JP2007216493A - Minute structure, mold for transferring minute structure, mold for replica, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To duplicate a plurality of molds in each of which a minute structure is formed accurately in a nano-imprint method of a pattern transfer technique for forming a structure having a minute shape. <P>SOLUTION: In the minute structure formed by pushing a mold with a minute uneven pattern formed on the surface to a transcribed body and a mold for transferring a minute structure for forming the minute uneven pattern on the surface of the transcribed body, the minute structure and the mold for transferring the minute structure duplicate the minute unevenness of the mold accurately by reacting a monomer or an oligomer having a terminal reactive functional group which is packed in the minute uneven shape of a master mold. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a fine structure, a fine structure transfer mold, a replica mold, and a method for manufacturing the same, and in particular, a mold having a fine uneven pattern formed on the surface is pressed against a transfer target, The present invention relates to a microstructure transfer mold for forming an uneven pattern.

  2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography equipment has been improved in accuracy as a pattern transfer technique for realizing fine processing. However, the processing method has approached the wavelength of the light source for light exposure, and the lithography technology has also approached its limit. Therefore, in order to advance further miniaturization and higher accuracy, an electron beam drawing apparatus, which is a kind of charged particle beam apparatus, has been used in place of lithography technology.

  Unlike the batch exposure method in pattern formation using a light source such as i-line or excimer laser, pattern formation using an electron beam takes a method of drawing a mask pattern. The exposure (drawing) takes time and the pattern formation takes time. For this reason, as the degree of integration is dramatically increased to 256 mega, 1 giga, and 4 giga, the pattern formation time is remarkably increased correspondingly, and there is a concern that the throughput is extremely inferior. Therefore, in order to increase the speed of the electron beam lithography system, development of a collective figure irradiation method that combines various shapes of masks and collectively irradiates them with electron beams to form complex shapes of electron beams has been promoted. Yes. As a result, while miniaturization of the pattern is promoted, the electron beam lithography apparatus must be enlarged and a mechanism for controlling the mask position with higher accuracy is required. was there.

  On the other hand, techniques for performing fine pattern formation at low cost are disclosed in Patent Documents 1 and 2 and Non-Patent Document 1 described below. This is to transfer a predetermined pattern by embossing a resist film layer formed on the surface of the substrate to be transferred with a mold having the same pattern as the pattern to be formed on the substrate. According to the nanoimprint technology described in Document 2 and Non-Patent Document 1, a silicon wafer is used as a mold, and a fine structure of 25 nanometers or less can be formed by transfer.

US Pat. No. 5,259,926 US Pat. No. 5,772,905 S. Y. Chou et al. , Appl. Phys. Lett. , Vol. 67, p. 3114 (1955)

  However, in the imprint technique capable of forming a fine pattern, a technique for replicating a plurality of replicas with high accuracy from one master mold has been demanded.

  In view of the above technical problems, the present invention is highly accurate and finely used in a nanoimprint method, which is a pattern transfer technique for forming a fine-shaped structure in a manufacturing process of biodevices, semiconductor devices, storage media, and the like. It is an object to duplicate a plurality of molds having a structure.

  The present inventor considered that as a factor hindering the replication of the high-precision master mold, it was caused by the fact that the mold material for replication could not be completely filled in the fine uneven shape of the master mold, and reached the present invention.

  That is, the present invention is an invention of a replicated microstructure and a mold for transferring a microstructure, a microstructure having a fine uneven pattern formed on the surface thereof, pressed against the transfer object, and In the microstructure transfer mold for forming a fine uneven pattern on the surface of the transfer object, the microstructure and the mold for transferring the microstructure master a monomer or oligomer having a reactive or polymerizable functional group at the end. After filling in the fine uneven shape of the mold, a monomer or oligomer having a reactive functional group at the terminal is polymerized to replicate the fine unevenness of the mold with high accuracy. Here, the monomer or oligomer having a reactive functional group at the terminal is a powder that becomes a liquid before reaction or becomes a fluid by heating, and is filled into the fine uneven shape of the master mold. A low-viscosity liquid is preferred. Furthermore, the thing which reacts by adding energy, such as a heating, pressurization, and light irradiation within the fine uneven | corrugated shape of a master mold, and becomes solid is preferable.

