a partition wall. Substrates that are inductively heated in the preparation chamber can be rapidly transferred to the plating/etching tank through a sliding door in the partition wall. 
     The substrates may be inductively heated using either continuous wave (cw) or pulse heating in the inert atmosphere to remove inhibiting oxide or other films. The frequency of the radiated electromagnetic field produced by the induction coil at least in part determines the depth of heating of the substrate. The higher the frequency of the radiated electromagnetic field the greater is the localized surface-like nature of the heating of the substrate, due to the well known electromagnetic skin depth effects. In most instances, there is no need to heat the bulk of the substrate for simply removing the inhibiting surface films. For localized surface heating, which is most effective for removal of inhibiting surface films, it may be desirable to use induction frequencies greater than 60 kHz. A practical frequency regime is at least 100 kHz or greater. Subjecting the substrate to GHz microwave radiation, which is typically generated by a magnetron, may be especially effective in removing the inhibiting film by localizing the heating to a thin surface region. A magnetron-microwave system for removing inhibiting films is also shown in  FIG. 11 . 
     Induction heating or microwave irradiation heating for removing surface inhibiting films may be most effective in a preparation chamber separate from the plating/etching bath in order to prevent heating of plating/etching solution itself. 
     In some instances, induction heating also may be exploited to heat substrates that are submerged in a plating/etching solution. Such induction heating is likely to also heat the plating/etching solution. Circulation and/or cooling of the plating/etching solution may overcome any undesirable or excessive heating of the plating/etching solution caused by induction heating. 
       FIG. 12  shows a preparation chamber  1201  in which microwave or induction coil heating is used to remove a thin oxide or inhibiting film from trenches in a substrate prior to plating action. The substrate may, for example, be a semiconductor silicon substrate that has trenches built in its surface as part of common semiconductor device fabrication processes or steps.  FIG. 12  shows a substrate topography with only one trench for purposes of clarity in drawing. It will be understood that the substrate may be a silicon wafer substrate, which in typical semiconductor device fabrication processes may have thousands or several thousands of such adjacent trenches in close proximity to each other. In current semiconductor device fabrication processes, it is desirable to be able to plate copper in the trenches for making electrical conductor lines. To plate copper on silicon to make electrical conductor lines, a liner (e.g., a thin film of Ta or TaN) is first deposited in the trenches onto the silicon trench surface itself or on an intermediary thin layer of silicon dioxide. 
     As an alternative or in addition to the induction heating and/or magnetron heating techniques already described, ion beam heating may be used to prepare substrates for plating. The ion beam heating technique may be particularly suited for preparing “trenched” substrate topography for plating/etching.  FIG. 13  shows an arrangement  1300  with a movable ion gun (e.g., ion gun  1301  with lateral and rotational motion). The arrangement may be used for an ion beam process to prepare an array of trenches on a wafer surface for subsequent plating action. As shown in  FIG. 13 , a directed ion beam generated by the ion gun can be made to scan the wafer surface in swivel and/or raster pattern. Typically, the wavelength of ion beam is in the submicron range so that the beam can reach into the trenches in a manner that is not possible by typical wavelength laser light. The energy of the ion beam determines the effective particle wavelength. For example, for a 400 eV argon ion beam, the wavelength is on the order of 1 A. The wavelength or energy of the ion beam can be adjusted by changing the number of electron volts of acceleration voltage applied to the ion beam. The ion beam energy is adjusted so that it is sufficiently energetic to remove the inhibiting layer without affecting the liner as shown in  FIG. 13 . 
       FIG. 14  shows the use of an induction coil (or magnetron) heating arrangement  1400  in a reel-to-reel system for plating/etching continuous substrates (e.g. shim stock). In the configuration shown in  FIG. 14 , an induction coil or magnetron is provided in a preparation chamber  1401 . The raw substrate material from the stock reel passes through the preparation chamber, which may contain an inert gas or a vacuum. The passing substrate material is inductively heated in chamber  1401  using either a cw or pulsed mode radiation. The substrate material then passes directly into the plating/etching bath after which it is rewound on a take-up reel. The system of  FIG. 14  is similar to the reel-to-reel systems described, for example, with reference to  FIGS. 8   a - 8   d , except for the manner in which the substrates are prepared for plating/etching. The systems of  FIGS. 8   a - 8   d  use direct current heating or the mechanical abrading of the raw substrate as it is unwound from the reel prior to entering the plating/etching bath followed by rewinding on a take-up reel. In contrast, the system of  FIG. 14  uses induction heating of the raw substrate material prior to metal plating/etching. 
