Method for producing fine pattern formation body, fine pattern formation body, and fine pattern formation solution

Abstract

To provide a method for producing fine pattern-formation bodies, which can form fine patterns having excellent characteristics such as heat resistance, etching resistance, and mechanical strength, by a process that allows pressing at low pressure, reduces load on the mold, has excellent shape reproducibility, does not require heating and cooling steps, is high in production efficiency, and low in environmental load.SOLUTION: A fine pattern is formed by coating a substrate with a solution of polyorganosilsesquioxane dissolved in a high boiling point solvent, pressing a mold while the solution maintains its fluidity to transfer a fine pattern, and irradiating it with high-energy rays such as electron beams to crosslink the polyorganosilsesquioxane.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a method for producing a fine pattern formed body, etc. More specifically, the present invention relates to a method for producing a fine pattern formed body, a fine pattern formed body, and a solution for forming a fine pattern, which can be pressed at a low pressure, do not require a heating and cooling process, and can form a fine pattern having excellent properties such as heat resistance, etching resistance, and mechanical strength. [Background technology]

[0002] Nanoimprinting is known as a method for forming minute nanoscale projection and recess patterns. This is a technology that improves the resolution of embossing, in which a die with a highly accurate projection and recess pattern created by electron beam lithography or other techniques is pressed against a resin material on a substrate to transfer the projection and recess pattern.

[0003] This technology makes it possible to efficiently replicate nanoscale uneven patterns using a simple process, and research and development is being conducted into the fields of manufacturing processes for electronic devices such as semiconductors, functional films with anti-glare properties, and optical and magnetic recording media.

[0004] In nanoimprint technology, process development of molds, press conditions, etc. is underway to improve repeatability, shape reproducibility, manufacturing efficiency, etc. In addition, development of materials such as thermoplastic, thermosetting, and photosetting resins that can be used as transfer materials is also underway to improve the heat resistance, etching resistance, mechanical strength, and other properties of the fine patterns to be formed.

[0005] For example, Patent Document 1 discloses a fine pattern transfer material that contains an organosilicon compound such as polyphenylsilsesquioxane and a specific metal compound as a transfer material that can suitably form a fine pattern by nanoimprint molding. It states that the use of this material makes it possible to form a fine pattern with excellent heat resistance, which is necessary in semiconductor manufacturing processes and the like.

[0006] Non-Patent Document 1 discloses a room-temperature nanoimprinting technique in which a hydrosilsesquioxane solution is spin-coated onto a substrate, crosslinked and cured by reacting with moisture in the air, and then a mold is pressed at room temperature to transfer the solution. This technique does not require heating / cooling or UV light irradiation, and enables high-aspect-ratio patterning only through room-temperature processes, and it is described as being able to form fine patterns made of siloxane polymers with excellent etching resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2008-194894 A [Non-patent literature]

[0008] [Non-Patent Document 1] Kenichiro Nakamatsu, Shinji Matsui, "Room Temperature Nanoimprint Technology", Surface Technology, 2008, vol.59, No.10, p.648-653 Summary of the Invention [Problem to be solved by the invention]

[0009] However, in the nanoimprint molding disclosed in Patent Document 1, a solution in which polyphenylsilsesquioxane and a metal alkoxide compound are dissolved in an organic solvent is spin-coated onto a substrate to form a thin film, and then the substrate is pressed at a high pressure of 118 MPa using a Ni mold. The pressure for pressing the mold is described as preferably 100 to 200 MPa.

[0010] Since the solution is made of polysilsesquioxane and highly reactive metal alkoxide, the crosslinking reaction is likely to proceed, and pre-baking is also performed as necessary, so pressing with high pressure is required. Therefore, distortion is observed in the transferred pattern formed in Figures 1 and 2. The mold is easily damaged, the repeatability of transfer and the reproducibility of the shape are poor, and there is a risk of the mold and the substrate bonding.

[0011] In addition, the room temperature nanoimprinting technology disclosed in Non-Patent Document 1 uses hydrosilsesquioxane as a transfer material, which undergoes hydrolysis with moisture in the air and polymerizes explosively, so the storage stability of the raw material is low and it is difficult to control the coating and pressing processes. Since crosslinking and hardening progresses due to hydrolysis and condensation reactions after coating, pressing at high pressures of several MPa to 10 MPa is necessary.

[0012] To improve the etching resistance of the fine pattern, annealing at 500 to 1000 °C is performed after transfer to remove SiO X However, annealing at a temperature within an acceptable range is sufficient from the viewpoint of the impact on the substrate and manufacturing costs. X However, there is a limit to how far the transfer can be carried out, making it difficult to obtain a siloxane polymer with the desired properties. After transfer, a heating and cooling process with a wide temperature range is required, which significantly reduces production efficiency.

[0013] As described above, conventional room-temperature nanoimprinting techniques have problems in the process of transferring the fine pattern of a mold to a transfer material, and problems also exist in the shape and physical properties of the molded body to which the fine pattern is transferred. At present, there is no room-temperature nanoimprinting technique that solves these problems.

[0014] The present invention has been made in consideration of the above-mentioned problems, and aims to provide a method for producing a fine pattern forming body, a fine pattern forming body, and a solution for forming a fine pattern, which are capable of forming a nanoscale uneven pattern having excellent properties such as heat resistance, etching resistance, mechanical strength, and transparency by a method that can be pressed at low pressure, does not require heating and cooling, and is highly productive and easy to control.

[0015] As a result of intensive research into solving the above-mentioned problems, the inventors have discovered that a fine pattern-forming body having the desired molecular structure and physical properties can be produced in an easily controllable manner with high production efficiency by coating a solution of polyorganosilsesquioxane dissolved in a high-boiling point solvent onto a substrate, pressing the solution while the fluidity is maintained against a gas-permeable mold to transfer a fine pattern, and irradiating the solution with high-energy rays to crosslink and harden the polyorganosilsesquioxane. As a result of further research, the inventors have completed the present invention.

[0016] That is, the present invention is a method for producing a fine pattern forming body, comprising the steps of: dissolving a polyorganosiloxane compound mainly composed of polyorganosilsesquioxane in a high boiling point solvent to prepare a transfer material solution; coating the transfer material solution on a substrate surface to form a transfer film; pressing the transfer film surface against a transfer surface of a mold made of a gas permeable polymeric elastomer, on which a fine pattern is formed, while the transfer material solution constituting the transfer film maintains its fluidity; filling the fine pattern with the transfer material solution, and then separating the transfer film surface from the transfer surface; and irradiating the transfer film surface to which the fine pattern has been transferred with high energy rays to crosslink the polyorganosiloxane compound mainly composed of polyorganosilsesquioxane, thereby hardening the fine pattern.

[0017] A solution of polyorganosilsesquioxane dissolved in a high-boiling point solvent is coated onto a substrate, and then a gas-permeable mold is pressed onto the substrate while the solution maintains its fluidity to transfer a fine pattern. This makes it possible to transfer fine nanopatterns with high precision using a low-pressure press and raw materials that are easy to handle at room temperature.

[0018] Then, by irradiating the transferred fine pattern with high-energy rays such as electron beams to promote the crosslinking reaction, the heating and cooling steps become unnecessary, and the curing can be achieved in a short time, thereby improving production efficiency. Furthermore, by controlling the irradiation conditions of the high-energy rays, it becomes possible to control the molecular structure of the crosslinked polysiloxane polymer, and a fine pattern-forming body having desired properties such as heat resistance, etching resistance, mechanical strength, and transparency can be produced.