  Furthermore, the terminal-reactive functional group of the present invention is preferably a reaction that does not produce a by-product during the reaction, in order to replicate a highly accurate fine uneven shape. In particular, the phenylethynyl group that initiates the reaction at a temperature higher than the melting temperature of the monomer and oligomer and does not produce a reaction byproduct is the reactive function of the monomer or oligomer used in the microstructure and the mold for forming a microstructure of the present invention. Preferred as a group. In addition, a vinyl group, a (meth) acrylate group, an N-substituted maleimide group, an epoxy group, and the like can be given. However, the reactive functional group of the present invention is not limited to this. Since the microstructure and the mold for transferring a microstructure of the present invention are composed of a polymer of a monomer or oligomer having a reactive functional group at the terminal, the monomer or oligomer is finely uneven in the master mold during replication. Filling into the shape surely and curing without generating a by-product during the reaction makes it possible to replicate the master mold with high accuracy.

  Furthermore, the present inventor considered the cause of insufficient strength of the microstructure and mold material to be replicated as a factor hindering the replication of a plurality of high-precision molds from the master mold, leading to the present invention.

  That is, the present invention is an invention of a replicated microstructure and a mold for transferring a microstructure, and a mold having a fine concavo-convex pattern formed on the surface is pressed against the transfer object, In the microstructure transfer mold for forming a fine uneven pattern on the surface of the transfer body, the microstructure and the microstructure transfer mold are organic compounds having a breaking strength of 100 MPa or more.

  The present inventor, when replicating the microstructure and the microstructure transfer mold from the master mold, when using an organic compound having a small breaking strength, especially in the transfer of the micro uneven shape having a large aspect ratio, It was confirmed that a part of was damaged and the shape was not accurately transferred. For example, when peeling a fine structure and a fine structure transfer mold from a master mold, or when making a replica from a replicated fine structure transfer mold by Ni plating or the like, the fine structure is obtained from a replica after plating. It was confirmed that the above pattern breakage was occasionally observed when the transfer mold was peeled off.

  Furthermore, it has been found that such breakage frequently occurs in the case of a material having a fracture strength of the microstructure and the microstructure transfer mold of less than 100 MPa. Here, the organic compound of 100 MPa or more is preferably a monomer or oligomer polymer having a reactive functional group at the terminal in the production of a highly accurate replica. These monomers or oligomers preferably have an imide bond for making a structure having a high breaking strength. In particular, a polymer having the following structural formula is polymerized without a reaction by-product after the melting temperature of the monomer or oligomer and the reaction start temperature of the reactive functional group are different and filled in the fine uneven pattern of the master mold, And it is preferable at the point whose breaking strength is 100 Mpa or more. However, the organic compound of the present invention is not limited to this.

以上の結果、微細構造体および微細構造体転写用モールド材料として破断強度が１００ＭＰａ以上の有機化合物材料を用いることでアスペクト比の高いマスターモールドに対しても、高精度な微細構造体および微細構造体転写用モールドの複製が実現できると共に微細構造体転写用モールドから更に複数の複製モールドを作製することができる。

As a result of the above, a highly accurate microstructure and microstructure can be obtained even for a master mold having a high aspect ratio by using an organic compound material having a breaking strength of 100 MPa or more as a microstructure and a mold transfer material for microstructure. The transfer mold can be replicated and a plurality of replica molds can be produced from the microstructure transfer mold.

  By using a polyimide oligomer having a reactive group at the terminal of the present invention, the filling property in the master mold is improved, and replication with a high filling rate is possible. As a result, a highly accurate replica can be realized. Furthermore, since a breaking strength of 100 MPa or more can be realized, a plurality of replicas can be produced without destroying the structure when replicated. Further, the glass transition temperature is high, and it can be applied as a microstructure transfer mold for thermal nanoimprint.

