JP2007191327A - Fine-processing method for glassy carbon, glassy carbon-processed article, and finely-processed article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fine-processing method for a glassy carbon which can be suitably used for the formation of an optional uneven pattern on a glassy carbon, which has been difficult heretofore. <P>SOLUTION: The fine-processing method for the glassy carbon comprises the processes of: coating the glassy carbon substrate with an ultraviolet ray-sensitive resin used in the development of a photograph; forming the resin into a desired micropattern by the exposure and development of the resin; dry-etching the resin, to transfer the micropattern onto the glassy carbon substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fine processing method of a glassy carbon substrate used as a molding die at the time of glass or resin press processing, a glassy carbon processed product, and a fine processed product. In particular, dry etching is performed and a fine pattern is formed on a glassy carbon substrate. The present invention relates to a fine processing method of glassy carbon provided with a process of transferring to glass, a glassy carbon processed product manufactured using the same, and a fine processed product manufactured using the same.

  Currently, development of press transfer technology for fine shapes on glass and resin is underway in various fields. As the press transfer molding die, a silicon wafer, a glass wafer, or a self-solid body of an electroformed film such as nickel to which those shapes are transferred is mainly used.

  These substrate materials are highly reactive with glass at high temperatures, are inconvenient as mold materials for glass, and are not used except for resins. On the other hand, glassy carbon is known to be amorphous as carbon, very stable up to high temperatures in an oxygen-free atmosphere, with little reaction with glass, and very promising as a glass mold. .

Moreover, dry etching, electric discharge machining, machining, etc. have already been proposed as the fine machining method. Of these, dry etching, which is a particularly effective technique, uses the etching action of carbon by oxygen radicals, so a film resistant to oxidation, for example, a metal such as aluminum or chromium, or a ceramic film such as SiO ₂ is used as a mask. Has been.

  However, in the conventional dry etching processing method, there is a problem that the processing surface is greatly roughened due to material defects and processing damage at the time of mirror surface processing, and when a metal or ceramic film is used as a mask, Although the inclined shape can be formed by controlling the anisotropic etching conditions, it is difficult to give an arbitrary curvature.

  Regarding the problem of the former processing surface, the inventor proposes an improvement method by high-temperature processing in Japanese Patent Application No. 2005-105848, and realizes greatly suppressing the appearance of scratches and defects.

  However, due to the latter problem, it was still difficult to make an arbitrary protrusion shape.

Patent Document 1 describes a method for producing silica glass that can transfer fine patterns and transfers using a glassy carbon mold, and Patent Document 2 (paragraph [0010]) describes dry etching of a glassy carbon mold. Is disclosed.
JP 2004-284893 A JP 2004-338999 A

  The present invention has been made in consideration of the above-mentioned circumstances. It is possible to form an arbitrary uneven shape on glassy carbon, and it is possible to form a glassy carbon with a glass shape by pressing a difficult shape so far. An object is to provide a processing method.

  In addition, a glassy carbon processed product is manufactured by using the glassy carbon fine processing method, and the glassy carbon processed product is used as a molding die. The purpose is to provide.

  The present inventors have found that a fine arbitrary shape can be formed in glassy carbon by using a resin mask and anisotropic etching, and have completed the present invention.

  That is, an arbitrary shape (pattern) can be transferred to the glassy carbon by preparing a resin mask having a fine pattern formed on the glassy carbon and simultaneously etching the mask and the glassy carbon. Thus, by arbitrarily forming the shape of the resin mask, it is possible to easily transfer the shape to a glassy carpon that is difficult to process.

  In order to achieve the above-described object, the glassy carbon microfabrication method according to the present invention includes a step of applying an ultraviolet photosensitive resin for photographic development to a glassy carbon substrate, and exposure and development of the ultraviolet photosensitive resin. And a step of forming an ultraviolet photosensitive resin into a desired fine pattern and a step of performing dry etching to transfer the fine pattern of the ultraviolet photosensitive resin to a glassy carbon substrate.