[0019] The present invention also provides a coating film comprising a substrate and a coating film disposed on a part or the whole region of at least one of the outer surfaces of the substrate, the coating film being formed with a fine pattern on a surface thereof, the coating film being made of a crosslinked product of a polyorganosiloxane compound mainly composed of polyorganosilsesquioxane, and the coating film being formed with a fine pattern on a surface thereof, the coating film being made of a crosslinked product of a polyorganosilsesquioxane compound mainly composed of Si-R 1 Bond (where R 1 is a hydrocarbon group, and is a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms which may have a substituent that does not contain oxygen or nitrogen atoms, or a phenyl group which may have a substituent that does not contain oxygen or nitrogen atoms) and a peak intensity (P1) derived from a Si-O-Si bond at 1050 cm -1 The ratio (P1 / P2) of the intensity of the peak to the intensity (P2) of the peak in the vicinity is 0.7 or less.

[0020] By controlling the irradiation conditions of high-energy rays such as electron beams, functional groups and terminal groups in the silsesquioxane molecules are converted into siloxane bonds and the crosslinked polyorganosilsesquioxane is made to have the above-mentioned specific structure, and the heat resistance, etching resistance, mechanical strength, etc. of the formed fine pattern can be improved, and the desired characteristics according to the application can be imparted.

[0021] For example, chlorine-based dry etching is used in the microfabrication of high dielectric constant materials such as HfO2, but inorganic resists are used because organic resists have poor etching resistance to chlorine-based gases. In this process, inorganic resists such as SiO2 are formed into a film by deposition or the like, and then patterned by photolithography and etching to form an etching mask, which requires many steps and increases costs. By using the method for producing a fine pattern-forming body of the present invention, a fine pattern made of a polyorganosiloxane crosslinked body that can withstand chlorine-based dry etching can be formed in a single process with fewer steps, and the efficiency of the chlorine-based dry etching process can be significantly improved and costs can be significantly reduced.

[0022] Furthermore, the present invention relates to a solution for forming a fine pattern, which contains a polyorganosiloxane compound having polyorganosilsesquioxane as a main component and a high-boiling point solvent, and the content of the polyorganosilsesquioxane compound having polyorganosilsesquioxane as a main component is in the range of 10.0 to 12.5 wt % with respect to the total amount of the solution.

[0023] A solution in which polyorganosilsesquioxane is dissolved in a high boiling point solvent can stably maintain its properties for a period of one year or more when stored in a freezer. In addition, by setting the content within the above-mentioned specific range, it becomes possible to maintain the shape of the transferred fine pattern for a long period of time without crosslinking and curing, thereby improving the flexibility of the nanoimprint manufacturing process and the ease of handling of intermediate products. Effect of the Invention

[0024] According to the method for producing a fine pattern forming body of the present invention, the raw materials can be easily handled, pressing can be performed at low pressure, and heating and cooling are not required, resulting in a highly efficient production method which can produce a fine pattern forming body with high precision and excellent properties such as heat resistance, etching resistance, and mechanical strength.

[0025] In addition, the fine pattern forming body of the present invention has a high-precision fine pattern having excellent properties such as heat resistance, and is suitable for etching processes of electronic devices such as semiconductors, products having functional surfaces, etc., and can improve the production efficiency and product performance of these. Furthermore, by using the fine pattern forming solution of the present invention, the flexibility of the nanoimprint manufacturing process and the handleability of intermediate products can be improved. [Brief description of the drawings]

[0026] [Figure 1] 1 shows SEM images showing the change in shape retention depending on the polyorganosilsesquioxane content of the fine pattern formed body produced in Test Example 1. [Diagram 2] 1 is an SEM observation image 1 showing the change in heat resistance depending on the electron beam irradiation dose of the fine pattern forming bodies produced in Example 1 and Test Example 1. [Diagram 3] 2 is an SEM observation image 2 showing the change in heat resistance depending on the electron beam irradiation dose of the fine pattern forming body produced in Example 1. [Figure 4] 1 is a graph showing an FT-IR spectrum indicating a change in peak intensity depending on the amount of electron beam irradiation measured in Example 1. [Diagram 5] 1 is a graph showing the relationship between the electron beam irradiation dose and the peak intensity ratio (Si—CH 3 / Si—O—Si) calculated in Example 1. [Figure 6] Graph 2 shows an FT-IR spectrum showing the change in peak intensity depending on the electron beam irradiation dose measured in Example 2.

[0027] [Figure 7] Graph 2 showing the relationship between the electron beam irradiation dose and the peak intensity ratio (Si—CH 3 / Si—O—Si) calculated in Example 2. [Figure 8] 1 is a graph showing FT-IR IR spectra indicating changes in peak intensity due to the electron beam irradiation dose and heat treatment measured in Test Example 2. [Figure 9] Graph 3 shows an FT-IR spectrum indicating the change in peak intensity depending on the electron beam irradiation dose measured in Example 3. [Figure 10] 1 shows external images of samples of the nanohole-forming body produced in Example 4 at each step. [Figure 11] 11 shows SEM images showing the surface state of a sample in each process of the nanohole-forming body produced in Example 4. [Figure 12] 13 is a graph showing the wavelength dependence of light transmittance of Al nanoholes produced in Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] The method for producing a fine patterned body, the fine patterned body, and the solution for forming a fine pattern of the present invention will be described in detail below. Note that the composition, structure, production method, etc., for which description is omitted, may be the same or substantially the same as those known to those skilled in the art.

[0029] In the present invention, a fine pattern is a structure in which a plurality of fine projections and recesses are repeatedly formed, each having a front-to-back or left-to-right width and a top-to-bottom height of 10 μm or less, preferably 1 μm or less, in plan or side view. Each projection and recess unit may be of the same or different shape, may be symmetrical or asymmetrical in the front-to-back, left-to-right and top-to-bottom directions, and may be formed at equal or unequal intervals in the front-to-back and left-to-right directions. Examples of such a fine pattern include a circuit pattern of a semiconductor element, a moth-eye structure of a functional surface, and a microlens array of an optical element.

[0030] In the method for producing a fine patterned body of the present invention, a polyorganosiloxane compound mainly composed of polyorganosilsesquioxane is used as a transfer material for transferring a fine pattern of a mold. Silsesquioxane is a siloxane-based compound having a trifunctional T3 unit represented by the following general formula (1) as a repeating unit. [R 1 SiO 3 / 2 ]···(1)

[0031] In the above general formula (1), R 1Polyorganosilsesquioxane, which has an organic functional group R, has excellent storage stability as a raw material, is easy to control in the manufacturing process, and has good solubility in organic solvents and good crosslinking properties when exposed to high-energy rays. 1 Polyhydrosilsesquioxane, in which each R is a hydrogen atom, is undesirable because it reacts violently with moisture in the air and undergoes hydrolysis, resulting in poor storage stability and difficulty in controlling the production process.

[0032] In the formula, R 1 is a hydrocarbon group, and examples thereof include a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms which may have a substituent that does not contain oxygen or nitrogen atoms, and a phenyl group which may have a substituent that does not contain oxygen or nitrogen atoms. From the viewpoints of storage stability, solubility in a solvent, good crosslinkability, ease of availability, etc., R 1 is preferably a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group, more preferably a methyl group or a vinyl group, and most preferably a methyl group. 1 may be a hydrogen atom, or may have two or more different functional groups. The terminal groups of the molecular chain are exemplified by hydroxyl groups and lower alkoxy groups such as ethoxy groups.

[0033] The molecular weight of the polyorganosilsesquioxane is not limited as long as it has excellent stability as a raw material and good solubility in high-boiling point solvents. It may be a small oligomer or a large polymer. The weight average molecular weight (Mw) is, for example, in the range of 1000 to 10000. The high-order structure of polysilsesquioxane may be a cage type or a ladder type, and either structure may be used. There is no significant difference in transferability as a transfer material, but the ladder type is preferable in terms of crosslinkability.