  First, a general nanoimprint method will be described with reference to FIG. A mold having a minute pattern on the surface of a silicon substrate or the like is produced. A resin film is provided on another substrate (a). Using a press device having a heating / pressurizing mechanism (not shown), the mold is pressed onto the resin film at a temperature (T) higher than the glass transition temperature (Tg) of the resin at a predetermined pressure (b). Next, the resin film is cooled and cured to a temperature (T) as low as Tg (c). The mold and the substrate are peeled off, and the fine pattern of the mold is transferred to the resin film on the substrate (d). Further, instead of the heat curing step, a photo-curable resin may be used, and after pressure molding, the resin may be irradiated with light to be cured. At this time, by using a light-transmitting mold such as glass, after pressing, light can be irradiated from above the light-transmitting mold, the resin can be photocured, and the pattern can be transferred.

  According to the nanoimprint method, (1) the integrated ultra-fine pattern can be efficiently transferred, (2) the device cost is low, (3) the complex shape can be handled, and the pillar can be formed. There is.

  Regarding the application fields of nanoimprinting methods, i) various biodevices, ii) immune system analyzers such as DNA chips, disposable DNA chips, etc. iii) semiconductor multilayer wiring, iv) printed circuit boards and RF MEMS, v) light or magnetism Examples include storage, vi) optical devices such as waveguides, diffraction gratings, microlenses, polarizing elements, photonic crystals, vii) sheets, viii) LCD displays, and ix) FED displays. The present invention applies to these fields.

  In the present invention, nanoimprint refers to transfer in which the height and width of the formed irregularities are in the range of several hundreds μm to several nm.

  In the present invention, the mold and the master mold have a fine pattern to be transferred, and the method for forming the pattern on the mold and the master mold is not particularly limited. For example, it is selected according to desired processing accuracy such as photolithography or electron beam drawing. As materials for the mold and master mold, silicon wafers, various metal materials, glass, quartz, ceramics, plastics and the like may be used as long as they have strength and workability with required accuracy. Specifically, Si, SiC, SiN, polycrystalline Si, glass, Ni, Cr, Cu, and those containing one or more of these are exemplified as preferable examples. Moreover, it is more preferable that the mold and the master surface are subjected to a release treatment for preventing adhesion with an organic compound. As the surface treatment method, a fluorine-based coupling agent is preferable in addition to a silicone-based release agent.

  In the present invention, the breaking strength is a force required for breaking per unit area of the material constituting the microstructure and the microstructure transfer mold.

  In the present invention, the transfer target to which a fine structure is transferred is not particularly limited, but is selected according to the desired processing accuracy. Specifically, polyethylene, polypropylene, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyvinyl chloride, polystyrene, ABS resin, AS resin, acrylic resin, polyamide, polyacetal, polybutylene terephthalate, glass reinforced polyethylene terephthalate, polycarbonate, modified Thermoplastic resins such as polyphenylene ether, polyphenylene sulfide, polyether ether ketone, liquid crystalline polymer, fluororesin, polyarate, polysulfone, polyethersulfone, polyamideimide, polyetherimide, thermoplastic polyimide, phenol resin, melamine resin, urea Resin, epoxy resin, unsaturated polyester resin, alkyd resin, silicone resin, diallyl phthalate resin, poly Bromide bismaleimide, poly bisamide thermosetting resin triazole and the like, and it is possible to use two or more kinds of these blended material.

  These resins are formed on the substrate surface from several nm to several tens of μm. Further, the substrate itself may be made of these resins, and a fine structure may be formed on the surface by transfer.

  In the present invention, the support substrate is a substrate that supports the cured organic material on which the fine structure is formed, and the material thereof is not particularly limited, but has a predetermined strength, and is an organic compound that forms the fine structure. It is sufficient if the surface on the side is flat. Specifically, silicon, various metal materials, glass, ceramics, plastics and the like are exemplified as preferable ones.

  In the present invention, the cylindrical base material is a columnar cast product or a cylindrical molded product, and has a predetermined strength and is rotatable around a central axis. Although there is no restriction | limiting in particular in a material, An alloy like stainless steel, ceramics, an engineering plastic etc. are illustrated as a preferable thing from points, such as intensity | strength and a moldability. Further, a material whose surface is covered with an elastic body such as rubber is desirable because it has excellent followability to the substrate during transfer.

