JP2010258410A - Method for forming pattern of metal film, and component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method of a metal film by which a lamination amount of metal is optionally controlled using a polymer compound having superior heat resistance and durability by small number of processes. <P>SOLUTION: A pattern of a metal film is formed by the steps of: covering a substrate surface containing silicone-based resin with a shielding material having a desired pattern; forming an irradiated portion and a non-irradiated portion by irradiating the substrate surface covered with the shielding material with an active energy beam of 1,000 to 1,000,000 mJ/cm<SP>2</SP>in cumulative amount of light; and laminating metal on the substrate surface having the irradiated portion and non-irradiated portion. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a metal film pattern forming method and a member manufactured by the metal film pattern forming method.

  Metal films having various patterns are used for various applications. Examples thereof include electrode members and wiring members of electronic devices, light shielding films for photomasks used in photolithography, and various optical members.

Conventionally, a photolithography method has been used to form a metal film in a desired pattern. The photolithography method includes a step of forming a metal film on the upper surface of a substrate; a step of applying a resist on the upper surface of the metal film; a step of evaporating a solvent in the resist; a step of exposing the resist to a desired pattern shape using a photomask. A step of eluting an exposed portion of the resist with a developer; a step of washing the resist with pure water to remove the developer; and a step of heating at a predetermined temperature to remove the developer / rinse solution remaining in the resist; Many steps were required, such as a step of etching the underlying metal film using a resist; a step of removing an unnecessary resist with an oxidizing solvent.
In addition, there are many problems such as 90% or more of the resist solution being wasted in the resist coating process, and the use of a large amount of an organic solvent that may adversely affect the environment in the development process or the peeling process. there were.

  In recent years, various metal film pattern forming methods that can replace the photolithography method have been proposed. For example, Patent Document 1 proposes a method for forming a magnesium film pattern by utilizing the fact that 1,2-diarylethene derivative, which is a kind of photochromic molecular material, is isomerized to change the vapor deposition property of magnesium. Yes.

  However, special low molecular weight organic compounds such as 1,2-diarylethene derivatives are very complicated to synthesize and are expensive to manufacture. Further, it is difficult to arbitrarily control the amount of metal lamination. Furthermore, since it is a low molecular organic compound, the heat resistance and durability of the member are inferior.

JP 2007-188854 A

  It is an object of the present invention to provide a metal film pattern forming method that uses a polymer compound having excellent heat resistance and durability with a small number of steps and that can arbitrarily control the amount of metal laminated.

The present invention includes a step of coating a surface of a substrate containing a silicone resin with a shielding material having a desired pattern, and an active energy ray with an integrated light amount of 1,000 to 1,000,000 mJ / cm ^{2 on} the surface of the substrate coated with the shielding material. A metal film pattern forming method including a step of irradiating to form an irradiated portion and an unirradiated portion, and a step of laminating a metal on a substrate surface having the irradiated portion and the unirradiated portion.

  Moreover, this invention is a member manufactured by the pattern formation method of this metal film.

  The metal film pattern forming method of the present invention can arbitrarily control the metal lamination amount with a small number of steps. In addition, since the polymer compound is used, it is expected that the member is excellent in heat resistance and durability.

It is the graph which showed the reflectance in 380-780 nm of the irradiated part of the active energy ray of the member obtained in Example 3, and the non-irradiated part.

The substrate surface of the present invention contains a silicone resin.
Examples of the silicone resin of the present invention include linear silicone resins and silicone resins having a crosslinked structure.

The linear silicone resin is usually obtained by polymerizing a silicone monomer component containing a bifunctional silicone monomer. Examples of the linear silicone resin include polydialkylsiloxane and polyalkylphenylsiloxane.
The silicone resin having a crosslinked structure is usually obtained by polymerizing a silicone monomer component containing a bifunctional, trifunctional or tetrafunctional silicone monomer. Examples of the silicone resin having a crosslinked structure include a condensation type thermosetting silicone resin, an addition type thermosetting silicone resin, and a photocurable silicone resin.

  As the condensation type thermosetting silicone resin, for example, based on polydimethylsiloxane having a silanol group at the terminal, polydimethylhydrogensiloxane is blended as a crosslinking agent, and organic acid metal salts such as organotin or amines are used. Silicone resin synthesized by heat condensation in the presence of a catalyst; silicone resin synthesized by reacting a polydiorganosiloxane having a reactive functional group such as a hydroxyl group or an alkoxy group at the end; trifunctional or higher functional chlorosilane or A silicone resin synthesized by condensing silanol obtained by hydrolyzing the mixture may be used.

