US20080210664A1 - Method of Surface Treatment and Surface-Treated Article - Google Patents

Method of Surface Treatment and Surface-Treated Article Download PDF

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Publication number
US20080210664A1
US20080210664A1 US11/909,658 US90965806A US2008210664A1 US 20080210664 A1 US20080210664 A1 US 20080210664A1 US 90965806 A US90965806 A US 90965806A US 2008210664 A1 US2008210664 A1 US 2008210664A1
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Prior art keywords
water
plasma
article
contact angle
water vapor
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US11/909,658
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Masamoto Uenishi
Shinfuku Nomura
Hiromichi Toyota
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Mitsubishi Chemical Corp
Ehime University NUC
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Mitsubishi Rayon Co Ltd
Ehime University NUC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02054—Cleaning before device manufacture, i.e. Begin-Of-Line process combining dry and wet cleaning steps
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
    • H01L21/02315—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
    • 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/14—Plasma, i.e. ionised gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/20—By influencing the flow
    • B01D2321/2066—Pulsated flow
    • B01D2321/2075—Ultrasonic treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes

Definitions

  • the present invention relates to a method of surface treatment of articles having a hydrophilic surface, and a surface-treated article by the method.
  • Patent Document 10 of the method (IV) discloses that the surface modification of fibers can be carried out by contacting the plasma bubbles to the fiber.
  • Raw materials of the fibers are not especially limited.
  • the plasma bubbles have high temperature of approximately 5000 K; on the other hand, the polymeric organic material does not usually have sufficient heat resistance which can withstand such high temperature.
  • a melting point and a softening point of the material are lower than the temperature of the plasma bubbles, it can be expected that the material will melt and flow, or will be thermal-decomposed or broken by contacting the plasma bubbles. It is difficult to apply the fiber using such material to the plasma bubbles.
  • Patent Document 10 discloses a carbon fiber as an example; however, the carbon fiber is extremely thin and a part of the fiber which contacted the plasma bubbles being partially high temperature is excessively graphitized by heat though the degree of graphitization changes in accordance with the pattern of crinkles of the surface of the fiber, the level of graphite structure of the surface of the fiber, and the level of flame resistance. Therefore, it is considered that the fiber becomes brittle locally and mechanical properties of the fiber decreases as a whole.
  • Patent Document 10 does not disclose whether the fiber can be washed without changing the pattern of the surface thereof. As described above, Patent Document 10 does not disclose regarding election of material.
  • An object of the present invention is to provide a method of surface treatment in which organic substances such as fouling which adheres to an article can be decomposed or removed without scattering in the atmosphere and damage of the article can be suppressed; a method for surface-treatment for etching the surface of the article with suppressing damage of the article; an article having little damage which is highly washed the surface thereof; an article having no damage which is etched by etching the surface thereof.
  • a method of surface-treatment of the present invention is characterized by contacting, in a liquid containing water, plasma generated in water vapor bubbles in the liquid to a material in which a contact angle to water is 90° or less.
  • An article of the present invention is an article surface-treated by the above method of surface-treatment.
  • the organic substances which adheres to an article can be decomposed or removed without scattering in the atmosphere and damage of the article can be suppressed. Furthermore, the surface of the article can be etched with suppressing damage of the article.
  • the article obtained by the method for surface-treatment of the present invention is highly etched or washed, and has little damage.
  • FIG. 1 is a schematic diagram showing an example of a plasma generating device.
  • FIG. 2 is a diagram showing a contact angle of water to the surface of an article.
  • FIG. 3 is a graph showing contact angle dependency of an etching speed by water vapor bubbles in the plasma state (hereinafter, referred to water vapor bubble plasma).
  • FIG. 4 is a typical diagram of a multilayer interconnection Damascene process.
  • FIG. 5 is a diagram showing emission spectrum from water vapor bubble plasma (Example 1).
  • FIG. 6 is electron microscope photographs of the surface of a hollow fiber membrane sample which is clogging.
  • FIG. 7 is electron microscope photographs of the surface of a hollow fiber membrane sample after treating the surface.
  • a method for surface-treatment of the present invention is a method of contacting, in liquid containing water, plasma generated in water vapor bubbles in the liquid to a material having hydrophilic surface.
  • An index of a hydrophilic material in the present invention is a material having a contact angle to water being 90° or less.
  • a plasma generating device used in the present invention a plasma generating device disclosed in Japanese Unexamined Patent Application, First Publication No. 2003-297598 or Japanese Unexamined Patent Application, First Publication No. 2004-152523 may be used.
  • the method for surface-treatment of the present invention is explained by using a specific plasma generating device as an example as follows.
  • FIG. 1 is a schematic diagram showing an example of a plasma generating device which is used in the method for surface-treatment of the present invention.