  In the present invention, the flexible belt-like base material is a flat belt-like material that can be stretched over two or more cylinders and can be rotated, and has a predetermined strength and is suspended. It is preferable to have a flexibility that allows the side surface to smoothly move in close contact. The material is not particularly limited, but stainless steel foil, Ni foil, polyimide film, and the like are exemplified as preferable materials from the viewpoint of strength and flexibility.

  The replica mold of the present invention is a mold replicated from a master mold, and is an intermediate mold for further producing a replica from the replica mold. The reverse pattern of the present invention refers to a pattern shape in which the concave and convex portions of the pattern are reversed. Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings.

  FIG. 2 is a flowchart showing a method for manufacturing the microstructure, the microstructure transfer mold, and the replica mold of the present invention. Hereinafter, the microstructure, the microstructure transfer mold, and the replica mold replication method from the master mold of the present invention will be described.

  First, a method for synthesizing an oligomer having a reactive functional group at the terminal, which will be a mold material for a microstructure transfer and a replica mold according to the present invention will be described. First, 4 mmol of bis (4-aminophenyl) ether (ODA) is taken into a 100 ml eggplant flask substituted with an inert gas, and 20 ml of dehydrated distilled N-methyl-2-pyrrolidone (NMP) is added and dissolved. While gently stirring this reaction solution at room temperature, 2 mmol of 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was added as a solid and stirred at room temperature for 3 to 5 hours. . Furthermore, 4 mmol of 4-phenylethynyl phthalic anhydride (PEPA) is added to this reaction solution, and the mixture is stirred at room temperature for 3 to 5 hours. Thereafter, 8 mmol of acetic anhydride and pyridine were added and stirred at room temperature for 3 to 5 hours to obtain a polyimide oligomer solution. The prepared polyimide oligomer solution was dropped into 800 ml of methanol, and the resulting precipitate was filtered and dried to obtain a polyimide oligomer powder having phenylethynyl groups at both ends.

  Next, as shown in FIG. 2, (a) the polyimide oligomer powder 1 is allowed to stand on a master mold 2 on which fine irregularities are formed, and (b) a silane coupling-treated 8-inch Si substrate 3. Were stacked so as to face the master mold pattern surface on which the polyimide oligomer was arranged as shown in the figure, and (c) the polyimide oligomer was cured by applying pressure and heating at 2 MPa and 370 ° C. for 1 hour. Finally, (d) the microstructure 4 after the thermosetting reaction of the polyimide oligomer powder on which fine irregularities were formed was peeled from the master mold.

  In order to examine the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1, differential scanning calorimetry was performed. The measurement was performed by weighing 5 mg of the polyimide oligomer powder and 10 mg of alumina powder as a target sample, putting them in an aluminum cell for measurement, and heating at a rate of 10 ° C./min. From the measurement results, the melting temperature of the polyimide oligomer was around 140 ° C., and the peak temperature range showing the thermosetting reaction was 320 to 400 ° C.

In order to evaluate the mechanical properties of the cured product obtained by subjecting the polyimide oligomer powder 1 to a thermosetting reaction, the tensile modulus, breaking stress, and glass transition temperature were measured by the following methods. Test samples for tensile tests and dynamic viscoelasticity measurements were produced by the following method (FIG. 3).
(A) A polyimide oligomer powder 1 and a spacer 5 having a thickness of 50 μm are arranged on a lower substrate 6 subjected to a release treatment.
(B) The upper substrate 7 is disposed so as to face the lower substrate 6 on which the polyimide oligomer is disposed.
(C) Pressurization and heating at 2 MPa and 370 ° C. for 1 hour.
(D) The cured product 8 is peeled off from the substrates 6 and 7.

