WO2000073856A2 - Article et procede hybride de modification d'une surface - Google Patents

Article et procede hybride de modification d'une surface Download PDF

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Publication number
WO2000073856A2
WO2000073856A2 PCT/US2000/014797 US0014797W WO0073856A2 WO 2000073856 A2 WO2000073856 A2 WO 2000073856A2 US 0014797 W US0014797 W US 0014797W WO 0073856 A2 WO0073856 A2 WO 0073856A2
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WO
WIPO (PCT)
Prior art keywords
pattern
machining
plateaus
substrate
resist
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PCT/US2000/014797
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English (en)
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WO2000073856A3 (fr
Inventor
Jeffrey M. Johnston
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Bmc Industries, Inc.
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Publication date
Application filed by Bmc Industries, Inc. filed Critical Bmc Industries, Inc.
Priority to EP00939399A priority Critical patent/EP1145083A2/fr
Priority to KR1020017001315A priority patent/KR20020010562A/ko
Priority to JP2001500912A priority patent/JP2003501687A/ja
Priority to CA002338346A priority patent/CA2338346A1/fr
Priority to MXPA01000994A priority patent/MXPA01000994A/es
Publication of WO2000073856A2 publication Critical patent/WO2000073856A2/fr
Publication of WO2000073856A3 publication Critical patent/WO2000073856A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H3/00—Electrochemical machining, i.e. removing metal by passing current between an electrode and a workpiece in the presence of an electrolyte
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H9/00—Machining specially adapted for treating particular metal objects or for obtaining special effects or results on metal objects
    • B23H9/008—Surface roughening or texturing

Definitions

  • the present invention relates to methods and apparatus for producing surfaces with designed texture thereon and articles having those surfaces.
  • the processing technology relates to a combination of chemical milling (such as photochemical milling) and Electrical Discharge Machining (EDM).
  • Modern technology requires a vast array of manufacturing techniques to meet the specialized needs of different operating systems.
  • One of the most important aspects of efficient machines is the control of the surface properties, particularly at the interface of different parts.
  • the most usual design consideration of surface properties is attempting to reduce the friction between moving parts that contact each other.
  • controlled friction is also a major design consideration as friction between parts is often essential to their performance, as with a clutch plate, nip rollers, coating rollers, tires, drive wheels and the like.
  • the earliest forms of controlling or modifying the friction properties contributed by surfaces comprised various forms of grinding, lapping, polishing or abrading surfaces to make them as smooth or as rough as the task required.
  • polymers and resins are capable of being molded to form microreplicated surfaces, with complex textures and patterns thereon (e.g., 3M TrizactTM surfaces).
  • This technology is completely inappropriate for use with metals, however, primarily because the material forming the replication has to be thermally or chemically softened to a state above its flow temperatures. Those flow temperatures tend to be very high for most useful metals, particularly machineable metals, and the replication molds must endure high temperatures and extreme cooling conditions, and tend to suffer extreme wear with metals being molded.
  • Metals can have their surfaces textured by mechanical milling (e.g., diamond milling, lapping, abrading, roughening), chemical milling (e.g., chemical etching, photochemical etching), high energy milling (e.g., ablation or etching with high energy beams such as with plasma, excimer lasers, laser diodes, and the like), and other treatments capable of controlled removal of material in designed or patterned areas.
  • mechanical milling e.g., diamond milling, lapping, abrading, roughening
  • chemical milling e.g., chemical etching, photochemical etching
  • high energy milling e.g., ablation or etching with high energy beams such as with plasma, excimer lasers, laser diodes, and the like
  • Other materials are formed or molded with the surface characteristics and shapes determined by the walls of the mold.
  • EDM electrical discharge machining
  • the electrode cutting device may be a wire or a shaped head (e.g., with a tapered or pointed cutting extension) that literally melts its way through the surface to be textured as would a hot knife through butter.
  • the mechanism for texturing the surface is not precisely melting.
  • the electrode is moved towards the workpiece until the space between the electrode and the workpiece is such that the voltage in the gap can ionize a dielectric fluid (coolant) that is placed on the workpiece surface.
  • the ionization allows a spark to pass from the electrode to the workpiece.
  • the EDM operates by providing these spark discharges at a very high frequency of at least 50,000 discharges per second, usually at least 100,000 discharges per second and preferably at least 250,000 discharges per second.
  • the spark move the shortest distance across the gap, to the nearest or highest place on the workpiece.
  • the amount of material removed from the surface with each spark is proportional to the amount of energy in each pulse.
  • Each spark melts, ablates or vaporizes a small area of the workpiece surface. This vaporized material will then be cooled in the dielectric fluid (explaining its alternative description as the coolant).
  • the removed material is carried away from the surface by movement of the dielectric.
  • the texturing may be essentially two dimensional or three dimensional, depending upon the workpiece and the design sought in the texturing.
  • EDM removes metal with electrical discharges instead of with an actual mechanical or abrading action, the hardness of the workpiece does not determine whether or not a material can be machined by EDM.
  • a relatively soft electrode made of graphite or metal can easily machine hardened steel tools or tungsten carbide.
  • wire-cut EDM The basic principles of wire-cut EDM are essentially the same as the die- sinking or plunge EDM described above. The major difference is that instead of using an electrode with a specific shape, in wire EDM the electrode is a simple wire, typically with a 5 to 15 mil diameter. The wire will follow a horizontal path through the workpiece. Filtered water (e.g., filtered deionized water) is typically used as the coolant in wire EDM processes.
  • EDM is a very desirable and effective method of providing specific textures and patterns to surfaces, it is relatively expensive when a large and/or deep pattern must be machined.
  • the process is also relatively slow, with the die-sinking electrode machining only a narrow path with long durations needed for deeper patterns, and wire EDM is also relatively slow and is limited to making linear machine tooling as the wire must maintain significant tension to prevent gravity bowing or mechanical deflection.
  • Chemical milling is the generic term applied to any surface modification of a material by the application of chemical materials to the surface and the resulting chemical activity removing or texturing the surface.