  Another method for finely processing glassy carbon according to the present invention includes a step of applying a curable resin coating agent to a glassy carbon substrate and semi-curing, and forming a fine pattern in the semi-cured resin coating agent. A step of transferring the fine pattern to the resin coating agent by pressing the formed mold, and a step of transferring the fine pattern of the resin coating agent to the glassy carbon substrate by performing dry etching after the resin coating agent is cured. And

  Moreover, the glassy carbon processed material which concerns on this invention is manufactured by the said fine processing method of glassy carbon.

  Moreover, the resin-made or glass-made fine processed product according to the present invention is manufactured using the glassy carbon processed product as a mold.

  According to the microfabrication method for glassy carbon according to the present invention, it is possible to form an arbitrary uneven shape on the glassy carbon, and it is possible to form a glassy carbon that enables glass forming by pressing a difficult shape so far. A processing method can be provided. It is particularly suitable for the production of a convex portion having a semicircular cross section.

  Further, according to the glass microfabricated product according to the present invention, a glassy carbon processed product produced using the above-mentioned glassy carbon microfabrication method is produced, and this glassy carbon worked product is used as a mold. Therefore, an object is to provide an inexpensive and highly accurate resin or glass microfabricated product.

  Hereinafter, a glassy carbon microfabrication method according to a first embodiment of the present invention will be described with reference to the accompanying drawings.

  FIG. 1 is a process diagram of a fine processing method for glassy carbon according to the first embodiment.

  As shown in FIG. 1, the fine processing method of glassy carbon according to the first embodiment includes the following steps.

  For example, the resin layer 2 is formed on the surface of the glassy carbon substrate 1 subjected to mirror finishing (P1).

  The resin layer coating and forming method may be any method such as a spin coating method, a dip coating method, a doctor blade method, or a spray coating method that is generally used in a semiconductor device manufacturing process. There is no particular limitation as long as it can be applied. Further, as the resin having high resistance to oxygen plasma, it is preferable to use a resin that contains as little molecular oxygen as possible and has many carbon six-membered ring structures.

  The resin layer needs to be appropriately selected depending on the method for forming a fine shape. For example, a fine pattern is formed by photolithography, which is a semiconductor device manufacturing process, and glassy carbon is formed by dry etching such as inductively coupled plasma (ICP) etching using oxygen plasma or reactive ion etching (RIE). If a fine pattern is transferred, it is necessary to use a photoresist agent having oxygen plasma resistance.

  On the other hand, when a fine pattern shape on glassy carbon is transferred by a physical dry etching method that does not use oxygen plasma, oxygen plasma resistance is not particularly required, and a wider range of photoresist agents can be selected.

  Here, the resin fine pattern formed on the surface of the glassy carbon needs to be etched together with the glassy carbon during dry etching.

  Furthermore, the master pattern 3 is exposed to the photosensitive resin layer 2 using ultraviolet rays U by photolithography (P2).

  Thereafter, development is performed with a predetermined developer to obtain a resin fine pattern 2 '(P3).

  Further, the fine pattern 2 'is deformed by bringing the glassy carbon substrate 1 to a temperature equal to or higher than the glass transition point of the resin layer in accordance with the required shape, thereby obtaining a fine pattern 2 "having an arbitrary curvature (P4).

  By controlling the change in the shape of the resin due to this heating, it is possible to give an arbitrary curvature to the fine shape formed on the glassy carbon substrate 1.

  Thereafter, anisotropic dry etching is performed using the oxygen plasma P, the fine pattern 2 ″ is transferred, and the fine pattern 1a is transferred to the glassy carbon substrate 1 (P5).