  A film-like cured product having a thickness of 50 μm was formed by the above method, and then cut into strips having a length of 60 mm and a width of 5 mm to obtain test samples. In the tensile test, a tensile tester (manufactured by Shimadzu Corporation) is used, 15 mm of both ends in the length direction of the test sample are sandwiched between test jigs, and the initial length is 30 mm, the width is 5 mm, and the thickness is 50 μm. The test was carried out at a tensile speed of 10 mm / min. From the test results, the cured product tensile elastic modulus after thermosetting reaction of the polyimide oligomer powder 1 was 2.66 GPa, and the breaking stress was 129 MPa. In the dynamic viscoelasticity measurement, 10 mm of both ends in the length direction of the sample are sandwiched between measurement jigs, the initial length is 40 mm, the width is 5 mm, and the thickness is 50 μm of the test portion for performing the dynamic viscoelasticity measurement. It was performed at 5 ° C./min. From the measurement results, the glass transition temperature of the cured product after the thermosetting reaction of the polyimide oligomer powder 1 was 415 ° C. The results are shown in Table 1.

  Furthermore, the height of the unevenness formed by observing the shape with an SEM was measured, and the ratio to the height of the master mold was defined as the filling rate and evaluated.

  FIG. 4 shows an appearance photograph (a) and a surface SEM image (b) of the microstructure obtained. The microstructure obtained by the above method has an uneven pattern opposite to the master mold formed on the surface. Since this microstructure has a glass transition temperature of 300 ° C. or higher and is higher than the glass transition temperature of general thermoplastic resins such as polystyrene, the microstructure transfer for thermal nanoimprint using these thermoplastic resins as the transfer target It can also be used as a mold. Moreover, since the obtained microstructure has a breaking strength of 100 MPa or more and can be replicated with a high aspect ratio by plating or the like, it can also be used as a replica mold.

  The polyimide oligomer of Example 1 was synthesized by adding 3 mmol of ODA, 2 mmol of 6FDA, 2 mmol of PEPA, and 6 mmol of acetic anhydride and pyridine to synthesize polyimide oligomer powder. Next, a replica mold was produced in the same manner as in Example 1. After applying palladium colloid to the surface of the replica mold, treatment was performed at 60 ° C. for 3 minutes with Top Chemi-Alloy 66 (Okuno Pharmaceutical Co., Ltd.), which is an electroless nickel plating solution, to form an electroless nickel plating film.

  Next, using this electroless Ni film as an electrode, electrolytic Ni plating was applied to a sulfamine bath at 50 ° C. for 120 minutes at a current density of 0.5 A / dm. Finally, the Ni plating formed from the replica mold was peeled off to produce a Ni plating replica similar to the original master. This method was repeated five times as shown in FIG. 5 to produce five Ni plated replicas. FIG. 5 shows surfaces (a) to (e) and a cross-sectional SEM image (f) of the Ni plating replica produced. Thus, five Ni replicas having a high aspect ratio could be produced from one replica mold. Here, the depth of the unevenness was measured with the SEM, and the ratio to the height of the master mold was defined as the filling rate.

  Further, differential scanning calorimetry was performed in the same manner as in Example 1, and the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1 were measured. Test samples were similarly prepared for the tensile test and dynamic viscoelasticity measurement, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition temperature was measured from the dynamic viscoelasticity measurement. The results are shown in Table 1.

  The synthesis of the polyimide oligomer of Example 1 was performed by adding 4 mmol of ODA, 3 mmol of 6FDA, 2 mmol of PEPA, and 8 mmol of acetic anhydride and pyridine, thereby preparing a polyimide oligomer powder. Further, a fine structure was produced on the glass substrate by the same method as in Example 1 using a 0.7 mm thick glass substrate as the substrate.

  The formed fine structure shape was observed by SEM, the height of the unevenness was measured, and the ratio to the height of the master mold was defined as the filling rate and evaluated. Further, differential scanning calorimetry was performed in the same manner as in Example 1, and the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1 were measured. Test samples were similarly prepared for the tensile test and dynamic viscoelasticity measurement, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition temperature was measured from the dynamic viscoelasticity measurement. The results are shown in Table 1.