  Addition-type thermosetting silicone resins include, for example, silicones based on polydimethylsiloxane containing vinyl groups, blended with polydimethylhydrogensiloxane as a crosslinking agent, and reacted and cured in the presence of a platinum catalyst. Based resins. Specifically, a silicone resin of SYLGARD 184 (trade name, manufactured by Toray Dow Corning Co., Ltd.) can be mentioned. Examples of the polymerization system of the addition type thermosetting silicone resin include a solvent system, a water dispersion system, and a solventless system. In these, since the handleability of a silicone type resin is excellent, a solventless type is preferable.

  Examples of the photocurable silicone resin include a silicone resin synthesized using a photocationic catalyst; and a silicone resin synthesized using a radical curing mechanism.

The silicone resin of the present invention is based on polydimethylsiloxane, and a part of the methyl group of the polydimethylsiloxane is an alkyl group such as ethyl group, propyl group, butyl group; phenyl group, tolyl group, xylyl group. Aryl groups such as benzyl group and phenethyl group; halogen atoms such as chlorine atom and fluorine atom; alkoxy group; hydroxyl group; amino group; epoxy group;
Among these, since the contrast between the irradiated part of the silicone resin and the non-irradiated part when irradiated with active energy rays is excellent, polydimethylsiloxane or a part of the methyl group of polydimethylsiloxane is an alkyl group. Alternatively, those substituted with an aryl group are preferred, and polydimethylsiloxane is more preferred.

  Various additives may be added to the silicone-based resin of the present invention as necessary. For example, fuming silica, calcined silica, precipitated silica, titania, zinc oxide, clay, mica, pulverized calcium carbonate, magnesium carbonate, Examples include fillers such as quartz, diatomaceous earth, barium sulfate, wollastonite, leaf wax, kaolin, and calcium sulfate; viscosity modifiers; stabilizers; colorants;

  The substrate of the present invention may be a silicone resin itself or any material that can be coated with a silicone resin.

  Examples of optional materials to which the silicone resin of the present invention can be applied include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, cyclic polyolefin, polynorbornene, polystyrene, styrene-acrylate copolymer, acrylonitrile-styrene copolymer, polyethylene. Polymer materials such as naphthalate, polyethersulfone, polysulfone, nylon, polyurethane, cellulose diacetate, cellulose triacetate, polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride, quartz, glass, silicon wafer, ceramics, metal, etc. An inorganic material is mentioned.

  Examples of the method for applying the silicone resin of the present invention include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.

  When the silicone resin of the present invention is applied, the solid content concentration of the silicone resin may be adjusted using any kind or amount of solvent or solute depending on the application method or the like. For example, when a silicone resin is applied by spin coating, the solid content concentration of the silicone resin solution is generally 5 to 50% by mass.

  As a film thickness at the time of apply | coating the silicone resin of this invention, 0.001-5000 micrometers is common.

The active energy ray of the present invention is not particularly limited as long as it can decompose organosiloxane, and examples thereof include ultraviolet rays, electron beams, and ion beams. Among these, ultraviolet rays are preferable because of the excellent decomposability of organosiloxane and the productivity of members.
Examples of the ultraviolet light source include laser oscillation devices such as excimer laser, argon laser, krypton laser, nitrogen laser; deuterium lamp, high pressure mercury lamp, low pressure mercury lamp, xenon lamp, mercury xenon lamp, halogen lamp, excimer lamp, arc Examples thereof include an ultraviolet lamp such as a discharge lamp obtained by discharge, corona discharge or silent discharge. Among these ultraviolet ray sources, deuterium lamp, high pressure mercury lamp, low pressure mercury lamp, xenon lamp, mercury xenon lamp, halogen lamp, and excimer lamp are preferable because of excellent balance of intensity, irradiation range, etc., low pressure mercury lamp Is more preferable.

Examples of the atmosphere when irradiating the active energy ray of the present invention include air, oxygen, nitrogen, ozone, water vapor, ammonia, and a mixture of the above gases. Among these, air, oxygen, and ozone are preferable because the pattern contrast between the irradiated portion and the non-irradiated portion is excellent.
The contrast between the irradiated part and the non-irradiated part of the active energy ray is due to the fact that the side chain of the organosiloxane is oxidized and decomposed in the atmosphere of air, oxygen and ozone in the irradiated part, and the generation of silanol groups and the surface elastic modulus increase. It is thought to occur.

  As a method of obtaining the surface having the irradiated part and the non-irradiated part of the active energy ray of the present invention, for example, it can be obtained by using a shielding material that shields the active energy ray, and the part irradiated with the active energy ray Is the irradiated part, and the part where the active energy ray is shielded by the shielding material is the unirradiated part. Examples of the shielding material include a photomask having a desired shape and black paper.