[0034] The polyorganosiloxane compound mainly composed of polyorganosilsesquioxane may contain, in addition to the polysilsesquioxane compound having a trifunctional T3 unit as a repeating unit, a polysiloxane compound having a bifunctional D2 unit or a tetrafunctional Q4 unit as a repeating unit, or a polysiloxane compound partially having a D2 unit or a Q4 unit as a repeating unit. The main component means that the composition ratio of the T3 unit is 51wt% or more with respect to the total amount of the compound. The composition ratio of the T3 unit is, for example, in the range of 60 to 80wt%.

[0035] A polyorganosiloxane compound, the main component of which is polyorganosilsesquioxane, is dissolved in a high boiling point solvent to prepare a transfer material solution. By using a high boiling point solvent, it is possible to suppress the evaporation of the solvent during the coating process and ensure the fluidity of the solution. The high boiling point solvent is preferably an organic solvent that can sufficiently dissolve the polyorganosiloxane compound and maintain the fluidity of the transfer material solution on the substrate. A high boiling point organic solvent with a boiling point equal to or higher than butyl acetate (boiling point 126°C) is preferable. Specifically, diethylene glycol monoethyl ether acetate (DGMEA) (boiling point 217.4°C), ethylene glycol monobutyl ether acetate (EGBEA) (boiling point 191.5°C), diethylene glycol monobutyl ether acetate (DEGBEA) (boiling point 246.8°C), etc. can be mentioned. Two or more of these organic solvents may be mixed and used.

[0036] In the examples described later, it has been confirmed that a mold made of a gas-permeable polymeric elastomer swells slightly due to a high-boiling point solvent in which a polyorganosiloxane compound is dissolved. Depending on the shape and use of the fine pattern forming body, the transfer surface on which the fine pattern of the mold is formed is required to have extremely high dimensional accuracy, so it is preferable that the high-boiling point solvent does not swell the polymeric elastomer. In order to suppress the swelling of the transfer surface, it is considered effective to increase the difference in solubility parameter (SP value: Solubility Parameter) between the high-boiling point solvent and the elastic polymer material constituting the gas-permeable polymeric elastomer.

[0037] The SP values ​​of the high boiling point solvent and the elastic polymeric material are estimated from the physical properties or molecular structure, and the SP values ​​of both are estimated using the same theoretical formula. Examples of the estimation method include Hildebrand, Hansen, Okitsu, Fedors, Hoy, etc. Hansen and Okitsu are preferred because they are widely used, and Fedors is preferred because it can be calculated relatively easily. The SP value can be obtained by estimating from the theoretical formulas described in "Hansen, CM, Journal of Paint Technology, vol. 39, No. 505, 104-117 (1967)", "Okitsu, Toshinao, Journal of the Adhesion Society of Japan, vol. 29, No. 5, 204-211 (1993)", "Fedors, RF, Polymer Engineering & Science, vol. 14, No. 2, 147-154 (1974)", etc. Also, the values ​​can be obtained based on these theoretical formulas by referring to literature values ​​described in various documents.

[0038] In fine patterns that require high dimensional accuracy, the difference (SP1-SP2) between the SP value of the high boiling point solvent (SP1) and the SP value of the elastic polymer material (SP2) is 2.5 (cal / cm 3 ) 0.5 More than 5.0 (cal / cm 3 ) 0.5 More preferably, 7.5 (cal / cm 3 )0.5 The above is more preferable. SP1 and SP2 are estimated based on the same theoretical formula and the difference is calculated. For example, it is determined that it is preferable if the difference satisfies the above numerical value by estimating based on any one of the theoretical formulas of Hansen, Okitsu, or Fedoz.

[0039] In order to increase the difference in SP value between the high boiling point solvent and the elastic polymer material, the SP value of the high boiling point solvent is set to 10.0 (cal / cm 3 ) 0.5 More than 12.5 (cal / cm 3 ) 0.5 More preferably, 15.0 (cal / cm 3 ) 0.5 The above is more preferable. For example, if the value is estimated based on one of the theoretical formulas of Hansen, Okitsu, or Fedoz and satisfies the above numerical value, it is judged to be preferable. The SP value of a mixed solvent in which two or more high boiling point solvents are mixed is estimated from the SP values ​​and volume fractions of the single solvents constituting the mixed solvent.

[0040] Specifically, examples of high boiling point solvents having a boiling point equal to or higher than butyl acetate (boiling point 126°C) and an SP value 2.5 or higher than polydimethylsiloxane (PDMS) (SP value 7.3 to 7.6) include ethylene glycol monobutyl ether (EGME) (boiling point 171.2°C, SP value 10.24), N-methyl-2-pyrrolidone (NMP) (boiling point 202°C, SP value 11.3), and tripropylene glycol monobutyl ether (TGME) (isomer mixture, boiling point 274°C, SP value 21.14). Note that these SP values ​​are literature values.

[0041] When the content of the polyorganosiloxane compound mainly composed of polyorganosilsesquioxane in the total amount of the transfer material solution is small, the fluidity of the transfer material solution is improved, coating is easy, and the pressing pressure can be reduced. When the content is large, the transfer material is easily filled into the fine pattern of the mold transfer surface during pressing. The content of the polyorganosiloxane compound is preferably in the range of 10.0 to 20.0 wt%.

[0042] In the examples described later, it has been confirmed that when the time interval between the separation of the transfer film surface on the substrate and the transfer surface of the mold and the irradiation of high energy rays to crosslink and harden is long, and the content of the polyorganosiloxane compound mainly composed of polyorganosilsesquioxane is high, the transferred fine pattern tends to collapse. Although the mechanism is not necessarily clear, it is considered that when the content increases, the density increases and the weight increases, the fine pattern cannot withstand its own weight and collapses. Therefore, in a production line in which the time interval between the separation of the transfer film surface and the transfer surface and the irradiation of high energy rays is long, the content of the polyorganosiloxane compound is preferably in the range of 10.0 to 15 wt%, more preferably in the range of 10.0 to 12.5 wt%.

[0043] A transfer material solution in which a polyorganosilsesquioxane-based polyorganosiloxane compound is dissolved in a high-boiling point solvent can stably maintain its properties for a period of one year or more when stored in a freezer (below -18°C). In addition, a transfer material solution prepared so that its content falls within the above range can stably retain a transferred fine pattern without being limited by process conditions or product structure, and can be suitably used as a fine pattern forming solution to improve process flexibility and product quality.

[0044] The prepared transfer material solution is coated on a substrate or base material on which a fine pattern is to be formed. The coating method is not limited as long as it is a method capable of forming a uniform transfer film on the substrate or base material. When the substrate or base material has a small area and a smooth shape, spin coating or bar coating is preferred, and when the substrate or base material has a large area or is a continuous process using a roll-to-roll method, spray coating is preferred. The thickness of the film to be transferred is optimally set depending on the height of the uneven shape of the fine pattern to be transferred and the use of the fine pattern forming body. For inorganic etching masks for semiconductor device manufacturing, a film thickness range of 100 to 300 nm is preferred, for functional films having a moth-eye structure that exhibits anti-glare properties, a film thickness range of 300 to 800 nm is preferred, and for optical parts having a microlens array, a film thickness range of 500 to 1000 nm is preferred.

[0045] The transfer surface of the mold on which the fine pattern is formed is pressed against the surface of the film to be transferred formed on the substrate or base material while the transfer material solution maintains its fluidity. By pressing the transfer surface of the mold while the transfer material solution maintains its fluidity, the transfer material resin can be completely filled into the fine pattern of the transfer surface even with low pressing pressure.