  • chemical milling usually applies to the removal of material to generate a patterned or uniform topography to a surface, it has also been used in the art to encompass anodization, controlled oxidation, reduction and the like.
  • milling is referred to in the present invention as applicable to only the removal of material from the surface.
  • Photochemical milling for example, is a technology wherein a photosensitive response usually in the form of a photoresist layer) is provided to a surface. After chemical milling compositions are then applied to the surface after exposure to activating (actinic) radiation, the milling tends to result in a patterned removal of material from the surface.
  • the photoresponsive material in a photochemical milling process may be, for example, photoresist materials, whether positive-acting or negative-acting.
  • Thermal resist materials that are responsive to differential patterns of heat
  • electrographic resists that are responsive to differential patterns of charge, as, for example, applied by a stylus
  • Photoresist materials are layers that alter their solubility in a specific or general class of solvents after sufficient irradiation by electromagnetic radiation to which the layer is sensitive.
  • a water-developable positive-acting photoresist layer sensitive to ultraviolet (UN) radiation within the wavelength range of 230 to 380 nanometers
  • the initial (unexposed to UN radiation) layer will not be highly soluble in water.
  • the areas of the layer that have been sufficiently irradiated a fluence of radiation that exceeds a threshold amount
  • the imagewise exposed layer is then washed (sprayed, immersed, scrubbed, mildly agitated, etc.) With water and the more soluble areas are removed, leaving a pattern of coating on the surface corresponding to the non-imaged areas of the original coating.
  • the chemical milling agents contacts only exposed areas of the substrate and thereof only those exposed areas of the substrate that contact the chemical milling surface are milled (or etched) by the activity of the solution.
  • Negative-acting photoresists are used in a similar manner, except that the coating becomes less soluble where exposed to actinic radiation.
  • a coating composition comprising organic solvent soluble binder, polymerizable components (e.g., monomers, comonomers, polymerizable oligomers, or polymerizable polymers) and a photosensitive compound that assists in or initiates the polymerization (e.g., a photocatalyst, photoinitiator, photolabile halogen materials, photolabile acid generators, and the like, with or without spectral sensitizers).
  • the coated composition Upon irradiation by electromagnetic radiation to which the composition is sensitive, the coated composition polymerizes (often referred to in certain arts as hardening), becoming less soluble in the organic solvent.
  • the imagewise exposed layer is then washed (sprayed, immersed, scrubbed, mildly agitated, etc.) with the appropriate organic solvent and the more soluble areas are removed, leaving a pattern of coating on the surface corresponding to the imaged areas of the original coating.
  • the chemical milling agents Upon application of chemical milling agents to the substrate with the patterned coating thereon, the chemical milling agents contacts only exposed areas of the substrate and thereof only those exposed areas of the substrate that contact the chemical milling surface are milled (or etched) by the activity of the solution.
  • the process is performed by either a) first chemical machining to obtain the fundamental pattern and approximate depth of texturing desired in the final product and refining the grooves, walls and troughs of the patterned surface by subsequent electrical discharge machining or b) using electrical chemical machining to define a pattern of troughs, grooves and walls, and then extending the depth of those grooves with chemical machining (in combination with a resist over the surface of the plateaus of the initial pattern).
  • the initial product from alternative b) may be followed by a further electrical discharge machining to refine the groove characteristics.
  • the plateaus illustrated in Figure la) represent plateaus produced by photochemical machining.
  • the plateaus illustrated in Figure lb) represent plateaus produced by electrical discharge machining. Significant differences can be seen in the characteristics of the plateaus made by the various processes. For purposes of comparing the illustrations, a valid assumption that the height (h) of each plateau is the same.
  • the dashed line t represents a line within the plane at the top of the plateau and an extension of an edge 2.
  • the dashed line b represents a line parallel to t that lies within a plane defined by the lowest point in a trough adjacent a plateau.
  • a corner 10 is formed by intersection of edge 2 with edge 8.
  • Line v represents a vertical line that passes through corner 10.
  • the edge 12 of the face extending from edge 8 rapidly diverges away from vertical line v.
  • the angle theta formed by a line defining the slope of the edge 12 or the face 14 diverges from vertical line v by at least 30 degrees when about 30% of h has been achieved moving down from t in the case of photochemical machining.
  • the slope of the edge 12 or the face 14 diverges from vertical line v by at least 30 degrees when about 25%, about 20%, or even 15% of h has been surpassed moving down from t in the case of photochemical machining.
  • the slope characteristics of the chemical machining are important from a number of perspectives.
  • the slope of the edge 12 or the face 14 diverges from vertical line v by less than 25 degrees when about 70%, about 75%, or even 85% of h has been surpassed moving down from t in the case of photochemical machining.
  • the electrical discharge machined grooves, troughs, plateaus and channels offer a very sharp design (with smooth walls, sharp, unrounded features, uniform angles, etc.), these characteristics are not necessarily beneficial in all technical environments.
  • the sharp features and right angles reduce the structural support of the plateaus, providing areas where stress can attack the bases of plateaus.
  • the sharp right angles create vortex generating points for the flow of fluids, which can assist in causing bubbles or foaming with liquids.
  • the sharp angles at the base of the plateaus also allows the raised areas to shift more easily under lateral stress.
  • the plateau configuration of the product of the present invention is also unique, and is not identifiable as the product of PCM or EDM, alone. In terms used to characterize the faces and edges in Figure la), the same lines would be better described as ordinarily, the angle theta formed by a line defining the slope of the edge 12 or the face 14 diverges from vertical line v by less than 20 degrees when about 30% of h has been surpassed moving down from t in the case of the hybridized process of electrical discharge machining and photochemical machining.
  • the slope of the edge 12 or the face 14 diverges from vertical line v by more than 25 degrees when about 60%, 70%, about 75%, or even 85% of h has been surpassed moving down from t in the case of the hybridized process of electrical discharge machining and photochemical machining.
  • many of the beneficial characteristics of both the electrical discharge machining and the chemical machining are provided in the finished surface of the present invention.