  The synthesis of the polyimide oligomer of Example 1 was conducted using 4 mmol of ODA, 2 mmol of biphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride (BPDA) instead of 6 FDA, 4 mmol of PEPA, acetic anhydride and pyridine. 8 mmol each was added to prepare a polyimide oligomer powder. A flexible microstructure transfer mold was prepared in the same manner as in Example 1 using a polyimide film (Upilex R: manufactured by Ube Industries) having a width of 20 cm and a thickness of 50 μm as a substrate. Five pieces of this microstructure transfer mold cut into 10 cm × 15 cm were produced. This was pasted on a seamless steel belt having a width of 20 cm and a circumference of 75 cm with a silicone-based adhesive (KE1820: manufactured by Shin-Etsu Silicone) to produce a belt-shaped microstructure transfer mold.

  Furthermore, the height of the unevenness formed by observing the shape with an SEM was measured, and the ratio to the height of the master mold was defined as the filling rate and evaluated. Further, differential scanning calorimetry was performed in the same manner as in Example 1, and the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1 were measured. Test samples were similarly prepared for the tensile test and dynamic viscoelasticity measurement, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition temperature was measured from the dynamic viscoelasticity measurement. The results are shown in Table 1.

  The synthesis of the polyimide oligomer of Example 4 was performed by adding 3 mmol of ODA, 2 mmol of BPDA, 2 mmol of PEPA, and 6 mmol of acetic anhydride and pyridine to prepare a polyimide oligomer powder. Next, as shown in FIG. 6, (a) a polyimide film having a thickness of 50 μm is arranged as a spacer 5 on the master mold 2 whose surface has been subjected to mold release treatment, and the polyimide oligomer powder 1 of this embodiment is allowed to stand inside. did. (B) Next, the release-treated Si wafer 9 was placed on the polyimide oligomer powder 1. (C) This was placed in a vacuum press, and after vacuum deaeration, it was pressurized and heated at 2 MPa and 370 ° C. for 1 hour. (D) Finally, the cured product was peeled from the master mold 2 and the Si wafer 9 to produce a film-like microstructure 4. A photograph of the appearance of the produced microstructure is shown in FIG.

  The height of the irregularities formed by observation with this SEM was measured, and the ratio to the height of the master mold was defined as the filling rate and evaluated. Further, differential scanning calorimetry was performed in the same manner as in Example 1, and the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1 were measured. Test samples were similarly prepared for the tensile test and dynamic viscoelasticity measurement, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition temperature was measured from the dynamic viscoelasticity measurement. The results are shown in Table 1.

  Synthesis of the polyimide oligomer of Example 4 was performed by adding 4 mmol of ODA, 3 mmol of BPDA, 2 mmol of PEPA, and 8 mmol of acetic anhydride and pyridine, to prepare a polyimide oligomer powder. Next, a microstructure transfer mold in which a microstructure was formed on a Si substrate was produced in the same manner as in Example 1.

  Furthermore, the height of the unevenness formed by observing the shape with an SEM was measured, and the ratio to the height of the master mold was defined as the filling rate and evaluated. Further, differential scanning calorimetry was performed in the same manner as in Example 1, and the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1 were measured. Test samples were similarly prepared for the tensile test and dynamic viscoelasticity measurement, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition temperature was measured from the dynamic viscoelasticity measurement. The results are shown in Table 1.

  Using a powder of PETI-330 (manufactured by Ube Industries) as a polyimide oligomer containing PEPA as a raw material, a film-like microstructure was produced in the same manner as in Example 5.

  Furthermore, the height of the unevenness formed by observing the shape with an SEM was measured, and the ratio to the height of the master mold was defined as the filling rate and evaluated. Further, differential scanning calorimetry was performed in the same manner as in Example 1, and the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1 were measured. Test samples were similarly prepared for the tensile test and dynamic viscoelasticity measurement, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition temperature was measured from the dynamic viscoelasticity measurement. The results are shown in Table 1.

  By the method of Example 2, five Ni replica molds having a length of 10 cm and a width of 15 cm were produced. Next, these were welded and the welded portion was polished to prepare a seamless belt-shaped Ni mold having a circumference of 75 cm.