  This dry etching is performed when the resin has a certain degree of oxygen plasma resistance. If the substrate temperature rises due to the influence of oxygen plasma during dry etching and the resin fine pattern is deformed, the resin is made before the dry etching. It is necessary to perform a treatment such as irradiating a fine pattern with ultraviolet rays for a long time to increase heat resistance.

  At the time of dry etching, a difference in etching rate between the resin and the glassy carbon substrate is taken into consideration.

  According to the glassy carbon microfabrication method of the first embodiment, glass molding having a shape that has been difficult so far is possible, and a glassy carbon processed product having an arbitrary uneven shape is obtained.

  Next, a glassy carbon micromachining method according to the second embodiment will be described.

  In the second embodiment, the first embodiment applies an ultraviolet photosensitive resin to a glassy carbon substrate, performs exposure and development, and molds the ultraviolet photosensitive resin into a desired fine pattern. A fine pattern is formed on the resin coating agent using a method.

  For example, as shown in FIG. 2, the resin coating agent 2 is formed on the surface of the glassy carbon 1 subjected to mirror finishing (P11). The resin coat layer is preferably semi-cured to such an extent that it can be molded by concave pressure.

  The mold 13 on which the fine pattern 13a is formed is pressed to transfer the fine pattern 2 ″ to the resin coating agent 2 (P12 to P14). Thereafter, the resin is cured.

  In the case of using an imprint method in which a mold having a fine pattern formed on a silicon wafer or the like is pressed against the resin to transfer the shape, the resin is a non-photosensitive resin such as polydimethylsiloxane. It is also possible to select thermoplastic resins such as (PDMS) and polymethylmethane acrylate (PMMA), thermosetting resins, and photocurable resins. In this case, it is necessary to appropriately select a resin in view of characteristics such as oxygen plasma resistance by selecting a shape transfer method to glassy carbon. Also in the second embodiment, the resin fine pattern formed on the surface of the glassy carbon needs to be etched together with the glassy carbon during dry etching.

  Note that the pattern mold used when using the imprinting method includes a silicon wafer or glass wafer formed with a fine pattern by dry etching or wet etching, or a reverse pattern copied by Ni electroforming, etc. Can be used. When producing the shapes of these molds, various known fine processing techniques can be applied, and this can greatly expand the range of shapes that can be formed on the glassy carbon substrate.

  Thereafter, anisotropic dry etching is performed using the oxygen plasma P, the fine pattern 2 ″ is transferred, and the fine pattern 1a is transferred to the glassy carbon substrate 1 (P15).

  According to the glassy carbon microfabrication method of the second embodiment, glass molding having a shape that has been difficult until now becomes possible, and a glassy carbon processed product having an arbitrary uneven shape is obtained.

  Further, the finely processed product according to the present invention is shown in FIG. 3 using a glassy carbon material processed by the above-described method for finely processing a glassy carbon substrate according to the present invention as shown in FIG. Are manufactured by subjecting the workpiece to precise micromachining.

  For example, the lower die 22 of the molding apparatus 21 is a split die, and the convex fitting portion 22a of the lower die 22 is integrally held by the concave fitting portion 23a of the pedestal 23, so that the lower die 22 and the upper die 24 are provided. Is preheated. A soft resin or silica glass M is stored in the concave molding surface 22b of the preheated lower die 22, the moving shaft 25 is lowered, the upper die 24 is lowered, and the resin or silica glass M is pressed. As a result, the resin or silica glass M is molded along the shapes of the lower mold 22 and the upper mold 24, and the resin or silica glass microfabricated product that has been subjected to precise microfabrication by the glassy carbon processed product (mold). can get.

  The resin having high oxygen resistance is, for example, a negative resist mainly composed of cyclized rubber or an aromatic novolak resin-based positive resist.

  The atmospheric gas during dry etching preferably contains 10 to 100% oxygen gas. When the oxygen content is less than 10%, the etching rate is slow, and the treatment at a practical rate becomes difficult.