  • a slightly curved facing, more typical of chemical machining is provided (enabling plateau support, distortion reduction, and controlled inter-groove flow characteristics), while the sharpness of the faces, the initial straightness of the edges moving down from the plateaus, and smoothness of the faces are more characteristic of electrical discharge machining.
  • the process according to the present invention may be practiced by first photochemical etching (or any other chemical etching process, such as thermal chemical etching) and then performing electrical discharge machining, or vice versa. It is preferred to practice chemical machining first, as that is a more rapid and economical method of deep machining, and the electrical discharge machining tends to provide a smoother face surface than chemical machining. That is another characteristic that can be microscopically seen that distinguishes between surfaces and plateaus that have been chemically machined versus EDM.
  • the surface that was chemically machined will show ripples, or wavy striations on the surface, a result of the liquid motions (e.g., eddies, vortexes, channeling etc.) of the chemical machining solution or etch solution on the surface.
  • electrical discharge machining is used before chemical machining, it may be desirable to refine the chemically machined surfaces by further electrical discharge machining.
  • the chemical machining would be performed, for example, by applying a resist to the surface of the plateaus or plateau outlines after electrical discharge machining (to significantly less than the final depth ultimately desired, e.g., from about 1-25% of the ultimate depth) to provide the resist pattern.
  • the resist pattern could be applied by printing the resist onto the plateaus (e.g., by roller application), avoiding significant penetration into the mini-troughs obtained by general application of a resist and imagewise exposure in register with the pattern from the electrical discharge machining, followed by wash-off development of the resist.
  • a wide variety of photocurable compositions and photo-reactive materials are known in the prior art.
  • ethylenically unsaturated compositions are described in U.S. Pat. ⁇ os. 4,544,621; 4,564,580, 4,668,601, and 4,798,877.
  • these photocurable compositions can comprise a photoinitiator, such as the onium compounds described in U.S. Pat. No. 4,632,891, and a polymerizable material which is activated by the photoinitiator.
  • U.S. Pat. No. 4,229,519 discloses that polymers containing quaternary nitrogen groups bearing ethylenically unsaturated groups may be cured with radiation under nitrogen in the presence of a suitable photoinitiator.
  • photocurable compositions which comprise a photoacid generating initiator are those described in U.S. Pat. Nos. 4,081,276; 4,551,418 and 4,610,952.
  • the most common photoacid generating systems are diaryliodonium and triarylsulfonium salts.
  • Recent work in photoacid generating compounds are described in proceedings of ACS Division of Polymeric Materials, Science and Engineering, Vol. 61, Fall Meeting 1989, in Miami Beach, Fla. J. V. Crivello, "Chemistry of Photoacid Generating Compound", p. 62.
  • those photocurable compositions are water incompatible and require organic solvents for preparation of coatings.
  • a photocurable composition is selectively exposed to actinic or other radiation in a desired pattern.
  • the portions of the composition which are not subjected to radiation can be removed or developed by immersion in a suitable solvent. This is commonly referred to as a negative photoresist.
  • a photocurable composition is rendered more soluble by exposure to radiation and this photoreacted area is removed during developing. Such compositions are referred to as positive photoresists.
  • Photocurable compositions are commonly used to form lithographic printing plates, inks cured with ultraviolet (UN) radiation or printed circuits. After development of the image on the desired substrate, the exposed surface may be etched by conventional techniques. Similar techniques can be used to manufacture integrated circuits and other microelectronic components. However, photoresists used in such applications must afford a very high degree of resolution because of the fine detail required in these miniaturized images. For accurate image formation in microlithographic applications it is desirable to have a relatively thin coating (typically about 0.1 to 2.5 microns, or more preferably from about 0.4 to 1.2 micrometers) of the photo-sensitive composition material. Further, it is desirable that the composition photocure (either polymerize or crosslink) relatively rapidly.
  • the need for thin coatings of a photo-sensitive composition is related to the limited depth of focus of typical exposure patterning equipment and to the minimization of light scatter from the film deposited.
  • the diffusing and spreading effect of the diffraction pattern of the exposing actinic radiation can limit the resolution of fine detail of the photoresist pattern.
  • the very short wavelength of the exposing wavelength of this resist will (proportionately) decrease the width of the diffraction pattern and increase the resolution of fine detail of the resist pattern.
  • the coating on the surface should be substantially free from pinholes and other blemishes, which would result in defects in the image produced.
  • Suitable photoinitiation systems for use in the invention are those which are thermally inactive but which generate free radicals upon exposure to actinic light at or below 185. degree. C.
  • the photoinitiation systems make up about 3 to 9 wt. % of the organic medium, with preferably 5 to 7 wt. %.
  • substituted or unsubstituted polynuclear quinones which are compounds having two intracyclic carbon atoms in a conjugated carbocyclic ring system, e.g., 9,10-anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1 ,4-naphthoquinone, 9, 10-phenanthrenequinone, benz(a)anthracene-7, 12-dione, 2,3-naphthacene-5,12-dione, 2-methyl-l ,4-naphthoquinone, 1 ,4-dimethyl-anthraquinone, 2,3-dimethylanthraquinone, 2-phenyl-anthraquinone, 2,3-diphenylanthraquinone, retenequinon
  • photoinitiators which are also useful, even though some may be thermally active at temperatures as low as 85 degree. C, are described in U.S. Pat. No. 2,760,863 and include vicinal ketaldonyl alcohols such as benzoin, pivaloin, acyloin ethers, e.g., benzoin methyl and ethyl ethers; alpha. -hydrocarbon-substituted aromatic acyloins, including .alpha-methylbenzoin, alpha-allylbenzoin and alpha-phenylbenzoin. Photoreducible dyes and reducing agents disclosed in U.S. Pat. Nos.