[0046] The suitable range of fluidity varies depending on the manufacturing conditions such as the uneven shape of the transferred fine pattern, the coating method, and the pressing pressure. The suitable range can be set by adjusting the temperature of the substrate or base material, the type and content of the polyorganosilsesquioxane, the type of the high-boiling point solvent, etc. As a guideline for fluidity, in the step of pressing the surface of the film to be transferred and the transfer surface on which the fine pattern of the mold is formed, the transfer material solution coated on the substrate surface is absorbed into the fine pattern of the mold, and the substrate surface is required to have a degree of fluidity that exposes the substrate surface.

[0047] The mold used in the method for producing a fine pattern-formed body of the present invention is composed of a gas-permeable elastic body. The entire mold may be composed of a gas-permeable elastic body, or only the transfer surface portion of the mold on which the fine pattern is formed may be composed of a gas-permeable elastic body. By pressing the gas-permeable transfer surface against the surface of the film to be transferred, the high-boiling point solvent contained in the transfer material solution can be volatilized, and even with a low-pressure press, the transfer material solution can be completely filled into the fine pattern formed on the transfer surface.

[0048] As a gas-permeable polymeric elastomer, it is desirable to use an elastic polymeric material that has the desired elasticity and durability, excellent repeatability and shape reproducibility, and good processability that allows the formation of fine patterns by coating on a master mold or electron beam drawing. Examples include organic and inorganic rubbers and elastomer resins with nanoporosity. Specific examples include polydimethylsiloxane (PDMS) and poly(1-trimethylsilyl-1-propyne) (PTMSP). From the viewpoints of processability of fine patterns and gas permeability, polydimethylsiloxane (PDMS) is preferred.

[0049] The suitable range of gas permeability varies depending on the manufacturing conditions such as the type of high boiling point solvent used, the coating method, and the pressing pressure. The optimum range can be set by adjusting the type of resin forming the mold, the thickness of the transfer surface of the mold, the nanoporous diameter after the resin is cured, etc. It is desirable that the nanoporous diameter is small enough not to affect the shape of the fine pattern, and is preferably 3 nm or less. An example of a method for setting gas permeability is to measure it using the method specified in JIS 7129 2008 Method for determining water vapor permeability of plastic films and sheets (instrumental measurement method). An example of a suitable gas permeability is a water vapor permeability coefficient of about 40,000 (barrer) at 30°C.

[0050] When the pressure for pressing the surface of the transfer layer and the transfer surface of the mold is low, the load on the mold and the substrate is reduced, preventing damage and improving repeatability of transfer. When the pressure is high, the transfer material solution is easily filled into the fine pattern, and filling defects can be suppressed. A range of 0.5 MPa to 10 MPa is preferable, and a range of 1 MPa to 3 MPa is more preferable. When the fine pattern on the transfer surface is composed of independent protrusions and is easily damaged and filling defects are unlikely to occur, a range of 0.1 MPa to 3 MPa is preferable, and a range of 0.25 MPa to 1.5 MPa is more preferable.

[0051] If the time for pressing the surface of the film to be transferred against the transfer surface of the mold is short, the load on the mold and the substrate is reduced and production efficiency is improved. If the time is long, the transfer material solution is easily filled into the fine pattern, and filling defects can be suppressed. With the above-mentioned specified pressure applied, the time is preferably in the range of 5 to 60 minutes, more preferably 10 to 30 minutes. After the pressure is stopped, the mold may be left as it is for a certain period of time.

[0052] After the fine pattern formed on the transfer surface of the mold is completely filled with the transfer material solution by the above pressing process, the transfer film surface and the transfer surface of the mold are gently separated, so that the fine pattern can be transferred to the transfer film surface. At this time, the transfer material may be partially peeled off together with the mold due to pressure and friction between the transfer material and the mold. In order to prevent partial peeling, it is desirable to separate the material as gently and slowly as possible within the range that is permissible in the process. A release layer such as a fluororesin may be formed on the transfer surface of the mold, or a release agent may be applied to improve the releasability between the transfer material and the mold.

[0053] After the surface of the film to be transferred is separated from the transfer surface of the mold, the surface of the film to which the fine pattern has been transferred is irradiated with high energy radiation to crosslink the polyorganosiloxane compound mainly composed of polyorganosilsesquioxane, thereby hardening the fine pattern. Examples of high energy radiation include high energy radiation such as electron beams, X-rays, and gamma rays, which have energy sufficient to crosslink the polysiloxane compound in a short time, and short wavelength electromagnetic waves such as far ultraviolet rays. Electron beams and X-rays are preferred because they can be used with existing sterilization equipment and the like, and irradiation control is easy, and electron beams are the most preferred.

[0054] The irradiation dose is set to an optimal range in consideration of the manufacturing cost such as irradiation cost and irradiation time, and the physical properties and applications required for the fine pattern forming body to be manufactured. The higher the irradiation dose, the more the crosslinking reaction can be promoted, and the properties such as heat resistance of the fine pattern can be improved. The smaller the irradiation dose, the more the manufacturing cost can be reduced, and the more the deterioration of the substrate and the transfer material can be suppressed. The irradiation dose is preferably in the range of 300 to 40,000 kGy, more preferably in the range of 500 to 30,000 kGy, and even more preferably in the range of 1,000 to 20,000 kGy. Irradiation may be performed in an air atmosphere, but a low-oxygen atmosphere or an inert gas atmosphere such as nitrogen gas is preferable to prevent deterioration of the resin material due to oxidation.

[0055] When the high-energy beam is an electron beam or an X-ray, the acceleration voltage is set in an optimal range in consideration of the type of transfer material and substrate, the film thickness, the shape of the fine pattern, and the like. The higher the acceleration voltage, the higher the penetration ability of the high-energy beam, and the deeper the transfer material can be modified. The lower the acceleration voltage, the lower the penetration ability, but the radiation dose can be reduced due to the effect of backscattering. In addition, the influence on the substrate can be reduced, and an inexpensive radiation device can be used. The acceleration voltage is preferably in the range of 30 to 1000 kV, more preferably in the range of 40 to 500 kV, and even more preferably in the range of 50 to 300 kV. In consideration of the use of an X-ray radiation device or a small electron beam radiation device, with an emphasis on reducing the radiation dose by utilizing backscattering, the acceleration voltage is preferably in the range of 10 to 500 kV, more preferably in the range of 15 to 400 kV, and even more preferably in the range of 20 to 300 kV.

[0056] In order to prevent the shape of the transferred fine pattern from being distorted, it is desirable that the time interval between the separation of the transferred film surface from the transfer surface of the mold and the irradiation of high energy rays to crosslink and harden the film is as short as possible within the range allowable in the process. It is preferable that the time interval is within 1 hour, and more preferably within 15 minutes. This makes it possible to suppress the tendency of the shape of the fine pattern to be distorted due to the increase in the content of the above-mentioned polyorganosiloxane compound. In the case of a continuous process such as the roll-to-roll method, it is preferable to install an irradiation process adjacent to the pressing process and irradiate quickly.

[0057] In the examples described later, the ratio (P1 / P2) of the peak intensity (P1) derived from the Si-CH3 bond in the molecular structure to the peak intensity (P2) derived from the Si-O-Si bond in the FT-IR analysis tended to decrease as the electron beam irradiation dose was increased. It is considered that the electron beam irradiation caused ring-opening polymerization of the four-membered cyclic siloxane of the polyorganosilsesquioxane, and also caused condensation reaction by detaching organic functional groups from the polysiloxane main chain, resulting in a change to a polyorganosiloxane crosslinked body with a three-dimensional network structure.

[0058] It is believed that by controlling the exposure dose of high-energy radiation, it is possible to control the molecular structure of the crosslinked polyorganosiloxane, and to impart the desired properties to the fine patterned product. The smaller the peak intensity ratio (P1 / P2), the higher the proportion of polysiloxane structure, which is preferable because it improves properties such as heat resistance, etching resistance, and mechanical strength. In the IR spectrum measured by the FT-IR method, Si-R 1 Bond (where R 1 is a hydrocarbon group, and is a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms which may have a substituent that does not contain oxygen or nitrogen atoms, or a phenyl group which may have a substituent that does not contain oxygen or nitrogen atoms) and a peak intensity (P1) derived from a Si-O-Si bond at 1050 cm -1 The ratio (P1 / P2) of the intensity of the peak to the intensity of the neighboring peak (P2) is preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.