Integrated light quantity of the active energy ray according to the invention are 1,000~1,000,000mJ / cm ^2, is preferably 5,000~400,000mJ / cm ^2, 10,000~80,000mJ / more preferably cm ^2. When the integrated light amount of the active energy ray is 1,000 mJ / cm ² or more, the metal film in the irradiated portion is sufficiently laminated, and the contrast of the pattern of the metal film in the irradiated portion and the unirradiated portion becomes clear. Further, when the integrated light amount of the active energy ray is 1,000,000 mJ / cm ² or less, the substrate or the metal film is not broken, such as a crack.
The integrated light amount of the active energy ray is indicated by time integration of the irradiation intensity of the active energy ray. If the irradiation intensity of the active energy ray is constant, the integrated light amount of the active energy ray is equal to the irradiation intensity of the active energy ray. It is shown as the product of irradiation time of active energy rays.

  The distance between the light source of the active energy ray and the substrate of the present invention can be appropriately set according to the irradiation intensity of the active energy ray.

  Examples of the metal lamination method of the present invention include dry processes such as vacuum deposition and sputtering; wet processes such as electroless plating. In these, since the contrast of the pattern of an irradiated part and an unirradiated part is excellent, a vacuum evaporation method is preferable.

The degree of vacuum in the vacuum deposition method is preferably as high as possible, preferably 1.0 × 10 ⁻² Pa or less, more preferably 1.0 × 10 ⁻³ Pa or less, and further preferably 1.0 × 10 ⁻⁴ Pa or less. When the degree of vacuum is 1.0 × 10 ⁻² Pa or less, it is less likely to take in gas molecules remaining in the system when metal atoms volatilized from the volatilization source are deposited, and the metal film in the irradiated part and the unirradiated part The contrast of the pattern becomes clear.

  The deposition rate of the vacuum deposition method is preferably 0.01 nm / second to 100 nm / second. When the vapor deposition rate is 0.01 nm / second or more, gas molecules remaining in the system during the deposition are hardly taken in, the performance of the formed metal film is not deteriorated, and the optical characteristics are excellent. Further, when the deposition rate is 100 nm / second or less, the contrast of the pattern of the metal film in the irradiated portion and the unirradiated portion becomes clear.

  The deposition source of the vacuum deposition method is preferably aluminum, magnesium, titanium, copper, silver, and gold because of its industrial utility such as conductivity, and aluminum and magnesium because of excellent contrast of the metal film pattern. Is more preferable.

  The member manufactured by the metal film pattern forming method of the present invention is suitable as a member such as an electrode member, a wiring member, an optical member, a reaction film or a protective film of an organic electronic device such as an organic EL, an organic TFT, or an organic memory. Can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

[Production Example 1] Production of substrate surface A thermosetting polydimethylsiloxane resin (trade name “SYLGARD 184”, manufactured by Toray Dow Corning Co., Ltd.) was poured into a silicon substrate equipped with a 2 mm thick Teflon spacer. It was heated and cured at 120 ° C. for 30 minutes, cut into a size of 30 mm × 10 mm, and a silicon substrate having a silicone resin on the surface was produced.

[Example 1]
A silicon substrate is set on an ultraviolet ozone cleaner (model name “UV253H”, manufactured by Philgen Co., Ltd.) with the surface having a silicone resin as the upper surface (irradiated surface), and the area of the irradiated surface is ½. Covered with a shielding material (black paper with a thickness of 0.5 mm), using a low-pressure mercury lamp as an ultraviolet ray source at atmospheric pressure, an irradiation time of 300 seconds, an irradiation start temperature of 27 ° C., an ultraviolet lamp irradiation intensity of 28 mW / cm ² , The surface of the silicon substrate was irradiated with ultraviolet rays under the condition that the distance between the ultraviolet lamp and the silicon substrate was 35 mm. The portion not covered with the shielding material was the irradiated portion, and the portion covered with the shielding material was the unirradiated portion.
The ultraviolet irradiation intensity at 254 nm on the surface of the silicon substrate was measured using an ultraviolet integrated light meter (model name “UIT-150”, manufactured by USHIO INC.) And found to be 16 mW / cm ² .

For the lamination of the aluminum film, a vacuum deposition apparatus (model name “SVC-700TM”, manufactured by Sanyu Electronics Co., Ltd.) was used. Silicon after removing the shielding material under the conditions of tungsten basket, 99.99% aluminum as the deposition source, vacuum degree 5.0 × 10 ⁻⁴ Pa, deposition rate 0.1 nm / second, room temperature Aluminum was evaporated on the substrate surface. Vapor deposition was carried out with a quartz oscillator film thickness monitor until the deposited film thickness reached 20 nm to obtain a member.