  • catalytically effective amount means a quantity sufficient to effect polymerization of the curable composition to a polymerized product at least to a degree to cause an increase in viscosity of the composition under the conditions specified;
  • substituents can be alkyl, alkoxy, aryl, phenyl, arylalkoxy, hydroxyl, cyano, carboxyl, amino, nitro, acetyl, halo (F, Cl, Br, I), etc;
  • organometallic salt means an ionic salt of an organometallic complex cation, wherein the cation contains at least one carbon atom of an organic group that is bonded to a metal atom of a transition metal series (F. A. Cotton, G. Wilkinson Basic Inorganic Chemistry, Wiley, 1976, p. 497);
  • polymerizable composition means a mixture of an initiator or catalyst and polymerizable monomer(s);
  • Polymerize and cure are interchangeable and mean to supply sufficient energy to a composition to alter the physical state of the composition, to make it transform from a fluid to less fluid state, to go from a tacky or non-tacky state, to go from a soluble to insoluble state, or to decrease the amount of polymerizable monomer by its consumption in a reaction.
  • Photosolubilize means to cause a composition to become more soluble in a specific solvent at a fixed temperature by the application of energy (usually by irradiation) to alter the chemical composition of at least one species within the composition.
  • catalyst or initiator salts initiator system contains an acid generator selected from the group consisting of diazonium, phosphonium, sulfonium, iodonium salts, halogen compounds, organometal/organhalogen combinations, benzoin esters and o-nitrobenzyl esters of strong acids, and N-hydroxyamide and N-hydroxyimide sulfonates, and aryl naphthoquinonediazide-4-sulfonates.
  • an acid generator selected from the group consisting of diazonium, phosphonium, sulfonium, iodonium salts, halogen compounds, organometal/organhalogen combinations, benzoin esters and o-nitrobenzyl esters of strong acids, and N-hydroxyamide and N-hydroxyimide sulfonates, and aryl naphthoquinonediazide-4-sulfonates.
  • initiator or catalyst salts that contain conventional counteranions, such as chloride, PF 6 , SbF 6 , or BF 4 , with simple salts, such as alkali or alkaline earth metal salts or alkylammonium salts, of the nonnucleophilic anions of the invention in a suitable solvent.
  • the initiated reactions may be carried out at temperatures ranging from about -80 degree, to about 150 degree. C, preferably at ambient temperature, or slightly elevated temperature.
  • Nonlimiting examples of suitable solvents include, water, alkaline solutions, aqueous organic solutions (e.g., water and alcohols); chlorocarbons, such as methylene chloride, and chloroform; ethers; aromatic hydrocarbons, such as toluene, and chlorobenzene; nitriles, such as, acetonitrile; alcohols, such as methanol and ethanol; nitrobenzene; nitromethane; ketones, such as acetone and methyl ethyl ketone; and other similar classes of organic solvents.
  • chlorocarbons such as methylene chloride, and chloroform
  • ethers such as toluene, and chlorobenzene
  • nitriles such as, acetonitrile
  • alcohols such as methanol and ethanol
  • nitrobenzene nitromethane
  • ketones such as acetone and methyl ethyl ketone
  • Mixtures of solvents are often desirable to control so
  • the typical photoresist comprises at least one crosslinkable or polymerizable component.
  • the polymerizable component may be a relatively higher molecular weight material (e.g., an oligomer or polymer with polymerizable groups, or may contain an inert binder ingredient to solidify the coating and prevent it from dripping or evaporating before photinitiation of the cure or polymerization.
  • Pigments or dyes may be present to assist in visualization of the layer, and even acid/base sensitive dyes may be present that change color during the polymerization or cure of the layer to enable prewash visualization of the resist layer.
  • the layer may contain solvents or be free of solvents in the coating composition.
  • most negative acting resist compositions tend to comprise materials having polymerizable groups, such as polymerizable groups selected from the classes of ethylenically unsaturated groups (e.g., vinyl, acryloyl, [meth] acryloyl, allyl, styryl, and the like), epoxy groups, silane groups, and the like.
  • Typical monomers might include acetic anhydride, acrylic acid, methacrylic acid, butyl acrylic acid, gamma-glycidoxytrimethoxysilane, gamma- acryloylpropyltrimethoxysilane, polymer backbones having pendant or terminal polymerizable groups (e.g., acryloyl or methacryloyl groups).
  • Additional conventional monomer components which may be used to modify the polymeric material include, but are not limited to, acrylic alkyl esters such as methyl methacrylate; ethyl methacrylate; 2-ethyl hexyl methacrylate; propyl methacrylate; cyclohexyl methacrylate; butyl methacrylate; benzyl methacrylate; benzyl acrylate; methyl acrylate; ethyl acrylate; propyl acrylate; butyl acrylate; styrene; acrylic alkyl amides such as N-butylacrylamide; N-octylacrylamide; acrylonitrile, styrene, p-methyl styrene; butadiene, isoprene.
  • acrylic alkyl esters such as methyl methacrylate; ethyl methacrylate; 2-ethyl hexyl methacrylate; propyl methacryl
  • Preferred monomers for resistance to alkaline processing solutions include aromatic monomers such as styrene or benzyl methacrylate or hydrophobic aliphatic monomers such as 2-ethylhexyl, butyl or cyclohexyl methacrylate. Small quantities (typically less than 5 mole %) of glycidyl methacrylate may be added as an adhesion promoter.
  • Some polymerizable or photosolubilizable compositions are initiated by the liberation of acid groups within the composition.
  • photoacid generators include diazonium, phosphonium, sulfonium and iodonium salts; halogen compounds; organometal/organohalogen combinations; benzoin esters and o-nitrobenzyl esters of strong acids, e.g., toluenesulfonic acid; and N-hydroxy amide and N-hydroxyimide sulfonates as disclosed in U.S. Pat. No. 4,371,605. Also included are aryl naphthoquinone-diazide-4-sulfonates.
  • Preferred photosolubilizing agents are the diaryliodonium or triarylsulfonium salts. These are generally present in the form of salts with complex metal halide ions such as tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate, and hexafluorophosphate.
  • photosensitive acid generators include oligomers and polymers comprising appended anionic groups having an aromatic onium acid photogenerator as the positive counter ion.