[0059] In the IR spectrum measured by the FT-IR method, Si-R 1 The position of the peak due to the bond is R 1 Although it depends on the type of organic functional group R 1 Select a peak having sufficient intensity derived from the molecular structure of the compound, and calculate the peak intensity ratio (P1 / P2). For example, 1 In the case of monomethyl group, the Si-CH bond-derived 1270 cm -1 Select a peak near 1050 cm due to the Si-O-Si bond. -1 The ratio (P1 / P2) of the intensity of the peak to the intensity of the neighboring peak (P2) is preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.

[0060] Similarly, the Si-C2H5 bond has a wavelength of 1250 cm -1 Peak near 1635 cm for Si-CH=CH2 bond -1 Peak near 1520 cm for Si-Ph bond -1 For example, nearby peaks are selected and the peak intensity ratio (P1 / P2) is calculated.

[0061] Since a certain correlation was found between the dose of electron beam and the peak intensity ratio (P1 / P2), it has been suggested that it may be possible to control the molecular structure by controlling the acceleration voltage and dose of high-energy beams within the range of practical manufacturing conditions, thereby setting the peak intensity ratio (P1 / P2) in the desired range. By making the peak intensity ratio (P1 / P2) as small as possible and creating a structure close to silicon oxide (silica), it is possible to dramatically improve the properties of the fine patterned product, such as heat resistance, etching resistance, and mechanical strength.

[0062] Depending on the application of the fine pattern forming body, a heat treatment step may be provided as necessary after the step of curing the fine pattern and the film to be transferred by irradiating high energy rays. By carrying out heat treatment, the ratio of siloxane structures can be increased in the deep part of the material to be transferred where high energy rays such as electron beams cannot reach depending on the shape of the fine pattern and the irradiation conditions. The heat treatment temperature is preferably in the range of 150 to 500°C, more preferably in the range of 200 to 350°C, taking into consideration the influence on the base material or substrate and the decrease in production efficiency due to heating and cooling. The heat treatment time is appropriately set in the range of 30 minutes to several hours, taking into account the balance between the heat treatment temperature and the production efficiency. The heat treatment may be performed in air, low oxygen, or inert gas atmosphere.

[0063] The fine patterns that can be produced by the present invention depend on the precision of the mold, but it is believed that periodic structures of several tens to several hundreds of nanometers can be produced. The aspect ratio (T / W) of the height (T) and width (W) of the concave or convex shape can be produced in the range of 1 to several times.

[0064] The fine pattern forming body of the present invention comprises a substrate or base material, and a coating film (transferred film) on which a fine pattern manufactured by the manufacturing method of the present invention is formed, which is disposed on a part or the entire region of at least one of the outer surfaces of the substrate or base material. The type of the substrate and base material varies depending on the member or product, and is not limited. Examples of the substrate and base material include metal materials such as aluminum and copper, inorganic materials such as silicon, quartz glass, sapphire, strontium titanate (STO), and strontium ruthenate (SRO), and resin materials such as polyethylene terephthalate (PET), triacetate cellulose (TAC), cycloolefin polymer (COP), and polycarbonate (PC). The area and shape of the region on which the coating film is disposed can be set according to the use of the member or product, and are not limited.

[0065] Specific examples of the fine pattern forming body of the present invention include electrodes and substrates on which dry etching masks or lift-off resists for producing electronic devices such as electronic components such as semiconductors and display panels for liquid crystal and the like are formed, functional films and members having functional surfaces exhibiting anti-glare properties, water repellency or hydrophilicity, optical elements such as LEDs having transmission or reflection type diffraction gratings or microlens arrays, display panels for liquid crystal and the like and their optical members, fluidic devices having microchamber arrays or microchannels, bioanalysis devices and their members, and the like. EXAMPLES

[0066] The method for producing a fine patterned body of the present invention will be specifically described below with reference to examples and test examples. Note that the present invention is not limited to these examples, and various modifications are possible without departing from the technical concept of the present invention.

[0067] [Test Example 1] A hydrosilsesquioxane (HSQ) solution (FOx15, DuPont-Toray) was spin-coated onto a 3-inch diameter silicon substrate to form an HSQ film with a thickness of 110 nm, which was then post-baked at 90°C for 2 minutes. An electron beam lithography system (ELS-S50, Elionix) was used to lithograph the surface of this HSQ film at an acceleration voltage of 50 kV, a current value of 1 nA, and an irradiation dose of 350 μC / cm. 2 A fine concave-convex pattern with a period of 800 nm was written under the condition of a field size of 1 mm square. After electron beam writing, the pattern was developed at room temperature for 30 minutes using a 2.38% tetramethylammonium hydroxide (TMAH) solution, and then washed with ultrapure water for 1 minute to produce an HSQ master mold.

[0068] The main agent and curing agent of ultraviolet-curable polydimethylsiloxane (PDMS) resin (Shin-Etsu Chemical Co., Ltd., KER-4690A / B) were thoroughly mixed and degassed, and the mixed solution was spin-coated on the HSQ master mold to form a PMDS film. After degassing the microbubbles at the interface between the master mold and the PMDS film by reducing the pressure, ultraviolet light with a wavelength of 350 nm was applied at an output of 10.5 mWcm. -2The PDMS resin was cured by irradiation with UV light for 5 minutes. The PDMS film was released from the master mold to produce a gas-permeable PDMS mold.

[0069] A polysiloxane resin (SR-13H, manufactured by Konishi Chemical Industry Co., Ltd.) whose main component is polymethylsilsesquioxane (PMSQ) was dissolved in a high boiling point solvent, diethylene glycol monoethyl ether acetate (DGMEA, boiling point 217.4°C), to prepare a PMSQ solution (transfer material solution). Three levels of solutions were prepared, with the content of resin components such as PMSQ relative to the total solution volume being 9.7, 11.5, and 12.9 wt%.

[0070] A 0.5 mL aliquot of PMSQ solution of each concentration was dropped onto a 3-inch silicon substrate, and spin-coated at 5000 rpm for 30 seconds to form a PMSQ film (transferred film). The film thickness was approximately 200 nm. While the PMSQ solution on the silicon substrate was still fluid, a transfer surface of a PDMS mold with a fine pattern was placed on the PMSQ film and pressed against it. A pressure of 1 MPa was applied for 10 minutes, and the PDMS mold was left to stand for 2 hours, allowing the fine pattern of the PDMS mold to be completely filled with the PMSQ solution. The transfer surface of the PDMS mold was gently pulled away from the PMSQ film surface, resulting in the transfer of a fine concave-convex pattern with an aspect ratio of approximately 1.0 and a period of 800 nm to the PMSQ film surface.

[0071] The surface shape of the micropatterns made from the PMSQ solutions of each concentration was confirmed by observing them with a scanning electron microscope (SEM) 24 hours after releasing the PDMS mold. The observed images are shown in Figure 1. In the micropattern formed from the 9.7 wt% solution, the PMSQ solution was not sufficiently filled in the recesses of the mold, and the convex shape of the transfer surface was dull. In the micropattern formed from the 11.5 wt% solution, the PMSQ was sufficiently filled in the recesses of the mold, and a sharp micropattern was formed. In the micropattern formed from the 12.9 wt% solution, a sharp micropattern was formed immediately after release from the mold, but the micropattern collapsed and disappeared 24 hours after release. This is thought to be because the micropattern cannot withstand its own weight when the density increases with the increase in PMSQ content, and the weight increases.