     Another mechanical surface film removal technique may be utilized to remove inhibiting coatings, for example, from substrates that are shaped by stamping processes. (See e.g.,  FIG. 15 ). In such processes, a stamping tool  1500  is driven by force against the substrate to change the latter&#39;s mechanical form into a desired pattern or shape. The stamping processes may be operated either at room temperature or heated temperatures. When sufficient force is used to drive the stamping tool, the stamping processes not only serve their primary function of mechanically shaping the substrate, but also can result in removal of the inhibiting coating (e.g., a thin oxide layer). 
     According to the present invention, a substrate stamping operation is conducted in conjunction with and in close proximity to the metal/plating operations. The stamping operation is conducted just prior to moving the resultant shaped substrate into a plating or etching bath. The shaped substrates, free of inhibiting coatings after stamping, are moved rapidly to the plating bath in a short time interval to prevent any significant re-oxidation. 
     The stamping operation can be carried out in air, vacuum, or an inert gas. With suitable selection of the stamping process parameters and conditions, the stamping operation makes it possible to plate onto the re-shaped metal substrates that normally cannot be plated or are difficult to plate due to inhibiting films. New types of substrate materials can be used to substitute or replace current substrate materials for industrial applications. For example, presently copper or copper alloys are used in the connector industry for making connectors. Conventional connectors are made by stamping copper substrates or sheets and then plating them (e.g., with gold). With the present invention, it will be possible to use aluminum or titanium metal for connectors with plating occurring after stamping. The combination of stamping operations with metal/plating operations according to the present invention is particularly suited for use by the connector industry in which stamping operations are usually undertaken prior to plating. 
       FIGS. 16 and 17  show other exemplary plating/etching cell arrangements, in which removal of the inhibiting oxide or film and subsequent plating operations are performed in two separate tanks. The provision of two separate tanks permits flexibility in selecting process conditions for the removal and plating processes independently.  FIGS. 16 and 17  shows a reel-to-reel system  6000  having two separate tanks  6005  and  6014  for oxide removal and plating, respectively. Tanks  6005  and  6014  may be enclosed in an optional inert atmosphere enclosure  6004 . In system  6000 , material  6002  is supplied from reel  6001  and processed material is picked up by reel  6003 . Material  6002  passes from supply reel  6001  by way of small tracking wheels  6015  into the bath of the first tank  6005  and then into tank  6014 . Tank  6005  may contain a bath (e.g., a acid such as sulfuric acid, or a base such as sodium hydroxide) in which the inhibiting layer on material  6002  is removed by application of a short electrical pulse from a high voltage pulser  6006  to the supply reel material  6002 . As seen in  FIG. 16 , high voltage pulser  6006  has closely spaced electrode contacts  6007  which make contact with material  6002 . The duration of the electrical pulse, which is applied across contacts  6007 , may be about 10 nanoseconds to about 100 milliseconds. The particular voltages selected for the electrical pulse may depend on the pulse duration. Higher voltages may be required for shorter pulses. Further, a repetition rate of pulser  6006  may be determined by the speed of the reels. In order to obtain a continuous inhibiting film removal, the pulse repetition rate may be about 1-10,000 times per second. 
     Alternatively or additionally, the inhibiting layer residing on material  6002  may be removed by means of laser heating or photoablation.  FIG. 17  shows an arrangement in which laser  6101  emits a laser beam  6102  while material  6002  is immersed in tank  6005  before it is plated in second tank  6014 .  FIG. 17  shows setup a similar to that shown in  FIG. 16  except that pulser  6006  supplying electric pulses to material  6002  in first acid/base tank  6005  is replaced by a pulsed or CW laser  6101  positioned external to tank  6005 . Laser  6101  is positioned and operated so that laser beam  6102  is incident on material  6002  in first tank  6005 . In operation for oxide or inhibiting film removal, the laser pulses may have a width in the range of 1 ns to 100 ms with a preferred value in the range of about 10 femtoseconds to 10,000 microseconds. The pulse repetition rate may be in the range of about 1-100,000 pulses per second. The laser wavelength may be in the range of about 0.1 to 10 micrometers. It will be understood that in the case where laser  6101  is a CW laser, suitable electromechanical and/or optical scanning mechanisms may be provided to scan the laser beam with respect to the surface of material  6002  undergoing plating or etching. 