  • examples of such polymers include those described in U.S. Pat. No. 4,661,429, column 9, lines 1 to 68, and column 10, lines 1 to 14, incorporated herein by reference.
  • a spectral sensitizer may be added to the system to adjust the spectral sensitivity to the available wavelength of actinic radiation.
  • the need will depend on the requirements of the system and the specific photosensitive compound used.
  • iodonium and sulfonium salts that only respond to wavelengths below 300 nm may be sensitized to longer wavelengths using benzophenone and derivatives thereof, polycyclic aromatic hydrocarbons such as perylene, pyrene, and anthracene, and derivatives thereof.
  • the decomposition of diaryliodonium and triarylsulfonium salts has been sensitized by bis-(p-N,N-dimethylaminobenzyliden)-acetone.
  • Anthracene bound sulfonium salts with chain lengths of three to four atoms, are efficient photosolubilizing agents. These compounds, which are disclosed in M. G. Tilley, Ph.D. Thesis, North Dakota State University, Fargo, ND (1988) [Diss. Abstr. Int. B, 49, 3791 (1989); Chem. Abstr., 111, 39942u], are a preferred class of photosolubilizing agents.
  • Another preferred acid generator is AT ASS, i.e., 3-(9-anthracenyl)propyldiphenylsulfonium-, hexafluoroantimonate.
  • anthracene and the sulfonium salt are bonded by a three carbon chain.
  • Additional examples of acid generators that may be used herein are diphenyliodium tosylate, benzoin tosylate, and triarylsulfonium hexafluoroantimonate.
  • the amount of acid generator in the photoresist composition should generally be as low as possible without unduly sacrificing sensitivity, generally from about 0.1% to about 10% by weight of the photoresist composition. Less than about 0.1% generally lead to insensitive compositions while weight percentages greater than 10% produce compatibility and control problems. For most acid-labile polymers, 0.5 to 6% by weight acid generator in the photoresist composition is preferred.
  • a sufficient amount of acid labile ester in the polymer is necessary to allow the exposed areas of the resist to be developable in all aqueous base either by dissolution or dispersion.
  • Preferred all aqueous developing solutions include, but are not limited to 0.5% sodium hydroxide or 1.0% sodium carbonate.
  • the addition of small amounts of surfactants or defoamers can be useful to aid development or to control foaming in the solution.
  • the exact amount of acid labile ester depends on the resist formulation, the polymer composition and molecular weight, and the glass transition of both.
  • Colorants such as dyes and pigments are useful adjuvants in dry film photoresists because the developed resist image can be inspected for defects and a determination of when the resist has been cleaned from the substrate during development is possible.
  • a preferred example of a colorant is Victoria Green dye. This material imparts a deep green color to a resist and upon exposure of the resist, it lightens in color in the irradiated areas. This creates an image of the artwork which is useful for inspecting the exposed sample for defects that might have been present in the artwork or dirt that accidentally was present during the exposure. Additives that create a visible image by forming a color or by a color change, e.g., leucolactones, would also be useful.
  • the present invention also provides polymerizable compositions comprising (a) at least one of cationic addition polymerizable monomers, ethylenically-unsaturated free radical monomers, mixtures of multifunctional monomers polymerizable by catalyzed step-growth polymerization or mixtures thereof and (b) a catalyst or initiator salt of the present invention and a method for the polymerization comprising the steps of:
  • Solvent preferably organic solvent
  • solvent may be present in an amount up to 99 weight percent, preferably in the range of 0 to 90 weight percent, and most preferably in the range of 0 to 75 weight percent, of the polymerizable composition can be used.
  • the catalyst or initiator salts can be present in a catalytically effective amount to initiate polymerization, and is generally in the range of 0.01 to 20 weight percent (wt %), preferably 0.1 to 10 wt % of the total composition.
  • Suitable cationically polymerizable monomers and/or oligomers typically contain at least one cationically polymerizable group such as epoxides, cyclic ethers, vinyl ethers, vinylamines, unsaturated hydrocarbons, lactones and other cyclic esters, lactams, cyclic carbonates, cyclic acetals, aldehydes, cyclic amines, cyclic sulfides, cyclosiloxanes, cyclotriphosphazenes and other cationically polymerizable groups or monomers described in G.
  • cationically polymerizable group such as epoxides, cyclic ethers, vinyl ethers, vinylamines, unsaturated hydrocarbons, lactones and other cyclic esters, lactams, cyclic carbonates, cyclic acetals, aldehydes, cyclic amines, cyclic sulfides, cyclosilox
  • Free-radically Polymerizable Monomers Another subclass of polymerizable species that may be used in the polymerizable photoresist compositions of the present invention includes free-radically polymerizable compounds containing at least one ethylenically unsaturated double bond, may be monomers and/or oligomers, such as acrylates and methacrylates, acrylamides, methacrylamides, and other vinyl compounds capable of undergoing free-radical polymerization. Such monomers and specific examples are more fully described in U.S. Pat. No. 4,985,340, and such description is incorporated herein by reference. Catalyzed Step Growth Polymerizable Monomers
  • a further subclass of polymerizble species is referred to in the art as catalyzed step growth polymerizations include but are not limited to, the reaction of multifunctional isocyanates (polyisocyanates) with multifunctional alcohols (polyols) to form polyurethanes, the reaction of multifunctional epoxies with multifunctional alcohols, and the cyclotrimerization of multifunctional cyanate esters to crosslinked polytriazine resins.
  • Suitable multifunctional cyanate esters that can be cured by catalyzed cyclotrimerization, using catalysts of this invention are described in U.S. Pat. Nos. 5,143,785 and 5,215,860 and such description is incorporated herein by reference.
  • the polymerizable components can be present in any proportion preferably with the minor component comprising at least 1.0 wt %.
  • Mixtures of aforementioned classes of monomers with additives such as tackifiers, hardeners, co-curatives, curing agents, stabilizers, sensitizers etc. can also be used in the polymerizable compositions of this invention.