  The mold for transferring a flexible microstructure produced in Example 4 was adhered to a roll surface having a diameter of 10 cm and a width of 20 cm with a silicone-based adhesive (KE1820: manufactured by Shin-Etsu Silicone) to produce a roll-type microstructure transfer mold. did.

(Comparative Example 1)
Polymethylmethacrylate (PMMA) having an average molecular weight of 950,000 was dissolved in ethyl cellosolve acetate to prepare a 12% solution. This was spin coated on the Si wafer surface and baked on a hot plate at 90 ° C. for 5 minutes to form a resin film having a thickness of 1 μm. Next, a master mold similar to that in Example 1 having fine irregularities formed on the surface was heated under pressure at 150 ° C./10 minutes under the condition of 4 MPa, and then the master mold was peeled off to produce a replica mold.

  The replica mold was plated with Ni in the same manner as in Example 2 to produce a nickel replica. The surface of this Ni replica was observed with SEM. The observation results are shown in FIG. When the Ni replica was peeled from the PMMA replica mold, it was confirmed that a part of the replica mold was broken and remained in the pattern of the Ni replica.

  About the sample for SEM evaluation produced by the same method, the shape was observed by SEM, the height of the unevenness | corrugation formed was measured, and the ratio with respect to the height of a master mold was defined as the filling rate, and was evaluated. Further, differential scanning calorimetry was performed in the same manner as in Example 1, and the melting temperature and thermosetting reaction temperature of the polyimide oligomer powder 1 were measured. Test samples were similarly prepared for the tensile test and dynamic viscoelasticity measurement, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition temperature was measured from the dynamic viscoelasticity measurement. The results are shown in Table 1.

(Comparative Example 2)
A fine structure was produced in the same manner as in Example 1. At that time, a polyimide film (Upilex-r: manufactured by Ube Industries) having a thickness of 50 μm was used instead of the polyimide oligomer powder 1. The pressure heating condition was 370 ° C./6 MPa for 1 hour. The surface shape of the transferred microstructure was observed with an SEM. An SEM image is shown in FIG. The height of the irregularities formed by observation with this SEM was measured, and the ratio to the height of the master mold was defined as the filling rate and evaluated. It was confirmed that the height was smaller than that of the microstructure according to the present invention in FIG. 4 and the shape was irregular. In addition, this film was formed in the same manner for the tensile test and dynamic viscoelasticity measurement by the same method as in Example 1, the tensile modulus and breaking stress were evaluated from the tensile test, and the glass transition was measured from the dynamic viscoelasticity measurement. The temperature was measured. The results are shown in Table 1.

The flowchart which shows the process of a general nanoimprint. The flowchart which shows a fine structure formation process. The flowchart which shows the sample preparation process for mechanical property evaluation. The external appearance photograph and SEM image of the microstructure produced by the Example of this invention. The surface and cross-sectional SEM image of the Ni replica produced by the Example of this invention. The flowchart which shows the microstructure preparation process of the Example of this invention. The external appearance photograph of the fine structure produced by the Example of this invention. The Ni replica surface SEM image by a comparative example. The microstructure surface SEM image by a comparative example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Polyimide oligomer powder, 2 ... Master mold, 3 ... Si substrate, 4 ... Fine structure, 5 ... Spacer, 6 ... Lower substrate, 7 ... Upper substrate, 8 ... Hardened | cured material, 9 ... Si wafer.

Claims (22)

  A mold having a fine uneven pattern formed on its surface is pressed against a transfer object, and the fine structure having a fine uneven pattern formed on the transfer object surface is an organic substance having a breaking strength of 100 MPa or more. A fine structure characterized by that.   The microstructure according to claim 1, wherein the microstructure contains a monomer or oligomer polymer having a reactive functional group at a terminal.   The microstructure according to claim 1, wherein the microstructure contains a monomer or oligomer polymer having a phenylethynyl group at a terminal. 2. The microstructure according to claim 1, wherein the microstructure contains a monomer or oligomer polymer having the following structure.