[0072] [Example 1] A fine pattern was transferred to the PMSQ film surface in the same manner as in Test Example 1, except that the content of the resin components such as PMSQ to the total amount of the solution was set to 12.0 wt%. Next, the PMSQ film surface to which the fine pattern was transferred was irradiated with an electron beam to crosslink the polysiloxane resin mainly composed of PMSQ, thereby hardening the fine pattern. The conditions of the electron beam irradiation were an acceleration voltage of 50 kV, a current value of 0.89 mA, and an atmospheric O2 concentration of 300 ppm, and the irradiation dose was set to five levels of 120, 240, 600, 1200, and 2400 kGy.

[0073] Next, the micropattern after electron beam irradiation was heated in an air atmosphere at 200°C for 10 minutes to confirm its heat resistance. SEM images of the micropattern heated after electron beam crosslinking are shown in Figures 2 and 3. It can be seen that the unirradiated micropattern collapses and disappears upon heating. On the other hand, the electron beam crosslinked micropattern shows a tendency for its shape to be maintained even after heating at higher irradiation doses. It can be seen that the shape of the micropattern is firmly maintained even after heating, particularly at 600 kGy or more.

[0074] The electron beam crosslinked micropattern was measured by Fourier transform infrared spectroscopy (FT-IR method) to analyze the relationship between the amount of electron beam irradiation and the change in the molecular structure of the crosslinked polyorganosiloxane resin mainly composed of polymethylsilsesquioxane (PMSQ). A Fourier transform infrared spectrophotometer (JASCO Corporation, model FT / IR-6300) was used at a wave number of 1500 cm -1 ~700cm -1 The IR spectrum was measured in the range of 100 nm to 150 nm. The spectra were normalized based on the maximum absorption intensity at each electron beam dose, and a graph is shown in Figure 4.

[0075] As shown in Fig. 4, without electron beam irradiation, -1 The peak at 1120 cm showed the maximum intensity. This is the absorption of four-membered cyclic siloxane bonds (T-type PSQ). On the other hand, with increasing electron beam irradiation dose, -1 The peak around 1050 cm weakens. -1 The peak at around 1270 cm showed the maximum intensity. This is the absorption of crosslinked linear siloxane bonds (Si-O-Si). In addition, as shown below, the peak at 1270 cm originating from Si-CH3 bonds -1 The peak intensity around the 100 nm region is relatively decreased. These facts indicate that the electron beam irradiation caused ring-opening polymerization of the four-membered cyclic siloxane, and that the methyl group of the organic functional group was eliminated from the polysiloxane main chain, causing a condensation reaction, resulting in a change to a crosslinked polyorganosiloxane with a three-dimensional network structure. This is thought to have improved the heat resistance of the fine pattern, allowing it to maintain its shape even when heated to 200°C.

[0076] From the measured IR spectrum, the 1270 cm -1 The peak intensity at around 1050 cm originating from the Si-O-Si bond (P1) -1 The peak intensity (P2) near the peak was obtained, and the peak intensity ratio (P1 / P2) was calculated. In addition, a linear approximation line was obtained by performing a regression analysis on the relationship between the electron beam exposure dose (kGy) and the peak intensity ratio (P1 / P2). The results are shown in Table 1 below and Figure 5.

[0077] [Table 1]

[0078] As shown in Table 1 and Figure 5, the peak intensity ratio (P1 / P2) tends to decrease as the electron beam irradiation dose increases. A linear approximation line was obtained by regression analysis, and the result was y = -0.0001x + 0.7205 (R 2 = 0.6658), and a correlation was observed. It is suggested that by increasing the dose of electron beam irradiation, the peak intensity ratio (P1 / P2) can be reduced to nearly zero, i.e., all of the organic functional groups and terminal groups in the molecular structure of the crosslinked polysiloxane resin, whose main component is PMSQ, can be converted to siloxane bonds.

[0079] [Example 2] Except for changing the electron beam irradiation conditions and the high boiling point solvent to butyl acetate, the polysiloxane resin mainly composed of PMSQ was crosslinked to harden the fine pattern in the same manner as in Example 1. Using an electron beam irradiation device (manufactured by Iwasaki Electric Co., Ltd., model EC250 / 30 / 180LS), the acceleration voltage was 80 kV, the current value was 1.93 mA, the atmospheric O2 concentration was less than 200 ppm, and the irradiation dose was set to 15 levels from 2500 to 50000 kGy.

[0080] Next, the micropatterns crosslinked at each electron beam irradiation dose were measured by FT-IR in the same manner as in Example 1, and the relationship between the electron beam irradiation dose and the change in the molecular structure of the crosslinked polysiloxane resin mainly composed of PMSQ was analyzed. A graph in which each spectrum was normalized based on the maximum absorption intensity at each electron beam irradiation dose is shown in Figure 6.

[0081] In Figure 6, without electron beam irradiation, the -1 The peak of the T-type PSQ showed the maximum intensity at 1050 cm. As the electron beam dose increased, the T-type PSQ peak weakened and -1 The intensity of the peaks of nearby cross-linked chain siloxane (Si-O-Si) increased. The shape of each peak changed from broad to sharp, indicating a significant change from methyl groups to siloxane bonds.

[0082] From the IR spectrum measured in the same manner as in Example 1, the 1270 cm -1 The peak intensity at around 1050 cm originating from the Si-O-Si bond (P1) -1 The peak intensity ratio (P1 / P2) to the peak intensity (P2) near the peak was calculated. In addition, a two-section moving average was calculated to show the relationship between the electron beam exposure dose (kGy) and the peak intensity ratio (P1 / P2). The results are shown in Table 2 below and Figure 7.

[0083] [Table 2]

[0084] As shown in Table 2 and Figure 7, the peak intensity ratio (P1 / P2) tends to decrease as the electron beam irradiation dose increases. When the two-section moving average was calculated, the degree of decrease was large up to 20,000 kGy, the degree of decrease became smaller between 20,000 and 40,000 kGy, and no decreasing trend was observed between 40,000 and 50,000 kGy, with the graph being almost horizontal. From these results, it can be seen that when the irradiation dose is 20,000 kGy or more, the conversion efficiency from methyl groups to siloxane bonds decreases, and when the irradiation dose is 40,000 kGy or more, the conversion from methyl groups to siloxane bonds does not proceed.

[0085] This is believed to be because, up to an irradiation dose of 40,000 kGy, the resin from the surface to the penetration depth of the electron beam is crosslinked in proportion to the irradiation dose, but even if irradiated with 40,000 kGy or more, the resin beyond the penetration depth cannot be crosslinked. The peak intensity ratio (P1 / P2) does not become zero, but decreases to 0.3 or less, and it is believed that the fine pattern formed from the crosslinked body of the polysiloxane resin mainly composed of PMSQ can be given properties such as very high heat resistance, etching resistance, and mechanical strength. Note that, since the acceleration voltage of the electron beam is 50 kV in Example 1 and 80 kV in Example 2, the latter has a higher penetration ability of the electron beam and a smaller number of backscattered electrons, resulting in a larger peak intensity ratio to the irradiation dose.

[0086] [Test Example 2] A polysiloxane resin (SR-13H, manufactured by Konishi Chemical Industry Co., Ltd.) whose main component is polymethylsilsesquioxane (PMSQ) was dissolved in butyl acetate to prepare a solution in which the content of resin components such as PMSQ in the total solution was 12.7 wt%. 0.5 mL of this PMSQ solution was dropped onto a silicon substrate with a diameter of 3 inches, and a PMSQ film (transferred film) was formed by spin coating at 5000 rpm for 30 seconds. The film thickness was approximately 300 nm. A fine pattern was written on the surface using an electron beam lithography system (ELS-S50, manufactured by Elionix Co., Ltd.). The conditions for electron beam lithography were an acceleration voltage of 50 kV, a current value of 20 pA, and an exposure dose of 200 μC / cm. 2 , field size 100μm square, vacuum degree 5×10 -5 It was around Pa.