  • adjuvants such as pigments, abrasive granules, stabilizers, light stabilizers, antioxidants, flow agents, bodying agents, flatting agents, colorants, inert fillers, binders, blowing agents, fungicides, bacteriocides, surfactants, plasticizers, and other additives as known to those skilled in the art can be added to the compositions of this invention. These can be added in an amount effective for their intended purpose.
  • photosensitizers or photoaccelerators in the radiation-sensitive compositions.
  • Use of photosensitizers or photoaccelerators alters the wavelength sensitivity of radiation-sensitive compositions employing the latent catalysts and initiators of this invention. This is particularly advantageous when the latent catalyst or initiator does not strongly absorb the incident radiation.
  • Use of photosensitizers or photoaccelerators increases the radiation sensitivity, allowing shorter exposure times and/or use of less powerful sources of radiation. Any photosensitizer or photoaccelerator may be useful if its triplet energy is at least 45 kilocalories per mole. Examples of such photosensitizers are given in Table 2-1 of the reference Steven L.
  • the amount of photosensitizer or photoaccelerator used in the practice of the present invention is generally in the range of 0.01 to 10 and preferably 0.1 to 1.0 wt % of photosensitizer or photoaccelerator based on the weight of the curable composition.
  • Solvents preferably organic, can be used to assist in dissolving the curing agent in the polymerizable monomers described supra and as a processing aid.
  • Representative solvents include acetone, methyl ethyl ketone, cyclopentanone, methyl cellosolve acetate, methylene chloride, nitromethane, methyl formate, acetonitrile, gamma-butyrolactone, and 1 ,2-dimethoxyethane (glyme).
  • an inert support such as silica, alumina, clays, etc., as described in U.S. Pat. No. 4,677,137.
  • energy-induced polymerization of the polymerizable compositions of this invention may be carried out at room temperature for the majority of energy curable compositions, although low temperature (e.g., -lO.degree. C.) or elevated temperature (e.g., 30. degree, to 400.degree. C, preferably 50. degree, to 300. degree. C.) can be used to subdue the exotherm of polymerization or to accelerate the polymerization, respectively.
  • Low temperature e.g., -lO.degree. C.
  • elevated temperature e.g., 30. degree, to 400.degree. C, preferably 50. degree, to 300. degree. C.
  • Temperature of polymerization and amount of catalyst will vary and be dependent on the particular curable composition used and the desired application of the polymerized or cured product.
  • the amount of curing agent (catalyst or initiator) to be used in this invention should be sufficient to effect polymerization of the monomers (i.e., a catalytically effective amount) under the desired use conditions. Such amount generally will be in the range of about 0.01 to 20 wt %, and preferably 0.1 to 10 wt %, based on the weight of the curable composition.
  • any source of radiation including accelerated particles (e.g., electron beam radiation) and radiation sources emitting active radiation in the ultraviolet and visible region of the spectrum (e.g., about 200 nm to 800 nm) can be used.
  • Infrared radiation may also be used, either as a source of heat that is focused in an imagewise manner (initiating thermal cure or thermally initiating a catalyst) or by spectrally sensitizing the composition to the infrared (e.g., with merocyanine dyes, squarine dyes, or the other classes of dyes known to spectrally sensitize in the infrared).
  • Suitable sources of radiation include fluorescent lamps, mercury vapor discharge lamps, carbon arcs, tungsten lamps, xenon lamps, lasers, light- emitting diodes, luminescent semiconductors, sunlight, etc.
  • the required amount of exposure to effect polymerization is dependent upon such factors as the identity and concentrations of the curing agent, the particular monomers, the temperature and thickness of the exposed material, type of substrate, intensity of the radiation source and the amount of heat associated with the radiation.
  • Thermal polymerization using direct heating or induction heating, infrared or microwave electromagnetic radiation as is known in the art, can be used to cure the compositions according to the teachings of this invention. Curing conditions, for both photocuring and thermal curing, including duration, wavelength, temperature are readily ascertainable by those skilled in the art.
  • two-stage polymerization by first activating the curing agent by irradiating the curable compositions and subsequently thermally curing the activated precursors so obtained, the irradiation temperature being below the temperature employed for the subsequent heat-curing.
  • the activated precursors may normally be cured at temperatures that are substantially lower than those required for the direct thermal curing, with an advantage in some cases in the range from 50.degree. to 1 lO.degree. C.
  • This two-stage curing also makes it possible to control the polymerization in a particularly simple and advantageous manner.
  • compositions of this invention may be applied, preferably as a liquid, to a substrate such as metals (e.g., steel, aluminum, copper, brass, tin, alloys, cadmium, zinc, ceramic, glass, paper, composites, wood or various plastic films such as poly(ethylene terephthalate), plasticized poly(vinylchloride), polypropylene, polyethylene, and the like, and irradiated.
  • metals e.g., steel, aluminum, copper, brass, tin, alloys, cadmium, zinc, ceramic, glass, paper, composites, wood or various plastic films such as poly(ethylene terephthalate), plasticized poly(vinylchloride), polypropylene, polyethylene, and the like.
  • compositions of this invention may be used in the production of articles useful in the graphic arts and electronics industry such as printing plates and printed circuits.
  • Methods of producing printing plates and printed circuits from photopolymerizing compositions are well known in the art (cfi, British Patent Specification No. 1,495,746).
  • the system may be arranged for use with an optical imagery unit such as a wafer stepper, for adequately illuminating a photoresist surface with an extremely detailed very high resolution image. Details of the control, positioning, auto focus and associated mechanisms of the wafer stepper are known and are not included for brevity.
  • Energizing light of a specific character is generated starting with an illuminator 10 including an excimer laser 12 of the KrF type, generating a rectangular beam of approximately Gaussian distribution at 248 nm in the ultraviolet region.
  • the excimer laser 12 generates a pulse series, at approximately 150 pulses per second, each pulse being of 1.2 xlO 8 seconds in duration and about 375 mJ/pulse.
  • this system can direct radiation of sufficient intensity onto a photoresist layer to record an image, and can do so within a usefully short time since the optical imaging system is of sufficiently high efficiency.