  In a microstructure transfer mold for pressing a mold having a fine concavo-convex pattern formed on the surface thereof to a transfer object to form a fine concavo-convex pattern on the surface of the transfer object, the mold has a breaking strength of 100 MPa or more. A mold for fine structure transfer characterized by being.   6. The microstructure transfer mold according to claim 5, wherein the microstructure transfer mold contains a monomer or oligomer polymer having a reactive functional group at a terminal.   6. The microstructure transfer mold according to claim 5, wherein the microstructure transfer mold contains a monomer or oligomer polymer having a phenylethynyl group at a terminal. 6. The microstructure transfer mold according to claim 5, wherein the microstructure transfer mold contains a monomer or oligomer polymer having the following structure.

  9. The microstructure transfer mold according to claim 5, wherein the microstructure transfer mold is formed on a flat support substrate.   9. The microstructure transfer mold according to claim 5, wherein the microstructure transfer mold is formed on a surface of a cylindrical base material.   9. The microstructure transfer mold according to claim 5, wherein the microstructure transfer mold is formed on a flexible belt-shaped substrate.   In the replica mold for forming the same pattern as the master mold from the reverse pattern after forming the reverse pattern from the master mold having fine irregularities formed on the surface, the replica mold has a breaking strength of 100 MPa or more. A mold for replicas, which is organic.   13. The replica mold according to claim 12, wherein the replica mold contains a monomer or oligomer polymer having a reactive functional group at a terminal.   13. The replica mold according to claim 12, wherein the replica mold contains a monomer or oligomer polymer having a phenylethynyl group at a terminal. 13. The replica mold according to claim 12, wherein the replica mold contains a monomer or oligomer polymer having the following structure.

  A microstructure transfer mold for pressing a mold having a fine concavo-convex pattern formed on the surface thereof to a transfer target to form a fine concavo-convex pattern on the transfer target surface. It is produced by obtaining a reverse pattern from a replica mold on which a pattern is formed and forming the same pattern as the master mold, and the replica mold is made of an organic material having a breaking strength of 100 MPa or more. Mold for structure transfer. 17. The microstructure transfer mold according to claim 16, wherein the replica mold contains a monomer or oligomer polymer having a reactive functional group at a terminal.
  17. The microstructure transfer mold according to claim 16, wherein the replica mold contains a monomer or oligomer polymer having a phenylethynyl group at a terminal. 17. The microstructure transfer mold according to claim 16, wherein the replica mold contains a monomer or oligomer polymer having the following structure.

  In a fine structure having fine irregularities formed on the surface, a step of leaving a polymerizable organic compound as a raw material on a substrate on which fine irregularities are formed, covering the organic compound left on the substrate The step of allowing the base material to stand, the step of pressurizing and heating the organic compound and the base material on the substrate on which fine irregularities are formed, and the step of curing the organic compound on the substrate on which fine irregularities are formed A method for producing a microstructure, comprising a step of peeling a substrate on which fine irregularities are formed and a cured organic compound.   In a microstructure transfer mold for pressing a mold having a fine concavo-convex pattern formed on its surface against a transfer target to form a fine concavo-convex pattern on the surface of the transfer target, on the master mold having the fine concavo-convex formed The step of leaving a polymerizable organic compound as a raw material, the step of standing a base material so as to cover the organic compound placed on the master mold, and heating the master mold, the organic compound and the base material under pressure And a method for producing a microstructure transfer mold, comprising: a step of curing an organic compound on a substrate on which fine irregularities are formed; and a step of separating the cured organic material from the master mold.   In a microstructure transfer mold for pressing a mold having a fine concavo-convex pattern formed on its surface against a transfer target to form a fine concavo-convex pattern on the surface of the transfer target, on the master mold having the fine concavo-convex formed The step of standing the polymerizable organic compound as a raw material, the step of standing the base material so as to cover the organic compound placed on the master mold, the master mold, the organic compound, and the base material being heated under pressure A step of curing the organic compound on a substrate on which fine irregularities are formed, a step of peeling off the cured organic compound from the master mold, a step of forming a plating film on the surface of the cured organic compound, and the curing A method for producing a microstructure transfer mold, comprising a step of peeling a plated film from an organic compound.

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