[0087] The PMSQ film after electron beam writing was heat-treated at 300°C for 1 hour in an air atmosphere. The three types of MPSQ films after film formation, after electron beam irradiation, and after electron beam irradiation and heat treatment were measured by FT-IR in the same manner as in Example 1 to analyze the relationship between the electron beam irradiation and heat treatment and the change in the molecular structure of the crosslinked polysiloxane resin mainly composed of PMSQ. The graph in Figure 8 shows each spectrum normalized based on the maximum absorption intensity in each sample.

[0088] In Figure 8, without electron beam irradiation, the -1 The peak of the 4-membered cyclic siloxane (T-type PSQ) near 1050 cm showed the maximum intensity, and the peak of the T-type PSQ weakened depending on the amount of electron beam irradiation. -1 The peak of cross-linked linear siloxane (Si-O-Si) in the vicinity of the electron beam was intensified. This tendency was further strengthened by heat treatment after electron beam irradiation. This indicates that by performing heat treatment after electron beam irradiation, the remaining methyl groups in the area beyond the penetration depth of the electron beam can be converted into siloxane bonds through a condensation reaction. It is suggested that by combining electron beam irradiation and heat treatment under optimal conditions, it is possible to efficiently reduce the peak intensity ratio (P1 / P2) to almost zero while keeping production costs down, i.e., to convert all organic functional groups and terminal groups in the molecular structure of the cross-linked polysiloxane resin into siloxane bonds.

[0089] [Example 3] A fine pattern was transferred onto the surface of the PMSQ film in the same manner as in Test Example 1 and Example 1. The surface of the PMSQ film onto which the fine pattern was transferred was then irradiated with an electron beam to crosslink the PMSQ and harden the fine pattern. The conditions for electron beam irradiation were an acceleration voltage of 50 kV and four levels of exposure dose of 10, 20, 30, and 40 MGy.

[0090] Next, the micropatterns crosslinked with each electron beam irradiation dose were measured by FT-IR, and the relationship between the electron beam irradiation dose and the change in the molecular structure of the crosslinked polyorganosiloxane was analyzed. -1 FIG. 9 shows a graph in which each spectrum was normalized based on the maximum intensity in the vicinity.

[0091] As in Examples 1 and 2, without electron beam irradiation, -1 The peak of the four-membered cyclic siloxane bond (T-type PSQ) near 1120 cm showed the maximum intensity, and with increasing electron beam irradiation dose, -1 The intensity of the peak near 1050 cm -1 The peak intensity of the siloxane bond (Si-O-Si) near 1050 cm increased. In addition, the peak intensities of the Si-CH3 bonds of the mono-, di-, and trimethyl groups all decreased significantly. -1 The peak near 1080 cm is shifted to the longer wavelength side, and the peak of the stretching vibration of the Si-O-Si bond of quartz is 1080 cm -1 These facts indicate that the four-membered cyclic siloxane underwent ring-opening polymerization, and that organic functional groups and other components were eliminated from the polysiloxane main chain, causing a condensation reaction, resulting in a change to a crosslinked polyorganosiloxane with a three-dimensional network structure.

[0092] From the measured IR spectrum, the 1270 cm 2 cation originating from the Si-CH3 bond of the monomethyl group was detected. -1 The peak intensity at around 1050 cm originating from the Si-O-Si bond (P1) -1The peak intensity ratio (P1 / P2) to the peak intensity (P2) around the peak was calculated. The results are shown in Table 3 below. Also shown are the measurement results of a fine pattern crosslinked under conditions of an acceleration voltage of 80 kV and an exposure dose of 40 MGy in Example 4 described later.

[0093] [Table 3]

[0094] As shown in Table 3, the peak intensity (P1 / P2) ratio decreases as the electron beam dose increases, and the P1 / P2 ratio could be reduced to nearly 0.1 under conditions of an accelerating voltage of 50 kV and an exposure dose of 40 MGy. In addition, comparing the results for accelerating voltages of 50 kV and 80 kV, it can be seen that by utilizing the effect of backscattering that occurs by reducing the accelerating voltage, the exposure dose required to obtain the same P1 / P2 ratio can be reduced to approximately 1 / 4.

[0095] [Example 4] <Creating nanohole patterns> An HSQ master mold (master plate) with a nanohole pattern was produced in the same manner as in Test Example 1. A gas-permeable PDMS mold was produced using the HSQ master mold. The nanohole patterns were three patterns: hole diameter 200 nm, period 400 nm, hole diameter 300 nm, period 600 nm, and hole diameter 400 nm, period 800 nm.

[0096] A 12.0 wt % PMSQ solution was prepared in the same manner as in Test Example 1. The PMSQ solution was spin-coated onto a quartz glass substrate with a diameter of 3 inches on which a 200 nm-thick Al thin film had been evaporated, and while the PMSQ solution was maintaining its fluidity, the transfer surface of a PDMS mold was pressed against the PMSQ film at a pressure of 0.5 MPa to transfer the nanohole pattern on the transfer surface to the PMSQ film.

[0097] Subsequently, the PMSQ film with the transferred nanohole pattern was crosslinked by irradiating it with an electron beam in the same manner as in Example 2. The acceleration voltage was 80 kV and the irradiation dose was 40 MGy. -1 The peak intensity at around 1050 cm originating from the Si-O-Si bond (P1) -1 The peak intensity ratio (P1 / P2) to the nearby peak intensity (P2) was approximately 0.32.

[0098] <Chlorine-based dry etching> Next, the Al thin film / quartz glass substrate with the nanohole pattern formed on the surface of the PMSQ crosslinked body was dry-etched using a chlorine-based mixed gas. An inductively coupled plasma (ICP) etching device (Samco, compound etching device NPF082) was used under the following etching conditions: Cl2 flow rate 5 sccm, BCl3 flow rate 15 sccm, ICP power 150 W, bias power 50 W, time 48 seconds, temperature 20°C, and pressure 0.5 Pa.

[0099] Figures 10(a)-(f) show the external appearance of the sample at each step. Figures 11(a)-(e) show scanning electron microscope (SEM) images of the sample surface at each step. From the images in Figures 11(d) and (e), it can be seen that the nanohole pattern made of the crosslinked PMSQ remains even after dry etching, and nanoholes are formed in the thin aluminum film, exposing the quartz glass substrate. It was demonstrated that the fine patterned product produced by electron beam crosslinking of PMSQ exhibits sufficient resistance to chlorine-based dry etching and can function as an etching mask.

[0100] <Spectroscopic characterization of nanoholes> The spectroscopic characteristics of the fabricated Al nanoholes were evaluated. Light was perpendicularly incident on an Al thin film with nanohole patterns of 400, 600, and 800 nm periods, and the transmittance was measured using a spectrophotometer (Shimadzu Corporation, SolidSpec-3700) to confirm the wavelength dependence of the transmitted light through the nanohole pattern. The measurement results are shown in Figure 12. Absorption and reflection peaks were observed at each period, confirming the occurrence of surface plasmons localized at the openings of the Al nanoholes. No light transmission peaks due to anomalous transmission caused by surface plasmon resonance were observed.

[0101] From the observation images in Figures 11(a) and (e), it can be seen that the side of the nanohole, which was almost vertical in the master, is slightly inclined in the nanohole formed by dry etching. It is considered that, for this reason, the abnormal transmission phenomenon due to surface plasmon generated at the sharp opening was not observed. The cause of this is presumed to be that the polydimethylsiloxane (PDMS) mold was swollen by the high boiling point solvent diethylene glycol monoethyl ether acetate (DGMEA) in which polymethylsilsesquioxane (PMSQ) was dissolved, and the nanopattern formed on the transfer surface was slightly deformed. If the side of the nanohole of the PMSQ crosslinked body that serves as the etching mask is inclined, oblique incident ions that cause side etching are generated, so it is desirable that the side of the nanohole is as vertical as possible.