  • This plasma generating device 10 is equipped with a container 12 storing liquid 11 , an electrode 13 for radiating electromagnetic wave which is provided in the container 12 , a counter electrode 14 opposed to the electrode 13 , supports 16 fixing an article 15 between the electrode 13 and the counter electrode 14 , an electromagnetic wave power supply such as high-frequency power supply (not shown) connected to the electrode 13 and the counter electrode 14 , and a vacuum pump (not shown) adjusting pressure of an air phase 19 (gas phase) which is placed over the liquid 11 of the container 12 .
  • an electromagnetic wave power supply such as high-frequency power supply (not shown) connected to the electrode 13 and the counter electrode 14
  • a vacuum pump not shown
  • the electrode 13 is connected to the electromagnetic wave power supply which can supply high frequency and high voltage. Since electromagnetic energy of this power supply is supplied to the electrode 13 , the electrode 13 is heated, the liquid 11 around the electrode 13 is vaporized, and then water vapor bubbles 17 containing water vapor as a main component is adhered around the electrode 13 .
  • Water vapor bubble plasma Light emission is shown in the specific wave range in the water vapor bubbles in the plasma state (hereinafter, referred to water vapor bubble plasma).
  • the kind of gas generated in the plasma bubbles can be known from this emission spectrum.
  • Table 1 shows a wavelength of the emission spectrum of the water vapor bubble plasma and the assignment of the kind of gas which is a light emitting component.
  • the fouling is decomposed or removed by two actions, namely, (1) thermal decomposition by heat of the water vapor bubble plasma and (2) oxidization by OH-radical in the water vapor bubble plasma.
  • the liquid 11 may be used as long as a liquid contains water.
  • Typical examples of the liquid 11 include water, an aqueous solution containing an organic solvent which can be mixed with water, and an aqueous solution in which an electrolytic ion is dissolved in water.
  • Examples of the organic solvent which can be mixed with water include alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; and acetone.
  • Examples of the electrolytic ion include Mg 2+ , Ca 2+ , Na + , Fe 2+ , Fe 3+ , Cl ⁇ , NO 3 ⁇ , NO 2 ⁇ , and OH ⁇ .
  • the electrolytic ion being in the liquid 11 , electric conductivity of water is improved and arc discharge current tends easy to flow from the electrode 13 radiating electromagnetic wave to the counter electrode 14 when the plasma is generated.
  • the organic solvent is carbonized by the plasma and the carbide may adhere to the article 15 . If the volume fraction of water in liquid composition decrease, as described later, cooling effect by water to the surface of the article 15 decreases, and therefore, the surface of the article 15 becomes easy to be damaged. Therefore, preferably, the liquid 11 does almost not include the organic solvent, and more preferably, the liquid 11 does completely not include the organic solvent. Most preferably, pure water or ultrapure water which is used in a process for manufacturing a semiconductor is used.
  • the method for generating the water vapor bubbles 17 is not limited to the method of heating the electrode 13 , but may be a method of providing an ultrasonic wave generating device, generating cavitation bubbles in the liquid 11 by ultrasonic wave from the ultrasonic wave generating device, vaporizing the ambient liquid 11 into the cavitation bubbles as vapor, and forming the water vapor bubbles 17 .
  • the frequency of electromagnetic wave to be radiated to the water vapor bubbles 17 is selected according to its usage in the range of 1 MHz to 100 GHz.
  • the water vapor bubbles 17 may be generated by decompressing the air phase 19 in the container 12 by a vacuum pump.
  • the air phase 19 in the container 12 is decompressed, the boiling point of the liquid 11 decreases, water vapor becomes easy to generate, vapor pressure in the water vapor bubbles increases, and the number of water vapor molecules to be converted to plasma increases; as a result, plasma discharge is easily carried out. If the inside of the water vapor bubbles arrives in the plasma state once, plasma generation in the bubbles maintains even if the vacuum pump is stopped and the pressure of the air phase 19 is returned to an atmospheric pressure.
  • an article having a hydrophilic surface is preferred.
  • the article 15 include a hydrophilic polymeric organic material, a glass, a ceramic, a silicon wafer, a metal (for example, aluminum, copper, tungsten, and the like), a graphite, and a carbon fiber.
  • the “hydrophilic surface” is defined by a value of contact angle ⁇ defined in FIG. 2 .
  • the “hydrophilic surface” in the present invention is a surface having 90° or less of the contact angle ⁇ of water (waterdrop 18 ) to the surface of the article 15 at 25° C.
  • the contact angle of water to the hydrophilic surface is preferably lower, specifically 80° or less is more preferable and the range of 70° to 0° is most preferable.
  • the definition of the contact angle ⁇ in the present invention is equal to that of the contact angle which is a usual index of wettability of a material to water.
  • the description of “Metallic Functional Surface”, written by Yukio Murakawa, published by Kindai Henshu-sya on 1984, pp. 133 is referred. According to the description, when a droplet is dropped to a smooth surface in which the droplet is not reacted with the surface, and the droplet is in the equilibrium state to the surface while keeping a certain contact angle, the following formula (1) is realized in FIG. 2 .
  • ⁇ SV ⁇ SL + ⁇ LV cos ⁇ (1)
  • wettability increases as the decrease amount of ⁇ LV cos ⁇ becomes larger, i.e., wettability becomes better as ⁇ becomes less if ⁇ LV has a constant value.