     The acid or base used in tank  6005  is preferably the same acid or base used in plating bath  6011 , which is contained in the second tank  6014 . The acid or base used in tank  6005  is free of plating metal ions. Cross-contamination or compositional change of plating bath  6011  in second tank  6014  may result if fluids from the first bath adhere to material  6002  upon exiting tank  6005  and are transferred to tank  6014 . To avoid such compositional change, material  6002  exiting tank  6005  may be wiped clean using, for example, wiper blades  6013 . Wiped liquids may be collected in and drained from drag-out container  6008 . Alternate methods of cleaning or drying (e.g. radiation from a heating lamp, a nitrogen gas blower and the like) can also be employed for the same purpose. 
     Plating of material  6002  takes place in plating bath  6011  in the second tank  6014 , either galvanostatically or potentiostatically, using galvanostat/potentiostat (or voltage source)  6010 . Material  6002  to be plated may be biased negatively relative to voltage source  6010  using grounded contact  6009 . A counter electrode/contact  6012  may be biased positively directly from voltage source  6010 . Both contacts  6009  and  6012  have ends positioned in second tank  6014  containing plating bath  6011  in order to contact material  6002 . Pulse plating, which is well known to those skilled in the art, also may be used. After exiting second tank  6014 , a third tank (not shown) may be used to rinse the plated material before it is re-wound on take-up reel  6003 . 
     It is noted that  FIG. 16  shows two power supplies—one power supply to apply pulses  6006  to material  6002  received from supply reel  6001  while in the first tank  6005 , and a second power supply to supply required plating voltages/currents while material  6002  is in second tank  1014 . The procedure in first tank  6005  removes the inhibiting film making material  6002  sufficiently clean to make plating possible in the second tank  6014 . 
     Additional examples of cell arrangements and plating/etching processes for substrates having inhibiting surface films are described herein with reference to  FIGS. 18-23 . 
       FIGS. 18 and 19  show plating/etching cell arrangements  1800  and  1900  for individual substrates and long lengths of wire or sheet flat stock substrates, respectively. With reference to  FIG. 18 , in cell arrangement  1800 , individual substrate  1803  and counter electrode  1804  are mounted facing one another and immersed in electrolyte  1805 . A voltage source  1806  is connected across counter electrode  1804  and individual substrate  1803 , which serves as a working electrode. For plating or deposition processes, the negative pole of voltage source  1806  may be connected to substrate/working electrode  1803 . Conversely, for etching processes, depending on the electrolyte used, either the positive pole or the negative pole of voltage source  1806  may be connected to the substrate/working electrode  1803 . Voltage source  1806  is configured to generate both high and low voltage pulses. In operation, a high voltage pulse (or a series of pulses) is followed by a low cw or modulated voltage signal for a period of time which is determined by the desired thickness of deposition or depth of etching. 
     The high voltage and low voltage pulses are applied between substrate/working electrode  1803  and counter electrode  1804 . (See  FIG. 18 ). First, a high voltage pulse  1801 , which is on the order of 20-2000V, is applied so that a current of at least about 120-200 A/cm 2  flows between substrate/working electrode  1803  and counter electrode  1804 . High voltage pulse  1801  may have a full width at half maximum on the order of 10 ns to 1 s. These voltage and current parameters for high voltage pulse  1801  correspond to energies of at least 5-14 Joules/cm 2  delivered to substrate/working electrode  1803 . Application of high voltage pulse  1801  results in removal of the inhibiting oxide or film on substrate/working electrode  1803 . Next, a low voltage pulse  1802  on the order of 0.01-5 volts is applied between substrate/working electrode  1803  and counter electrode  1804 . Low voltage pulse  1802  may have a pulse width of about 1 second, and may be modulated using suitable microprocessor or computer coupled to voltage source  1806 . The application of low voltage pulse  1802  is designed to activate the desired electrolytic plating or etching processes on the surface of substrate/working electrode  1803 . 