  • a suitable laser of this type is provided by the Lumonics Hyperex-460 Model HE-SM excimer laser, although a number of other systems are available that can be utilized with appropriate recognition of various factors enumerated hereafter.
  • the beam from the laser is spatially coherent to a substantial degree, and temporally coherent to about 1 part in 620, factors which are not consistent with the spatial and temporal distributions desired.
  • the laser operates in conjunction with a resonant tuning cavity, generally referred to as an etalon, which can raise the Q factor and the predictability of the lightwave train to be in step for as much as 124,000 wavelengths.
  • a laser with intracavity etalon tuning may be used to produce the same degree of temporal coherence.
  • excessive tuning is not desirable because of the possibility of introduction of interference fringe effects, so that the etalon is slightly detuned to reduce the temporal coherence to in the range of 1 in 10,000 wavelengths.
  • the beam After emergence from the laser, the beam may be enlarged in a double-prism beam expander which turns the rectangular beam of the excimer laser into a square beam about 1 " on a side.
  • This beam passes into a spatial coherence randomizer that includes a first quasi-random phase surface defined by quasi-random patterns of SiO 2 . deposited on an SiO 2 substrate.
  • the randomizer structure provides a light transmissive element that imparts a degree of phase randomization across its cross-sectional area.
  • Such a quasi-random phase surface may be achieved by evaporated patterns having average thicknesses of about 1 micron and average widths of about 10 microns.
  • a first field lens may transfer the beam to a reticle masking assembly which may, if desired, be motor driven.
  • the masking assembly limits the beam peripherally to a controllable object field outline of a selectable size, the beam then passing through onto a movable comer mirror that is dynamically shifted through a small arc as described below. From this comer mirror the beam is directed through an imaging relay lens which images the first quasi-random surface 19 onto a second quasi-random phase surface of similar character. The beam then passes onto a beam combining comer mirror toward the associated optics including a second field lens and to the wafer plane to which the image is directed. This angled beam path enables the laser, which requires substantial power and volume, to be placed well away from the image forming part of the system.
  • the positive acting resists normally comprise one of two types of systems.
  • a polymer or resin has a natural resistance to solubility in a solvent, but the action of the light or light-generated species (e.g., an acid, a base, a catalyst, etc.) causes the polymer or resin to undergo a chemical reaction that alters its relative solubility in the solvent.
  • Such chemical reactions include, for example, an internal rearrangement, a cleavage, neutralization, splitting off of a group, acidification, or the like.
  • the polymer or resins (e.g., usually a phenol-formaldehyde resin) contains a species that resists solubilization or prevents the solvent from penetrating the polymer that would normally be soluble in the solvent.
  • the species breaks down when struck by radiation, and the native solubility of the polymer is reinstated.
  • Ortho-quinone diazides are an example of the type of photosolubilizing species that are conventional used in phenol formaldehyde resins, although certain onium salts are also recognized as being able to perform that function, particularly diaryliodonium salts.
  • the phenol formaldehyde resins useful in the compositions are known to include products derived from hydrocarbon-substituted phenols having two available positions ortho or para to a phenolic hydroxy group for aldehyde condensation to provide polymers suitable for the preparation of epoxy novolaks include o- and p-cresols, o- and p-ethyl phenols, o- and p-isopropyl phenols, o- and p-tert-butyl phenols, o- and p-secbutyl phenols, o- and p-amyl phenols, o- and p-octyl phenols, o- and p-nonyl phenols, 2,5-xylenol, 3,4-xylenol, 2,5-diethyl phenol, 3,4-diethyl xylenol, 2,5-diisopropyl phenol, 4-methyl res
  • chloro-substituted phenols which can also be used in the preparation of phenol-aldehyde resins suitable for the preparation of the epoxy novolaks include o- and p-chloro-phenols, 2,5-dichloro-phenol, 2,3-dichloro-phenol, 3,4-dichloro-phenol, 2-chloro-3 -methyl-phenol 2-chloro-5-methyl-phenol, 3-chloro-2 -methyl-phenol, 5-chloro-2-methyl-phenol, 3-chloro-4-methyl-phenol, 4-chloro-3-methyl-phenol, 4-chloro-3 -ethyl-phenol, 4-chloro-3-isopropyl-phenol, 3-chloro-4-phenyl-phenol,
  • 3-chloro-4-chloro-phenyl-phenol 3,5-dichloro-4-methyl-phenol, 3,5-dichloro-5-methyl-phenol, 3,5-dichloro-2-methyl-phenol, 2,3-dichloro-5-methylphenol, 2,5 -dichloro-3 -methyl-phenol, 3 -chloro-4, 5 -dimethyl-phenol, 4-chloro-3,4-dimethyl-phenol, 2-chloro-3,5-dimethyl-phenol, 5-chloro-2,3-dimethylphenol, 5-chloro-3,5-dimethyl-phenol, 2,3,5-trichlorophenol, 3,4,5-trichloro-phenol, 4-chloro-resorcinol, 4,5-dichloro-resorcinol, 4-chloro-5-methyl-resorcinol, 5-chloro-4-methyl-resorcinol.
  • Typical phenols which have more than two positions ortho or para to a phenolic hydroxy group available for aldehyde condensation and which, by controlled aldehyde condensation, can also be used are: phenol, m-cresol,
  • di(hydroxyphenyl) sulfones such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone,
  • any aldehyde may be used which will condense with the particular phenol being used, including formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, heptaldehyde,, cyclohexanone, methyl cyclohexanone, cyclopentanone, benzaldehyde, and nuclear alkyl-substituted benzaldehydes, such as toluic aldehyde, naphthaldehyde, furfuraldehyde, glyoxal, acrolein, or compounds capable of engendering aldehydes such as para-formaldehyde, hexamethylene tetramine.
  • the aldehydes can also be used in the form of a solution, such as the commercially available formalin.
  • the preferred aldehyde is formaldehyde.