  • the reason that the contact angle ⁇ of the waterdrop is used for quantifying wettability is based on the formula (2).
  • the liquid is water and ⁇ LV is 72.8 dyn/cm at 20° C. (see “Chronological Scientific Tables 1993” Maruzen Co., Ltd., pp. 449).
  • the contact angle ⁇ in FIG. 2 is determined by preparing a material having a smooth surface, maintaining the surface horizontally, dropping a waterdrop to the surface, and measuring ( ⁇ /2) by a contact angle measure. If the surface of the material is porously or has a portion consisting of alternate lands and grooves, a smooth surface using the same material is prepared, and then the contact angle ⁇ is determined. If the surface has a portion consisting of alternate lands and grooves in an organic polymer, a metal, a glass, or a ceramic, the smooth surface can be obtained by melting the same material.
  • a smooth sheet consisting of a precursor raw material for example, polyacrylonitrile or polyimide
  • a precursor raw material for example, polyacrylonitrile or polyimide
  • the precursor raw material is calcined to obtain a sheet having the smooth surface consisting of carbon material.
  • the contact angle is measured by dropping a waterdrop to this sheet. Examples of water used in the measurement of contact angle include clean water such as ultrapure water and ion-exchanged water.
  • Typical contact angles ⁇ of water to the polymeric organic material and inorganic material at 25° C. are shown in Tables 2 and 3 (reference a: “Chemical Handbook, 4 th Edition, Basic II”, Maruzen Co., Ltd., 1993, II-83, 7.1.3 Contact Angle; reference b: “Wettability Technology Handbook” edited by Yoshio ISHII, Masazumi KOISI, and Mitsuo TUNODA, Techno Systems Inc., 2001, b1: pp. 418; b2: pp. 92; b3: pp. 96; b4: pp. 102-103; b5: pp. 161; and b6: pp. 198).
  • the solid surface tension of ⁇ -Fe is 1670 to 2127 dyn/cm according to results of the measurement in the molten state at high temperature and the solid surface tension of copper is approximately 1500 dyn/cm according results of the measurement in the molten state at high temperature, therefore, they are far larger than the surface tension of polymer.
  • the surface tension of water is 72.8 dyn/cm.
  • the surface of a clean metal is very easy to wet to water.
  • the surface treatment of the present invention can be applied to a clean metal material having high surface energy.
  • any material such as a polymeric organic material, a glass, a ceramic, a metal, a graphite carbon material, a carbon fiber, and the like can be applied as long as the material satisfies ⁇ 90°.
  • the wavelength of atomic hydrogen (H ⁇ : 656 nm) in plasma in the water vapor bubbles is converted into temperature, it is high temperature of approximately 5000 K. If the plasma gas having the above high temperature is contacted to an article consisting of a usual polymeric organic material, the article is completely destroyed at the instant of contact.
  • the present inventors have found that when the article consisting of a hydrophilic material satisfying ⁇ 90°, only organic substances adhered to the surface of the article can be decomposed and removed, and subsequently washed without damaging the surface of the article, and the surface can be etched without destroying a clean article obtained by washing.
  • FIG. 3 The idea of the present invention for overcoming thermal decomposition is schematically shown in FIG. 3 .
  • the contact angle ⁇ to water of a material is 90° or less when the material is contacted to the water vapor bubbles, contribution of pyrolytic etching by heat is decreased, and if the contact angle ⁇ to water of a material is larger than 90°, contribution of the pyrolytic etching is increased. The reason why this phenomenon occurs is described as follows.
  • the surface of the material satisfying ⁇ being 90° or less is coated by a layer of water in liquid containing water. Even if the water vapor bubble plasma closes to the material, water on the surface of the material is vaporized while consuming latent heat of vaporization around the material and water is continuously supplied to the hydrophilic surface. Therefore, a persistent cooling effect is affected to the surface of the material and temperature rise of the article is suppressed. As a result, the surface temperature of the article does not exceed a heat-resistant temperature of the material, contribution of etching by thermal decomposition is decreased, and the damage of the material is suppressed. These effects are also effective for preventing local excess graphitization by heat of plasma in the surface treatment of carbon fiber.
  • the fouling adhered to the surface of the material is decomposed by undergoing operations of thermal decomposition by heat of the water vapor bubble plasma and oxidative destruction by OH-radical.
  • the fouling decreases, a hydrophilic surface of the material appears and thermal decomposition is suppressed by cooling effect of water as described above, as a result, the surface of the material having little damage is obtained.
  • the material When the hydrophilic material having 90° or less of the contact angle is used, the material can be gradually etched by oxidative destruction by OH-radical while etching by thermal decomposition is suppressed.
  • Various hydrophilic materials can be etched by the oxidative destruction.
  • a hydrophilic polymer material, a metal material, and a ceramic, or a glass showing hydrophilicity, a carbon material showing hydrophilicity, and the like can be etched.