[0102] Depending on the shape and application of the fine pattern forming body, slight distortion of the fine pattern may become a problem. As a countermeasure, it is considered effective to increase the difference in solubility parameter (SP value) between the two so that the mold made of a gas-permeable polymeric elastomer does not swell with the high-boiling point solvent that dissolves the polyorganosiloxane compound. For example, since the SP value of PDMS is 7.3 to 7.6 and the SP value of DGMEA is 9.0, a high-boiling point solvent with a larger SP value is used. Specifically, ethylene glycol monobutyl ether (EGBE) with an SP value of 10.24, N-methyl-2-pyrrolidone (NMP) with an SP value of 11.3, tripropylene glycol monobutyl ether (TGME) with an SP value of 21.14, etc. can be mentioned. [Industrial Applicability]

[0103] The method for producing a fine pattern forming body of the present invention can produce a fine pattern forming body having excellent properties such as heat resistance, etching resistance, mechanical strength, and transparency, by a method with high production efficiency and low environmental load. Furthermore, the fine pattern forming body of the present invention can improve the production efficiency and product quality of electronic devices such as semiconductors, and the performance of products and members having functional surfaces. Furthermore, the fine pattern forming solution of the present invention can improve the flexibility of the production process and the handleability of intermediate products.

[0104] For example, in the microfabrication of high dielectric constant materials such as Al2O3, HfO2, and ZrO2, chlorine-based dry etching is performed because the volatilization temperature of fluoride is extremely high, but inorganic resists are used because organic resists have poor etching resistance to chlorine-based gases. In this process, inorganic resists such as SiO2 are formed into a film by deposition or the like, and then patterned by photolithography and etching to form an etching mask, which requires many steps and increases costs. By the method for producing a fine pattern-forming body of the present invention, a fine pattern made of a crosslinked polyorganosiloxane compound that can withstand chlorine-based dry etching can be formed in a single process with fewer steps, which significantly improves the efficiency of the chlorine-based dry etching process and significantly reduces costs.

[0105] Therefore, the method for producing a fine pattern forming body, the fine pattern forming body, and the fine pattern forming solution of the present invention are particularly useful in fields such as the manufacturing process of electronic devices in which dry and wet etching, which requires high etching resistance and heat resistance, is frequently used, films and members having functional surfaces such as anti-glare properties, which require durability and weather resistance, optical devices which require transparency and light resistance, and fluid devices and bioanalytical devices which require etching resistance to reagents.

Claims

1. A step of preparing a transfer material solution by dissolving a polyorganosiloxane compound mainly composed of polyorganosilsesquioxane in a high boiling point solvent; A step of coating the transfer material solution on a substrate surface to form a film to be transferred; a step of pressing a surface of the film to be transferred against a transfer surface of a mold made of a gas-permeable polymeric elastomer, the transfer surface having a fine pattern formed thereon, while the transfer material solution constituting the film to be transferred maintains its fluidity; a step of separating the surface of the film to be transferred from the transfer surface after filling the fine pattern with the transfer material solution; a step of irradiating the surface of the film to which the fine pattern has been transferred with high-energy radiation to crosslink the polyorganosiloxane compound mainly composed of polyorganosilsesquioxane, thereby hardening the fine pattern; A method for producing a fine patterned body comprising the steps of:

2. 2. The method for producing a fine patterned body according to claim 1, wherein the high energy beam is an electron beam or an X-ray.

3. 3. The method for producing a fine pattern forming body according to claim 2, wherein the accelerating voltage of the electron beam or X-ray is in the range of 10 to 500 kV and the exposure dose is in the range of 300 to 40,000 kGy.

4. 4. The method for producing a fine pattern forming body according to claim 1, wherein the time interval between separating the surface of the film to be transferred from the transferring surface and irradiating the high energy beam is within one hour.

5. The method for producing a fine pattern forming body according to any one of claims 1 to 3, wherein the content of the polyorganosiloxane compound mainly composed of polyorganosilsesquioxane contained in the transfer material solution is in the range of 10.0 to 20.0 wt % with respect to the total amount of the solution.

6. 4. The method for producing a fine pattern formed body according to claim 1, wherein the pressure for pressing the surface of the film to be transferred and the transferring surface is in the range of 0.5 MPa to 10 MPa.

7. 4. The method for producing a fine pattern formed body according to claim 1, wherein the gas-permeable polymeric elastomer constituting the mold is polydimethylsiloxane (PDMS) or poly(1-trimethylsilyl-1-propyne) (PTMSP).

8. The difference (SP1-SP2) between the SP value of the high boiling point solvent (SP1) and the SP value of the gas-permeable polymeric elastomer constituting the mold (SP2) is 5.0 (cal / cm ３ ) ０．５ The method for producing a fine pattern formed body according to any one of claims 1 to 3, wherein the method is as described above.

9. The present invention comprises a substrate and a coating film disposed on a part or all of an area of ​​at least one of the outer surfaces of the substrate, A fine pattern is formed on the surface of the coating film, The coating film is composed of a crosslinked body of a polyorganosiloxane compound mainly composed of polyorganosilsesquioxane, In the IR spectrum measured by the FT-IR method, Si-R １ Bond (wherein, R １ is a hydrocarbon group, and is a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms which may have a substituent that does not contain oxygen or nitrogen atoms, or a phenyl group which may have a substituent that does not contain oxygen or nitrogen atoms), and a peak intensity (P1) at 1050 cm originating from a Si-O-Si bond. －１ The ratio (P1 / P2) of the peak intensity to the nearby peak intensity (P2) is 0.7 or less.

10. R １ is a monomethyl group, and Si—CH ３ 1270 cm due to bond －１ The peak intensity (P1) near 1050 cm originating from the Si-O-Si bond －１ 10. The fine pattern formed product according to claim 9, wherein a ratio (P1 / P2) of a peak intensity to a nearby peak intensity (P2) is 0.7 or less.

11. 11. The method for producing a fine pattern formed body according to any one of claims 1 to 3, or the fine pattern formed body according to claim 9 or 10, wherein the fine pattern formed body is one selected from the group consisting of a substrate on which a dry etching mask or a lift-off resist for use in the manufacture of electronic devices has been formed, a functional film and member having a functional surface exhibiting anti-glare properties, water repellency or hydrophilicity, an optical device and member thereof having a diffraction grating or a microlens array, and a fluidic device and member thereof having a microchamber array or a microchannel.

12. A solution for forming a fine pattern, comprising a polyorganosiloxane compound mainly composed of polyorganosilsesquioxane and a high-boiling point solvent, wherein the content of the polyorganosilsesquioxane compound mainly composed of polyorganosilsesquioxane is in the range of 10.0 to 12.5 wt % with respect to the total amount of the solution.

13. 13. The method for producing a fine pattern forming body according to claim 1, wherein the high boiling point solvent has a boiling point of 126° C. or higher.

14. The solution for forming a fine pattern according to claim 12, wherein the high boiling point solvent has a boiling point of 126° C. or higher.

14. 13. The method for producing a fine pattern forming body according to claim 1, wherein the high boiling point solvent is at least one selected from the group consisting of diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, and tripropylene glycol monobutyl ether.

15. The SP value of the high boiling point solvent is 10.0 (cal / cm ３ ) ０．５ The method for producing a fine pattern forming body according to any one of claims 1 to 3, or the solution for fine pattern formation according to claim 12, which is as described above.

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