  When the fine pattern formed on the resin layer on the glassy carbon substrate is heated to a temperature equal to or higher than the glass transition point of the resin and deformed using surface tension, the shape is corrected by applying an etching treatment. This is preferable. This heating is preferably irradiated with ultraviolet rays.

  At the time of dry etching, if the temperature of the glassy carbon substrate rises above the glass transition temperature of the resin, the fine pattern may be deformed, so it is preferable to suppress the temperature rise.

  In order to suppress the temperature rise of the glassy carbon substrate, it is preferable to use any one of water cooling, air cooling, liquid nitrogen, helium circulation refrigerator, and Peltier element.

  Using diamond abrasive grains, 10 μm positive resist is applied to the surface of glassy carbon that has been mirror-polished on one side by spin coating, and a □ 9 μm dot shape is formed by photolithography at intervals of 5 μm. It was molded so as to have an array pattern of 800 vertical and 600 horizontal. A temperature higher than the glass transition point of positive resist was applied to the substrate on which this pattern was formed, and the substrate was reflowed to obtain a hemispherical shape. The resist was irradiated with ultraviolet rays to increase the heat resistance, and then the whole was etched by dry etching to finally obtain a molding die for a spherical microlens array having a height of 3 μm and a diameter of 14 μm.

The process drawing of the fine processing method of glassy carbon concerning a 1st embodiment of the present invention. The process drawing of the fine processing method of glassy carbon concerning a 2nd embodiment of the present invention. The conceptual diagram of the shaping | molding method of the glassy carbon fine processed material which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass-like carbon substrate 1a Fine pattern 2 Resin layer 2 'Fine pattern 2 "Fine pattern 3 Master pattern

Claims (12)

Applying a UV photosensitive resin for photographic development to a glassy carbon substrate, exposing and developing the UV photosensitive resin, forming the UV photosensitive resin into a desired fine pattern, and performing dry etching, A method for finely processing glassy carbon, comprising a step of transferring a fine pattern of an ultraviolet photosensitive resin to a glassy carbon substrate. Applying a curable resin coating agent to a glassy carbon substrate and semi-curing it, and pressing a mold with a fine pattern formed on the semi-cured resin coating agent to transfer the fine pattern to the resin coating agent A glass-like carbon microfabrication method comprising: a step of transferring a fine pattern of a resin coating agent to a glassy carbon substrate by performing dry etching after the resin coating agent is cured. 3. The glassy carbon microfabrication method according to claim 1 or 2, wherein the ultraviolet photosensitive resin or the resin coating agent is provided with high oxygen resistance and oxygen plasma is used for dry etching. 4. The glassy carbon microfabrication method according to claim 1, wherein the dry etching is anisotropic etching. The glassy carbon microfabrication method according to claim 3, wherein the atmosphere gas at the time of dry etching contains 10 to 100% oxygen gas. 6. The glassy carbon microfabrication method according to claim 5, wherein the etching method is an inductively coupled plasma etching method or a reactive ion etching method. The glassy material according to any one of claims 1 to 3, wherein the resin on which the fine pattern is formed is heated to a temperature equal to or higher than the glass transition point and deformed by utilizing surface tension, and then subjected to an etching treatment. Carbon fine processing method. 8. The method for finely processing glassy carbon according to claim 1, wherein the temperature of the glassy carbon substrate is prevented from rising above the glass transition temperature of the resin during the dry etching. 9. The method for finely processing glassy carbon according to claim 8, wherein any one of water cooling, air cooling, liquid nitrogen, helium circulation type refrigerator, and Peltier element is used to suppress temperature rise of the glassy carbon substrate. . 3. The glassy carbon microfabrication method according to claim 1, wherein ultraviolet rays are irradiated to raise the glass transition temperature of the resin before the dry etching. A glassy carbon processed product produced by the glassy carbon microfabrication method according to claim 1. A resin or glass microfabricated product produced using the glassy carbon processed product according to claim 11 as a mold.

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