  • time during contacting the article 15 and the water vapor bubble plasma (hereinafter, referred to a contact time) may be adjusted suitably in consideration of heat-resistant temperature of the article 15 , temperature in the bubble plasma, cooling effect of water generated on the surface of the article 15 , and a degree of fouling.
  • the “contact time” in the present invention is defined as, if the article 15 rests, time during generating plasma in the water vapor bubbles 17 by applying voltage to the electrode 13 and the counter electrode 14 , and if the articles 15 moves to a constant direction, the contact time is defined below.
  • the index of the heat-resistant temperature of the material changes in accordance with kinds of materials.
  • the heat-resistant temperature is defined as a temperature which is able to maintain the shape of the material.
  • the melting point in a crystalline material and the glass transition temperature in an amorphous are defined as indexes of heat-resistant temperature.
  • Glass transition temperatures (Tg) and melting point (Tm) of typical crystalline polymeric organic materials are shown in Table 4 (Joel R. Fried, “Polymer Science and Technology”, Prentice Hall, 1995, pp. 140).
  • a melting point is defined as an index of the heat-resistant temperature. Melting points (Tm) of typical ceramics are shown in Table 5 (Marcel Mulder, “Basic Principles of Membrane Technology, 2 nd Edition, Kluwer Academic Publishers, 1996, pp. 60).
  • a grass transition temperature is defined as an index of the heat-resistant temperature. Glass transition temperatures of typical optical glasses are shown in Table 6 (Optical application technique workshop text, “Optical Material III-9”, Japan Optomechatronics Association, 1988, pp. 30).
  • a melting point is defined as an index of the heat-resistant temperature. Melting points (Tm) of typical optical crystalline materials are shown in Table 7 (Optical application technique workshop text, “Optical Material III-9”, Japan Optomechatronics Association, 1988, pp. 55).
  • melting point is defined as an index of the heat-resistant temperature.
  • Melting points (Tm) of typical metals are shown in Table 8 (“Chronological Scientific Tables 1993” edited by National Astronomical Observatory of Japan, published by Maruzen Co., Ltd., pp. 469).
  • the melting temperature 3550° C. of a graphite single crystal of a related material is defined as an index of structural phase transition of the carbon material.
  • the heat-resistant temperature of carbon fiber is defined to the temperature which can maintain the shape of fiber because there are many cases that the carbon fiber has low degree of crystallinity, a clear identification of amorphous parts and crystal parts is difficult, and the specific structural phase transition point of crystal is not easily determined.
  • the surface treatment method of the present invention can be applied to (1) a washing step of an article in which organic substances such as a fouling are adhered (deposited) on the surface of the material, (2) an etching step of the surface of a hydrophilic material, and (3) a modifying step of imparting a portion consisting of alternate lands and grooves to the surface of the material.
  • the washing step (1) is explained below.
  • the organic substances include general organic substances, which exist in daily living, such as a virus, bacteria, yeast, mold, algae, protozoa, protein, blood, and component of blood; animal or plant cells; organic substances contained in hair, domestic refuse, garbage, drainage, and the like; and a fertilizer component.
  • washing articles according to the surface treatment method of the present invention.
  • Objects of washing are not limited by the following examples, but any material can be selected as long as the article has hydrophilicity and the contact angle ⁇ of water to the material is 90° or less.
  • the article can be washed when a process is suitably selected according to temperature of the plasma bubbles and the cooling effect condition.
  • a porous membrane is recycled by contacting plasma to the porous membrane having a hydrophilic surface used in a filtration treatment, and decomposing and removing filtration sediment consisting of the organic substances adhering to the surface of the membrane by thermal decomposition (or carbonization) or oxidation with OH-radical.
  • a biocompatible material is recycled by contacting plasma to the biocompatible material having a hydrophilic surface which is taken out from a human body after the biocompatible material is embedded in the human body, decomposing and removing the organic substances adhering the surface of the biocompatible material by thermal decomposition (or carbonization) or oxidation with OH-radical.
  • the biocompatible materials include polymethyl methacrylate resin, polylactic acid resin, polyurethane, hydrogel, cellose, polyvinyl alcohol, hydroxyapatite, and the like.
  • Cancer cells in an organ are decomposed and removed by contacting plasma to the organ having a hydrophilic surface which is taken out from a human body to thermal-decompose (or carbonize) the cancer cells or oxidize the cancer cells with OH-radical.
  • Bacteria adhering to a catheter or an artificial vascular graft having hydrophilic surfaces are eliminated by contacting plasma to the catheter or the artificial vascular graft before embedding in a human body, or organic substances adhering to a catheter or an artificial vascular graft having hydrophilic surfaces are decomposed and removed by contacting plasma to the catheter or the artificial vascular graft taken out from a human body to thermal-decompose (or carbonize) the organic substances or oxidize the organic substances with OH-radical. After decomposing and removing the organic substances, the catheter and the artificial vascular graft is disposed in safety.
  • a photoresist membrane is removed by contacting water vapor bubble plasma to the surface of a silicon wafer whose surface is coated by a lithography material such as the photoresist membrane. Or, a fouling on the silicon wafer is washed by contacting the water vapor bubble plasma to the silicon wafer in which the fouling adheres to the surface thereof.