     With reference to  FIG. 19 , cell arrangement  1900  is configured with a reel-to-reel material handling system for long length wire or sheet flat stock substrate  1903 . The reel-to-reel material handling system includes a supply reel  1901  and a take-up reel  1902  on which unprocessed and processed substrates  1903  are respectively wound. Substrate  1903 , which functions as a working electrode, passes through electrolyte  1907  facing split counter electrodes  1904  and  1905 . Voltage source  1908  is connected across substrate/working electrode  1903  and counter electrodes  1904  and  1905 . Voltage source  1908 , which like voltage source  1806  is capable of generating both high and low voltage pulses, may have a low voltage terminal, a high voltage terminal and a common terminal. The high voltage and low voltage terminals of voltage source  1908  are connected to counter electrodes  1904  and  1905 , respectively, while the common terminal is connected to substrate/working electrode  1903 . 
     In operation, voltage source  1908  generates high voltage pulses  2001  and low voltage pulses  2002  for reel-to-reel plating of substrate  1903 . (See  FIG. 21 ). High voltage pulses  2001  are applied across counter electrode  1904  and substrate/working electrode  1903 . A high voltage pulse  2001  (or a series of pulses), like high voltage pulse  1801 , is designed to result in removal of the inhibiting oxide or film on the portion of substrate/working electrode  1903  facing electrode  1904 . Each high voltage pulse  2001  may only be on for the order of at most a few milliseconds. Low voltage pulses  2002 , which may be cw or modulated cw signals, are applied across counter electrode  1905  and substrate/working electrode  1903  to portions of substrate  1903  that have traveled from facing electrode  1904  to facing electrode  1905 . Low voltage pulses  2002  may be continuous wave or modulated low voltage pulses that are designed to activate the desired plating or etching processes. With this arrangement, high voltage pulses  2001  may be applied with a repetition rate of “L/v” seconds, where L is the length of counter electrode  1904 , and v is the linear travel speed at which substrate/working electrode  1903  is pulled through electrolyte  1907  across electrode  1904  and electrode  1905 . The linear travel speed v may be adjusted so that low voltage pulses  2002  are applied across electrode  1905  to a portion of substrate/working electrode  1903  within less than a second after the application of high voltage pulse  2001  across electrode  1904  to the same portion of substrate/working electrode  1903 . The durations of low voltage pulses  2002  may be selected upon consideration of length of counter electrode  1905  and the rate of deposition or etching, which rate in turn depends on the type of electrolyte  1907  used for plating or etching and the type of substrate/working electrode  1903 . In practice, the durations of low voltage pulses  2002  may be on the order of at least several seconds, which is comparable to the time it takes for substrate/working electrode  1903  to travel across electrode  1905 . Additionally, low voltage pulses  2002  may remain on concurrently with high voltage pulses  2001 , or alternatively may be interrupted for the durations of high voltage pulses  2001  that are of the order of at most a few ms. 
       FIG. 22  shows another etching/plating cell arrangement  2200  for etching/plating of substrates with inhibiting surface films. Cell arrangement  2200  is advantageously configured for processing a three-dimensional substrate  2209 . Cell arrangement  2200  uses an electrolyte jet stream  2208  to etch or plate the surfaces of substrate  2209 , which is held by an electrically conducting robotic arm  2210 . A voltage supply  2216  is connected across substrate  2209  and electrode  2205  disposed in an electrolyte-holding pressure cell  2204 . Electrode  2205  serves as an anode and a cathode for plating and etching processes, respectively. Electrolyte jet stream  2208  is generated from electrolyte-holding pressure cell  2204  and directed by nozzle  2207  on to substrate  2209 . Further, nozzle  2207  may have a diameter in the range of from 100-10,000 microns for typical applications. Electrolyte  2213  is pressurized into jet stream  2208  through nozzle  2207  by pump  2214 , which forces electrolyte  2213  from reservoir  2212  into pressure cell  2204 . Electrolyte  2213  flows into pressure cell  2204  through an opening in electrode  2205 , which for electroplating processes is connected to the positive polarity of voltage supply  2216 . Different portions of the surfaces of substrate  2209  are presented to jet stream  2208  for processing by movement of robotic arm  2210  under the control of robotic control system  2211  and computer  2215 . 
     Cell arrangement  2200  further includes provisions for modifying the free-standing jet plating or etching processes with an electromagnetic energy beam (e.g., an intense laser beam) directed collinearly along jet stream  2208 . For this purpose, cell arrangement  2200  includes a pulsed laser  2210  which generates a laser beam  2202 . Pulsed laser  2210  is aligned so that laser beam  2202  passes through window  2203  into pressure cell  2204  and then through electrode  2205  along nozzle  2207 . On exiting pressure cell  2204 , laser beam  2202  is guided by jet stream  2208  which acts as a wave guide or light pipe causing laser beam pulse  2202  and jet stream  2208  to travel collinearly. This wave guide or light pipe arrangement permits laser beam pulse  2202  and jet stream  2208  to be incident collinearly on surface portions of substrate  2209  presented for processing. Modification of electroplating and etching processes with an intense laser beam have been described, for example, in U.S. Pat. No. 4,497,692. 