  • the products of the present invention find use in a wide variety of applications. For example, platens are provided for the manufacture and testing of circuit boards, chips, wafers, lenses, screens, and the like that comprise flat surfaces having patterns of grooves thereon to allow fluid flow under the article being manufactured or inspected. The allowance of fluid flow prevent any air seals from restricting the movement of the article being manufactured, and actually reduces the resistance to movement of an article supported on the grooved surface.
  • abrasive sheeting is manufactured with columns and rows of abrasive elements thereon, to enable the passage of coolant fluids and swarth below the abrading height of the sheet.
  • the present process would be highly adaptable for manufacture of precisely structured abrasive surfaces.
  • a non- limiting particular field within which the practice of the present technology is applicable includes a linear step motor positioning stage.
  • An open lopp linear step motor provides an economical linear motor driven positioning stage for integrated circuit manufacture and the manufacture of other precision elements.
  • Linear step motors incorporate a motor, positioning system and bearings (e.g., air bearings) into two components, a moving forcer and a stationary platen.
  • the invention provides a unique method for manufacturing the platen and unique resulting platen.
  • the platen in ordinarily a photochemically etched steel plate filled (in the grooves or troughs) with epoxy resin.
  • the surface is usually further ground and hard-chrome plated to provide an appropriate magentcially responsive differential on the surafe.
  • the magnetic force between the forcer and the platen provides a preload for the bearing system.
  • the integral bearing system e.g., air bearings, maintains the required air gap.
  • the uniformity and slope detail of the platen become important in enabling the linear motor to provide direct linear motion without mechanical transmission, without mechanical transmission devices.
  • the flatness and uniformity of the surface is important in providing uniform and controlled moevment of the linear motor and associated workpiece over the surface.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electrochemistry (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • ing And Chemical Polishing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

La combinaison ou hybridation de l'usinage chimique (notamment usinage photochimique, usinage chimique ou thermique utilisant une réserve) avec l'usinage par électroérosion permet d'obtenir une méthode d'usinage plus efficace présentant des caractéristiques d'attaque chimique unique et d'amélioration des coûts. La propriété de l'usinage chimique permettant d'usiner avec précision et rapidité un substrat à des profondeurs importantes est alliée à une meilleure planéité des surfaces de paroi ou pente de l'usinage à électroérosion plus lent, mais plus précis, et permet d'obtenir des configurations de surfaces tridimensionnelles dont les caractéristiques faciales sont uniques, obtenues rapidement et de haute qualité. Pour effectuer ce procédé, on a recours à : a) un premier usinage chimique pour obtenir la configuration de base et approcher la profondeur de texturation désirée dans le produit final et améliorer les gorges, les parois et les creux de la surface configurée par un autre usinage à électroérosion, ou b) l'usinage électrochimique pour obtenir une configuration de creux, gorges et parois, et ensuite augmenter la profondeur de ces gorges par usinage chimique (en combinaison avec une réserve sur la surface du plateau de la configuration initiale). Le produit initial obtenu à partir de l'alternative b) peut subir un autre usinage à électroérosion pour améliorer les caractéristiques des gorges.
PCT/US2000/014797 1999-06-01 2000-05-30 Article et procede hybride de modification d'une surface WO2000073856A2 (fr)

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EP00939399A EP1145083A2 (fr) 1999-06-01 2000-05-30 Article et procede hybride de modification d'une surface
KR1020017001315A KR20020010562A (ko) 1999-06-01 2000-05-30 혼성 표면 변성방법과 제조품
JP2001500912A JP2003501687A (ja) 1999-06-01 2000-05-30 複合表面変性法及び製品
CA002338346A CA2338346A1 (fr) 1999-06-01 2000-05-30 Article et procede hybride de modification d'une surface
MXPA01000994A MXPA01000994A (es) 1999-06-01 2000-05-30 Proceso de modificaciones de superficie hibrida y articulo.

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US09/323,979 1999-06-01

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Cited By (1)

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EP2692855A1 (fr) * 2012-08-03 2014-02-05 Robert Bosch GmbH Structuration de surface pour des applications médicales et/ou de biologie cellulaire

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US4436584A (en) * 1983-03-21 1984-03-13 Sperry Corporation Anisotropic plasma etching of semiconductors
US4599243A (en) * 1982-12-23 1986-07-08 International Business Machines Corporation Use of plasma polymerized organosilicon films in fabrication of lift-off masks
US5342481A (en) * 1991-02-15 1994-08-30 Sony Corporation Dry etching method
WO1998051506A1 (fr) * 1997-05-14 1998-11-19 Seiko Epson Corporation Procede de formation d'ajutage pour injecteurs et procede de fabrication d'une tete a jet d'encre
US5866482A (en) * 1996-09-27 1999-02-02 Taiwan Semiconductor Manufacturing Company, Ltd. Method for masking conducting layers to abate charge damage during plasma etching

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US4599243A (en) * 1982-12-23 1986-07-08 International Business Machines Corporation Use of plasma polymerized organosilicon films in fabrication of lift-off masks
US4436584A (en) * 1983-03-21 1984-03-13 Sperry Corporation Anisotropic plasma etching of semiconductors
US5342481A (en) * 1991-02-15 1994-08-30 Sony Corporation Dry etching method
US5866482A (en) * 1996-09-27 1999-02-02 Taiwan Semiconductor Manufacturing Company, Ltd. Method for masking conducting layers to abate charge damage during plasma etching
WO1998051506A1 (fr) * 1997-05-14 1998-11-19 Seiko Epson Corporation Procede de formation d'ajutage pour injecteurs et procede de fabrication d'une tete a jet d'encre

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OKUYAMA ET AL.: "Micromachining with SR and FEL" NUCLEAR INSTRUMENTS AND MEHODS IN PHYSICS RESEARCH B, vol. 144, 1998, pages 58-65, XP004142324 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2692855A1 (fr) * 2012-08-03 2014-02-05 Robert Bosch GmbH Structuration de surface pour des applications médicales et/ou de biologie cellulaire

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WO2000073856A3 (fr) 2001-07-19
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