  • the surface of a glass plate especially, a glass plate used for a liquid crystalline cell and the surface of a glass master used for a mastering process of an optical disk are required to be highly washed and cleaned.
  • the RCA washing technique using a chemical solution is used.
  • a washing technique without using the chemical solution is required.
  • a fouling adhering to the glass plate can be decomposed without impairing the surface of the glass plate by contacting OH-radical generated from the plasma bubbles to the glass plate and adjusting a contact time suitably.
  • the decomposed substances become carbide, carbon dioxide, or water, and also toxic waste water is not generated.
  • a fluorine electrolytic membrane used for a solid electrolytic membrane (for example, Nafion® membrane manufactured by Du Pont) has high hydrophobicity. In this case, if the electrolytic membrane is soaked in water to swell the membrane by water, the water content of the membrane is increased and the contact angle to water is decreased. The surface of the membrane having 90° or less of the contact angle can be washed by the technique of the present invention.
  • Examples of the etching step of the surface of a hydrophilic material (2) as described above are as follows.
  • FIG. 4 shows a schematic diagram of the Damascene process.
  • a process is progressed by a b c and a patterning of a metal for wiring is formed in c.
  • the metal film can be precisely treated while the metal atom is removed with an atomic level by an electrochemical reaction of the metal atom and an atomic hydrogen and OH-radical generated from the water vapor bubble plasma.
  • the speed of etching with OH-radical should be controlled suitably.
  • Al(001) is used for a cathode, they reported regarding a surface reaction elementary process that (1) if OH is bonded to the Al(001) surface atom, a binding affinity between the surface first layer and the second layer atom is decreases; and (2) if OH and H affect to a hydrogen-terminated Al(001) surface, all bonds between Al surface atoms are cut and the Al surface atoms are removed and treated as AlH 2 (OH) molecules.
  • H and OH are generated by the catalyst and an electrochemical reaction using the OH is used; however, any investigation result by OH-radical generated from the water vapor bubble plasma has not been disclosed.
  • the present inventors emphasize that the present technique is applicable to a precise etching process for removing a metal from the material while chemical bonds of atoms of the metal surface are cut, as well as the above document, by affecting OH-radical generated from the water vapor bubble plasma of the present invention to the metal because a clear metal has hydrophilicity to water.
  • the silicon wafer can be washed by soaking a dirty silicon wafer in water of the reaction device shown in FIG. 1 , and contacting the silicon wafer to the water vapor bubble plasma while rotating the silicon wafer.
  • porous membranes include a hollow fiber membrane made of polyethylene which is treated so as to be a hydrophilic one; a flat membrane; and a tubular membrane.
  • the dirty porous membrane is soaked in water and is anchored in the vicinity of an electrode radiating electromagnetic wave. If the electromagnetic wave is radiated from the electrode, water vapor bubbles are generated around the electrode, and simultaneously plasma is generated in the water vapor bubbles. If plasma generated in the water vapor bubbles is contacted to the surface of the porous membrane with a predetermined contact time, the organic substance adhering to the surface of the membrane is thermal-decomposed and blown out by plasma.
  • the hydrophilic surface exposed after the organic substance is blown out is coated by a water layer because the hydrophilic surface tends to wet with water. As a result, the hydrophilic surface is hardly affected by plasma and a microporous structure formed by the porous membrane is almost completely maintained.
  • the contact time is preferably 1 to 5 minutes. If the contact time is 1 minute or shorter, the organic substance such as a fouling adhering the surface of the porous membrane may be insufficiently removed. If the contact time is longer than 5 minutes, a part of the surface of the porous membrane starts melting.
  • Specific examples of (a) are described above, and the same process can be applied to each example of (a) to (m) for removing the fouling. In addition, the present invention can be applied to each etching of (n) to (o).
  • the surface treatment method of the present invention is applicable to a partial etching of the article. That is, if the article having both the hydrophobic surface ( ⁇ >90°) and the hydrophilic surface ( ⁇ 90°) is contacted to plasma, the speed of etching to the hydrophobic surface increases and a portion consisting of alternate lands and grooves is formed on the surface of the article.
  • This technique for forming the portion consisting of alternate lands and grooves is usable to etching of a material in a semiconductor lithography step, and a treatment process for forming a fine portion consisting of alternate lands and grooves of a plastic material (for example, a treatment process for imparting a non-glare function for preventing the reflection of an image to the surface of a transparent resin plate).
  • the decomposed organic substance from the article cannot be discharged into the atmosphere. Especially, without discharging virus, toxic organic substances, and the like into the atmosphere, they can be safely decomposed and removed in water.
  • the decomposed substance can be safely extracted from water by collecting the decomposed substance which is transferred into water with an adsorption filter and the like.