     In cell arrangement  2200 , a pulsed laser  2201  produces a set of one or more pulses  2202  of laser light for a total time on the order of 1 ps to 10 ms. The set of pulses  2202  is preferably triggered immediately after a new portion of the surfaces of substrate  2209  is presented to jet stream  2208  for processing by movement of robotic arm  2210 . The pulsing of laser  2201  may be co-ordinated with the movement of robotic arm  2210  by computer  2215  which is interfaced with the robotic arm control system  2211 . 
     In operation, laser pulses  2202  incident on substrate  2209  may be configured to have a power density on the order of 10 5  to 10 10  W/cm 2  in order to remove the inhibiting films from the surfaces of substrate  2209 . Each laser pulse  2202  may have a pulse width or duration on the order of about 10 ps to 10 ms, and have a fluence of 1-5,000 mJ/pulse. These parameters may be selected on consideration of the cross sectional area of jet stream  2208  as well as the thermal properties of sample  2209  and the coatings thereon. 
     While laser  2202  is operated in a pulsed mode, jet stream  2208  may be operated in a continuous mode (cw) to activate the desired plating (or etching) processes on the surface of sample  2209 . The desired plating or etching can occur after the inhibiting surface films have been removed by application of the high intensity laser pulses  2202 . Robotic arm  2210  can move substrate  2209  so that any surface portion of  2209  can be plated (or etched) as determined by computer  2215 , which synchronously controls robotic control system  2211  and the pulsing of laser  2201 . In some implementations of the invention, laser  2202  may be programmed so that after emitting a high intensity pulse  2202  that removes the inhibiting surface films, the laser emission drops to a much lower power level to induce laser-enhanced jet plating or etching as is well known in the literature. 
       FIG. 23  shows another cell arrangement  2300  for modification of electroplating and etching processes with an intense laser beam. Cell arrangement  2300 , like cell arrangement  2200 , includes pulsed laser  2201 , computer  2215 , voltage supply  2216 , and a computer controlled robot  2211  having an electrically conducting robotic arm  2210  for mounting substrate  2209  in electrolyte  2213 . However, electrolyte-holding cell  2206  and nozzle  2207  of cell arrangement  2200  shown in  FIG. 22  are replaced in cell arrangement  2300  by an insulating flexible curtain  2301 , which defines a volume  2303  of electrolyte  2213 . Flexible curtain  2301  preferably has a conical shape. Flexible curtain  2301  includes an inside electrode insert or extension  2302 . Electrode  2302 , which may be made of small strips of electrically conducting material, is disposed in curtain  2301  in close proximity to substrate  2209 . Voltage supply  2216  is connected across electrode  2302  and substrate  2209  with a suitable polarity orientation for either electrolytic plating or etching as desired. 
     In operation, different surface portions of substrate  2209  are moved under electrolyte volume  2303  by movement of robotic arm  2210  under the control of computer  2215 . Like in the operation of cell arrangement  2200 , pulsed laser  2201  generates a high intensity laser pulse (or a series of pulses) to remove inhibiting surface films from substrate  2209 . The high intensity laser pulse, which may have a duration of a few picoseconds to milliseconds, is directed inside the volume of curtain  2301  on to substrate  2209  to remove inhibiting surface films from surface portions of substrate  2209  under electrolyte volume  2330 . As described with reference to FIG.  22 , the desired plating/etching of substrate  2209  can occur after the inhibiting surface films have been removed by application of the high intensity laser pulse. Robotic arm  2210  moves substrate  2209  so that any surface portion of substrate  2209  can be plated (or etched) as determined by computer  2215 , which synchronously controls robotic control system  2211  and the pulsing of laser  2201 . 
     The movement of substrate  2209  caused by robotic arm  2210  results in curtain  2301  being slid along the surface of substrate  2209 . Curtain  2301  can have small holes to allow electrolyte  2213  to recirculate through volume  2303 . Alternatively, an auxiliary pump (not shown) can be used to maintain a desired level of electrolyte  2213  inside volume  2303  that is defined by conically shaped flexible curtain  2301 . 