The irradiated part of the obtained member had a metallic color due to the deposition of the aluminum film, and the unirradiated part did not change so as to be visually discernable.
Using a spectrophotometer (model name “U-4100”, manufactured by Hitachi High-Technologies Corporation), reflection of light having a wavelength of 380 to 780 nm with respect to the irradiated portion and the non-irradiated portion of the obtained member. The rate was measured. There was a difference in the reflectance between the irradiated part and the non-irradiated part.

From the above, it was confirmed that the pattern of the aluminum film was formed in the irradiated part and the non-irradiated part of the member.
In addition, it shows that there are many lamination amounts of an aluminum film, so that reflectance is high, and it shows that the contrast of the pattern of an aluminum film is clear, so that a reflectance difference is large.

[Examples 2-5, Comparative Examples 1-2]
The operation was performed in the same manner as in Example 1 except that the ultraviolet irradiation time was set as shown in Table 1.

  Table 1 shows the reflectance and the difference in reflectance at 400 nm between the irradiated part and the non-irradiated part of the active energy rays of the members obtained in Examples 1 to 5 and Comparative Examples 1 and 2. Moreover, the reflectance in 380-780 nm of the irradiated part of the active energy ray of the member obtained in Example 3, and the non-irradiated part is shown in FIG.

  As is apparent from Table 1, members having an aluminum film pattern could be obtained by the methods of Examples 1 to 5. As compared with Comparative Example 2, when the integrated light amount of the active energy ray was small, the reflectance of the irradiated portion was small, the amount of the aluminum film laminated was small, and the pattern contrast of the aluminum film was low.

[Examples 6-8, Comparative Examples 3-4]
The operation was performed in the same manner as in Example 1 except that the irradiation time of ultraviolet rays was as shown in Table 2, and the magnesium film was laminated and the amount of lamination was evaluated by the following method.

For the lamination of the magnesium film, a vacuum deposition apparatus (model name “SVC-700TM”, manufactured by Sanyu Electronics Co., Ltd.) was used. Magnesium was vapor-deposited on the surface of a silicon substrate using a molybdenum boat, using 99.9% magnesium as a vapor deposition source, under conditions of a degree of vacuum of 1.5 × 10 ⁻³ Pa, a vapor deposition rate of 1.5 nm / second, and room temperature. . Vapor deposition was carried out with a quartz oscillator film thickness monitor until the deposited film thickness reached 30 nm to obtain a member.

The irradiated part of the obtained member had a metal color due to the deposition of the magnesium film, and the unirradiated part was not observed to be visually distinguishable.
About the irradiated part and unirradiated part of the obtained member, the transmittance | permeability of the light of wavelength 550nm was measured using the spectrophotometer (model name "MultiSpec-1500", Shimadzu Corporation Corp. make). In Examples 6-8, the difference was seen in the transmittance | permeability of an irradiated part and an unirradiated part.

From the above, in Examples 6 to 8, it was confirmed that the pattern of the magnesium film was formed in the irradiated portion and the unirradiated portion of the member.
In addition, it shows that there are many lamination amounts of a magnesium film, so that the transmittance | permeability is low, and it shows that the contrast of the pattern of a magnesium film is clear, so that the transmittance | permeability difference is large. The results are shown in Table 2.

  As is clear from Table 2, members having a magnesium film pattern could be obtained by the methods of Examples 6-8. As compared with Comparative Example 4, when the integrated light amount of the active energy ray was small, the transmittance of the irradiated part was high, the amount of the magnesium film laminated was small, and the contrast of the magnesium film pattern was low.

  The member manufactured by the metal film pattern forming method of the present invention is suitable as a member such as an electrode member, a wiring member, an optical member, a reaction film or a protective film of an organic electronic device such as an organic EL, an organic TFT, or an organic memory. Can be used.

Claims (4)

A step of coating the surface of the substrate containing the silicone resin with a desired pattern of shielding material, and irradiating the surface of the substrate coated with the shielding material with an active energy ray having an integrated light quantity of 1,000 to 1,000,000 mJ / cm ^2. A metal film pattern forming method including a step of forming an irradiated portion and an unirradiated portion, and a step of laminating a metal on a substrate surface having an irradiated portion and an unirradiated portion.   The metal film pattern forming method according to claim 1, wherein the active energy rays are ultraviolet rays.   The metal film pattern forming method according to claim 1 or 2, wherein the metal is laminated by a vacuum deposition method.   The member manufactured by the pattern formation method of the metal film of Claims 1-3.

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