  • etching of a material according to the surface treatment of the present invention since OH-radical generated from water is used for decomposition without using an electrolytic solution or chemical agents such as sulfuric acid, hydrochloric acid, a hydrogen fluoride aqueous solution, and the like, waste water of the chemical agents is not generated after reaction. If the metal is etched, metal hydroxide is precipitated; however, since the metal hydroxide is insoluble to water, solid-liquid separation can be carried out, as a result, the toxic waste water to environment is not generated.
  • chemical agents such as sulfuric acid, hydrochloric acid, a hydrogen fluoride aqueous solution, and the like
  • the surfaced treatment using a carbon fiber suitable for the present invention When the surfaced treatment using a carbon fiber suitable for the present invention is carried out, excessive graphitization by high temperature of the water vapor bubble plasma is suppressed and the surface treatment such as etching or washing by OH-radical to the whole fiber can be uniformly carried out while it is maintained that the fiber is stably carbonized. Therefore, the carbon fiber can be continuously manufactured; that is a high value-added manufacture industrially.
  • a water-purifying device for home use (trade name: Cleansui 02) manufactured by Mitsubishi Rayon Co., Ltd. was prepared.
  • the hollow fiber membrane is a hollow fiber membrane having inner diameter of 270 ⁇ m and thickness of the membrane of 55 ⁇ m manufactured by Mitsubishi Rayon Co., Ltd.
  • fibrils made of polyethylene oriented in the direction of the fiber of the hollow fiber membrane the hollow fiber membrane had a pore structure being a slit form in which many fibrils were piled up in the direction of the thickness of the membrane.
  • the clogged hollow fiber membrane was washed by the following process.
  • the clogged hollow fiber membrane sample was fastened to a hollow fiber membrane which was treated so as to become a hydrophilic one (EX-540V polyethylene hollow fiber membrane manufactured by Mitsubishi Rayon Co., Ltd.) to prepare a sample for experiment.
  • a hydrophilic one EX-540V polyethylene hollow fiber membrane manufactured by Mitsubishi Rayon Co., Ltd.
  • a plasma generating device As a plasma generating device, a device shown in FIG. 1 was used. As an RF power supply, type T161-5766LQ manufactured by Thamway Co., Ltd. was used, and as a matching box, type T0202-5766LQ manufactured by Thamway Co., Ltd. was used.
  • the sample for experiment was soaked in a container filled by water and the container was provided in the vicinity of the electrode and was fixed by supports. Water was heated using exothermic heat of the electrode, and water vapor bubbles were generated in water by heated water.
  • FIG. 1 at reduced pressure environment of 30 hPa of vapor pressure, the water vapor bubbles were irradiated with electromagnetic wave (27.1 MHz) at an output of 300 W so that water vapor in the bubbles became plasma state, and subsequently the pressure was adjusted to the atmospheric pressure for maintaining generation of the water vapor bubble plasma.
  • An emission spectrum from the water vapor bubble plasma when the gas phase is at the atmospheric pressure is shown in FIG. 5 .
  • Spectrum intensity per wavelength of this emission spectrum was obtained by measuring light from the light-emitting bubbles using a PMA-11C-7473-36 Czeny-Turner type compact polychromator and a back-illuminated CCD linear image sensor both manufactured by Hamamatsu Photonics K.K. in the reaction device shown in FIG. 1 .
  • the number of light-detecting elements was 1024, the wavelength range was 200 to 950 nm, and exposure time was 19 ms.
  • the measurement was carried out using a polychromator and a linear image sensor in which sensitivity unevenness of wavelength was adjusted and each wavelength axis was calibrated.
  • Example 1 The same plasma generating device as Example 1 was used.
  • the sample for experiment was soaked in a container filled with water and the samples were fixed with supports in the vicinity of the electrode. Except using an ethylene/vinyl alcohol copolymer film (hereinafter, may be referred to EVAL film) shown in Table 9 as a sample, water vapor bubble plasma was generated and the plasma was contacted to the sample for 3 minutes at the same condition as Example 1.
  • EVAL film ethylene/vinyl alcohol copolymer film
  • Table 9 Table 9
  • Each film had the contact angle to water before contacting to plasma being within 64 to 71° and showed hydrophilicity.
  • Plasma durability 6) (Gas phase of reaction device: atmospheric pressure) 7) Measurement of contact angle of EVAL film Having durability 8) : EVAL film good Ethylene 1) ⁇ /2 2) ⁇ 3) RH 5) Not having Sample (mol %) (degree) (degree) T 4) (° C.) (% RH) durability 9) : not good D2908 29 32.2 64.4 25.4 37 Good DC3203F 32 33.6 67.2 25.5 38 Good ET3803 38 34.6 69.3 25.6 38 Good AT4403 44 35.1 70.1 25.6 38 Good H4815B 48 35.7 71.4 25.7 38 Good 1) Ethylene: ethylene content 2) ⁇ /2: value observed by a contact angle measure CA-DT manufactured by Kyowa Surface Science, Co., Ltd.
  • the surface of the film of sample DC3203F was marked by oil-based ink.
  • the marking part was irradiated with plasma, and as a result, the oil-based ink was decomposed by plasma and did not remain on the surface of the film.