     The foregoing merely illustrates the principles of the invention. Various modifications and alterations to the described embodiments will be apparent to those skilled in the art in view of the teachings herein. It will be appreciated that those skilled in the art will be able to devise numerous modifications which, although not explicitly described herein, embody the principles of the invention and are thus within the spirit and scope of the invention. For example, it will be readily understood by those skilled in the art that the removal/plating processes, which utilize two tanks with their respective baths, can also be used for individual pieces of material without the use of the reel-to-reel material handling system described with reference to  FIGS. 16 and 17 . In such case, a means of dipping the samples serially into the two tanks may be used instead of the reel-to-reel system. 
     Further, for example, a suitable contact patterning mask may be directly disposed on the substrate surface to define surface portions for plating or etching. The contact mask may be fabricated using any convenient materials (e.g., negative or positive photoresist layers). While photoresists are one of the most common types of contact masks, other insulating materials (e.g., various tapes, varnishes, paints and lacquers) also can be used. The in situ surface coating removal techniques described herein can be used to prepare the defined surface portions for plating or etching, for example, by removing surface coating layers in the contact mask openings by application of high voltage or discharge pulses. Immediately thereafter, a second voltage pulse can be applied to provide plating or etching action in the contact mask openings in which inhibiting surface coating layers have been removed by the discharge pulse, but without affecting the contact mask pattern. The second voltage pulse used for plating/etching, which may continuous or in the form of repetitive pulse, may have an amplitude on the order of about +/−1-3V. For galvanostatic plating/etching, the second voltage pulse amplitude may be considerably higher depending, for example, on sample size. After the plating/etching step, the substrate is removed for the electrolyte solution, and the masking material stripped. 
     The foregoing technique of directly masking the substrate for in situ patterned plating/etching advantageously avoids the conventional substrate patterning process steps that require oxide removal over the entire substrate surface prior to masking. The technique enables patterning to take place before the substrate is stripped of its oxide layers. The technique is particularly beneficial in applications involving substrate materials that are highly oxidizable (e.g. Al). For such substrate materials having rapid oxide growth, the substrates are conventionally patterned in an inert atmosphere. This process complexity or burden can be avoided by the foregoing technique of directly masking the substrate for in situ patterned plating/etching. 
     In laboratory demonstrations, electroplated patterns of copper on stainless steel 316 substrate have been obtained by first pattern masking the substrate, then applying a voltage pulse to remove surface oxides in the mask openings followed by plating.  FIG. 24  shows an exemplary substrate  24 - 103  used in the laboratory demonstrations. An electrically insulating patterning mask  24 - 104  is disposed on substrate  24 - 103  so that regions  24 - 102  are electrically insulating and therefore are not be subject to surface oxide removal and plating/etching. The exposed mask opening regions  24 - 104  are subject to surface oxide removal and plating/etching.  FIG. 25   b  shows a masked substrate  25 - 201  ( 24 - 103 ) disposed in an electrolyte  25 - 203  facing immersed counter electrode  25 - 202 . A power supply  25 - 204  is configured to apply potential pulses across electrodes  25 - 202  and  25 - 203  immersed in the electrolyte.  FIG. 25   a  shows an exemplary high voltage pulse  25 - 205 , which is applied to remove surface oxide layers from regions  24 - 104 . Exemplary high voltage pulse  25 - 205  may, for example, be on the order of 20 V or greater, and have a pulse width of about 1 ms. After the surface oxide removal pulse  25 - 205 , power supply  25 - 204  may be used to apply lower voltage pulses (e.g.,  25 - 206 ) for plating or etching action on the “prepared” oxide-free surface regions  24 - 104 . 
       FIG. 26  shows another view of the electrolytic cell and electrode arrangement of  FIG. 25   b  used of plating. For plating action, the negative polarity of supply  26 - 204  is connected to substrate  26 - 201  ( 24 - 103 ). A small voltage on the order of about 2.0 V is applied between substrate  26 - 201  and counter electrodes  26 - 202  for plating etching of oxide-free regions  24 - 104 . After completion of the plating process, the mask material may be conventionally removed (e.g., by stripping dissolving, ashing, etc.) leaving a pattern of plated material in regions  24 - 104  on substrate  24 - 201 . It will be understood that the same masking technique can be used for patterned etching in regions  24 - 104  on substrate  24 - 201 .