  • the film surface after washing was visually observed to be smoothly.
  • Nafion® 112 and Nafion® 1035 membranes manufactured by DuPont were soaked in ion-exchanged water at 25° C. for 5 minutes to swell the membranes, and the swollen membranes were taken out and the contact angles thereof were measured. The contact angles were shown in Table 10. Nafion® 112 and Nafion® 1035 shown in Table 10 were used as samples for plasma treatment.
  • Example 2 The same plasma generating device as Example 1 was used. The samples were soaked in a container filled with water and the samples were fixed with supports in the vicinity of the electrode. Subsequently, water vapor bubble plasma was generated at the same conditions as Example 1, and the plasma was contacted to the samples for 3 minutes. As shown in Table 10, both swollen Nafion® 112 and Nafion® 1035 membranes stood the heat of the water vapor bubble plasma, and their original forms were maintained.
  • the surface of the Nafion® 112 membrane was marked by oil-based ink.
  • the ink was firmly adhered to the membrane.
  • the marking part was contacted to the water vapor bubble plasma in water for 3 minutes, and then the marking part was visually observed.
  • the oil-based ink was decomposed by plasma and did not remain on the surface of the membrane.
  • the surface of the membrane after washing was visually observed to be smoothly.
  • Example 2 The same plasma generating device as Example 1 was used.
  • the sample for experiment was soaked in a container filled with water and the samples were fixed with supports in the vicinity of the electrode. Except using a glass plate which was optically polished (thickness: 5 mm, 100 mm ⁇ 100 mm) as a sample, water vapor bubble plasma was generated and the plasma was contacted to the glass plate for 3 minutes at the same condition as Example 1.
  • the glass plate stood the heat of water vapor bubble plasma and maintained its original form.
  • the contact angle to water of the glass plate before contacting to plasma was approximately 35°.
  • the surface of the glass plate was marked by oil-based ink.
  • the marking part was contacted to the water vapor bubble plasma in water for 3 minutes, and then the marking part was visually observed.
  • the oil-based ink was decomposed by plasma and did not remain on the surface of the glass plate.
  • the surface of the glass plate after washing was visually observed to be smoothly.
  • Example 2 The same plasma generating device as Example 1 was used.
  • the sample for experiment was soaked in a container filled with water and the samples were fixed with supports in the vicinity of the electrode. Except using an alumina ceramic sheet ( ⁇ -Al 2 O 3 sheet thickness: 3 mm, 100 mm ⁇ 100 mm) as a sample, water vapor bubble plasma was generated and the plasma was contacted to the alumina ceramic sheet for 3 minutes at the same condition as Example 1.
  • the contact angle to water of the alumina ceramic sheet before contacting to plasma was approximately 55°.
  • the surface of the alumina ceramic sheet was marked by oil-based ink.
  • the marking part was contacted to the water vapor bubble plasma in water for 3 minutes, and then the marking part was visually observed.
  • the oil-based ink was decomposed by plasma and did not remain on the surface of the alumina ceramic sheet.
  • the surface of the alumina ceramic sheet after washing was visually observed to be smoothly.
  • Example 2 The same plasma generating device as Example 1 was used.
  • the sample for experiment was soaked in a container filled with water and the samples were fixed with supports in the vicinity of the electrode.
  • An ethylene-vinyl alcohol copolymer film (ethylene content: 32 mol %) was as a substrate (thickness: 3 mm, 100 mm ⁇ 100 mm), a polyethylene film having 5 mm in width (thickness: 0.5 mm, 100 mm ⁇ 100 mm) was adhered to the substrate with interval of 5 mm by heat seal to prepare a sample composed of a hydrophilic surface and a hydrophobic surface (hydrophilic part: 5 mm in width, hydrophobic part: 5 mm in width).
  • the contact angle to water of the ethylene-vinyl alcohol copolymer film was 67° and the contact angle to water of the polyethylene film was 95°.
  • Example 2 Except using the prepared sample, water vapor bubble plasma was generated and the plasma was contacted to the whole sample for 3 minutes by the same method as Example 1. After contacting, when the sample was taken out from a reaction container, the polyethylene film which was the hydrophobic part was etched by plasma and then the average thickness thereof was 0.1 mm. On the other hand, the ethylene-vinyl alcohol copolymer film substrate was maintained the original smooth surface. Only hydrophobic part was etched by plasma.
  • a polytetrafluoroethylene film having 100 ⁇ m thickness in which hydrophilic treatment was not carried out (contact angle to water (25° C.): 110°), a polyethylene film (contact angle to water (25° C.): 95°), and a polypropylene film (contact angle to water (25° C.): 96°) were prepared.
  • the surfaces of these films were not adhered with organic substances such as fouling.
  • the surface treatment was carried out to these films using the same method as Example 1. The moment plasma was contacted to these films these films were thermal-decomposed by high temperature of plasma and were broken.
  • a polymeric organic porous flat membrane having 50 ⁇ m thickness in which hydrophilic treatment was not carried out (manufactured by Nihon Millipore K.K., hydrophobic polytetrafluoroethylene membrane, contact angle to water (25° C.): 110°, average pore size: 1 ⁇ m)
  • a polymeric organic porous flat membrane having 100 ⁇ m thickness (manufactured by Nihon Millipore K.K., hydrophobic polyethylene membrane, contact angle to water (25° C.): 94°, average pore size: 1 ⁇ m) were prepared.
  • the surfaces of these polymeric porous flat membranes were not adhered with organic substances such as fouling.
  • the surface treatment was carried out to these polymeric porous flat membranes using the same method as Example 1. The moment plasma was contacted to these flat membranes these flat membranes were thermal-decomposed by high temperature of plasma and were broken.
  • Example 3 Except using two kinds of Nafion® membranes (Nafion® 112 and Nafion® 1035) manufactured by DuPont which were left to stand at 25° C. and 55% RH for one week as samples, the water vapor bubble plasma was contacted to the samples at the same condition as Example 3.
  • Example 2 200 mL of pure water was prepared in a 300 mL volume beaker, the clogged hollow fiber membrane used in Example 1 was soaked in pure water of 25° C., and the hollow fiber membrane was washed by a 20 KHz ultrasonic washer with output of 100 W for one hour. The washed membrane was observed by an electron microscope. The organic substance clogging in the membrane surface was not removed.
  • Example 1 the electrode in the reaction device was heated to generate water vapor bubbles not in the plasma state and the water vapor bubbles were contacted to the clogged hollow fiber membrane sample for 3 minutes. As a result, the organic substance clogging in the membrane surface was not removed.
  • the present invention is a surface treatment method for decomposing and removing organic substances adhering to an article by contacting plasma generated in water vapor bubbles and the article having a hydrophilic surface without injuring the article.
  • This surface treatment method is usable to, for example, a water-purifying device for home use, a filter for industrial wastewater, a polymeric organic porous membrane for an air filter, recycle of a ceramic porous membrane, and safety disposal of a porous membrane.
  • the surface treatment method is usable to a method for safety recycling or disposing membranes contaminated or clogged by a substance containing bacteria such as a membrane filter for water of lavatory in a hospital, a membrane air filter for preventing hospital infection in hospital, a membrane air filter for a biohazard safety room, and the like.
  • the surface treatment method of the present invention is applicable to a treatment for safety disposing a biocompatible material by thermal-decomposing or carbonizing organic substances such as bacteria on the surface of the material after embedding the biocompatible material in a human body and using the material; a treatment for using for safety of a life by thermal-decomposition or carbonizing cancer cells coexisting with organs; a treatment for safety disposing spent contact lenses by thermal-decomposing or carbonizing organic substances such as bacteria, blood, and protein adhering to the lenses; and the like.
  • the surface treatment method of the present invention is also applicable to a treatment for eliminating bacteria from a catheter, an artificial vascular graft, and the like before being embedded in a human body and sterilizing bacteria and the like adhering to the catheter, artificial vascular graft, and the like after being taken out from the human body; a treatment for removing bacteria which is not an object of detection from a DNA sample detecting device; a treatment for safety disposing the spent DNA sample detecting device; a treatment for safety disposing an air filter, a mask, and the like in which non-woven fabric is used by thermal-decomposing or carbonizing bacteria adhering to the non-woven fabric; and the like.
  • the etching process of the present invention is usable for processing a privacy filter in which antireflection function for optical use and visibility at only specific view angle are developed by imparting a portion consisting of alternate lands and grooves finely to the surface of a hydrophilic transparent organic material. Furthermore, the surface of a metal film can be etched by a chemical species derived from a water molecule. As a result, since the cost of disposing treatment can be decreased in a Damascene process of high density multilayer interconnection in a semiconductor device, the present invention is effective for the decrease of manufacturing cost.
  • dielectric film Since this dielectric film has large pore volume and the material of the film has a hydrophobic contact angle to water, it is difficult to flatten the whole after etching a metal film in a conventional chemical mechanical polishing process because a polishing solution is repelled by the dielectric film.
  • the low dielectric constant film is etched by OH-radical in the water vapor bubble plasma and a structure of a flat dielectric film/a multilayer interconnection metal can be obtained.
  • the etching process of the present invention if the contact time to the water vapor bubble plasma is controlled to be short, only a hydrophobic part can be selectively etched.
  • This method is applicable to a selective etching process of the hydrophobic part in various materials such as an organic material, an inorganic material, and a carbon material containing both hydrophilic surfaces and hydrophobic surfaces.
  • materials such as the carbon material and a silicon wafer are difficult because the materials have a high heat-resistant temperature, the etching becomes easily according to the etching process of the present invention.

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TWI405608B (zh) 2013-08-21
KR20070113313A (ko) 2007-11-28
KR100938323B1 (ko) 2010-01-22
JP5518281B2 (ja) 2014-06-11
JPWO2006104043A1 (ja) 2008-09-04
TW200637648A (en) 2006-11-01
JP5725304B2 (ja) 2015-05-27

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