JP2008084984A - Photocuring composition for optical nano imprint lithography and pattern forming method employing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition excellent in adhesion to a mold. <P>SOLUTION: The photocuring composition for optical nano imprint lithography contains (a) total 88-99 mass% of polymerizing compound containing not less than 10 mass% of polymerizing compound whose polar factor (e value) in Q-e scheme is positive and polymerizing compound containing not less than 10 mass% of polymerizing compound whose e value is negative (b) 0.1-10 mass% of poto polymerization initiating agent and (c) 0.0005-5.0 mass% of at least one kind of surfactant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photocurable composition for optical nanoimprint lithography and a pattern forming method using the same.

  The nanoimprint method has been developed by developing embossing technology, which is well-known in optical disc production, and mechanically pressing a mold master (generally called a mold, stamper, or template) with a concavo-convex pattern onto a resist. This is a technology that precisely deforms and transfers fine patterns. Once a mold is made, it is economical because nanostructures can be easily and repeatedly molded, and it is a nano-processing technology that has few harmful wastes and emissions, so in recent years it has been expected to be applied in various fields. Yes.

 Two types of nanoimprint methods have been proposed: a case where a thermoplastic resin is used as a material to be processed (Non-Patent Document 1) and a case where a photocurable composition for optical nanoimprint lithography is used (Non-Patent Document 2). In the case of thermal nanoimprint, the mold is pressed onto a polymer resin heated to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer the microstructure to the resin on the substrate. Since it can be applied to various resin materials and glass materials, it is expected to be applied in various fields. Patent Documents 1 and 2 disclose a nanoimprint method for forming a nanopattern at low cost using a thermoplastic resin.

  On the other hand, in the optical nanoimprint method in which light is irradiated through a transparent mold and the photocurable composition for optical nanoimprint lithography is photocured, imprinting at room temperature becomes possible. Recently, new developments such as a nanocasting method combining the advantages of both and a reversal imprint method for producing a three-dimensional laminated structure have been reported. In such a nanoimprint method, there are roughly three stages of application. The first stage is when the molded shape itself has a function and can be applied as various nanotechnology element parts, and various micro / nano optical elements, high-density recording media, and optical films can be mentioned. As the second stage, a laminated structure is constructed by simultaneous integral molding of a micro structure and a nano structure, or simple interlayer alignment, and is intended to be applied to the production of μ-TAS and biochips. The third step is to apply high-precision alignment and high integration to the production of high-density semiconductor integrated circuits instead of conventional lithography, and to the production of liquid crystal display transistors. , Efforts toward commercialization are becoming active.

As an application example of the nanoimprint method, an application example to manufacturing a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the 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 increases dramatically, such as 256 mega, 1 giga, and 4 giga, the pattern formation time is also greatly increased, and there is a concern that the throughput is significantly inferior. Therefore, in order to increase the speed of the electron beam drawing apparatus, development of a collective figure irradiation method in which various shapes of masks are combined and irradiated with an electron beam collectively to form an electron beam with a complicated shape is underway. . 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, nanoimprint lithography, which has been proposed as a technique for performing fine pattern formation at low cost, has been proposed. For example, Patent Documents 1 and 3 disclose a nanoimprint technique in which a silicon wafer is used as a stamper and a fine structure of 25 nanometers or less is formed by transfer.
Patent Document 4 discloses a composite composition using nanoimprint applied to the field of semiconductor microlithography. On the other hand, studies to apply nanoimprint lithography to semiconductor integrated circuit fabrication such as micro mold fabrication technology, mold durability, mold fabrication cost, mold releasability from resin, imprint uniformity and alignment accuracy, inspection technology, etc. It started to become active.
However, the composition used in nanoimprint lithography is required to improve the mold releasability of the photocured film and reduce the adhesion to the mold while flowing and following the mold cavity properly. Nevertheless, these have not been fully studied.

  Next, an application example of nanoimprint lithography to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described. In recent years, optical nanoimprint lithography has attracted particular attention as an inexpensive lithography that replaces conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates as LCDs and PDP substrates increase in size and definition. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method. Etching photoresists used in conventional photolithographic methods are required to have high adhesion, uniformity of coatings, resist savings, adhesion to various substrates, etching resistance, and heat resistance. Similar characteristics are required for photo-nanoimprint resists instead of.

  With respect to the uniformity of the coating film, demands for various parts such as the coating film thickness uniformity and the dimensional uniformity, film thickness, and shape due to higher resolution are increasing as the substrate size increases. Conventionally, in the field of manufacturing liquid crystal display devices using a small glass substrate, a method of spinning after dropping at the center has been used as a resist coating method (Non-patent Document 3). Although the coating method that spins after dropping in the center can provide good coating uniformity, for example, in the case of a large substrate of 1 m square class, the amount of resist that is shaken off during spinning (during spinning) and discarded becomes considerably large. In addition, problems such as cracking of the substrate due to high-speed rotation and securing of tact time occur. Furthermore, since the coating performance in the method of spinning after dropping in the center depends on the rotational speed at the time of spinning and the amount of resist applied, a general-purpose motor that can obtain the required acceleration when it is applied to a fifth-generation substrate that is further enlarged. However, when such a motor is specially ordered, there is a problem that the cost of parts increases. In addition, even if the substrate size and the apparatus size are increased, the required performance in the coating process, such as coating uniformity ± 3%, tact time 60 to 70 seconds / sheet, etc., is not substantially changed. It has become difficult to meet demands other than coating uniformity. Under such circumstances, a resist coating method using a discharge nozzle method has been proposed as a new resist coating method applicable to large substrates after the fourth generation substrate, particularly the fifth generation substrate and beyond. The discharge nozzle type resist coating method is a method in which a photoresist composition is applied to the entire coated surface of a substrate by relatively moving the discharge nozzle and the substrate. For example, a plurality of nozzle holes are arranged in a row. A method of using a discharge nozzle having a discharge port and a slit-like discharge port and capable of discharging a photoresist composition in a band shape has been proposed. There has also been proposed a method of adjusting the film thickness by applying a photoresist composition to the entire surface of a substrate applied by a discharge nozzle method and then spinning the substrate. Therefore, in order to replace the conventional photolithography resist with the nanoimprint composition and apply it to the field of manufacturing these liquid crystal display elements, the coating uniformity on the substrate is important.

  Addition of fluorine-based and / or silicone-based surfactants, such as positive photoresists used in semiconductor integrated circuit manufacturing and liquid crystal display manufacturing, and pigment dispersed photoresists for color filter manufacturing. It is known to solve the problem of coating defects such as striations and scale-like patterns (unevenness of drying of resist film) that occur during coating (Patent Documents 5 to 7). In addition, fluorine-based surfactants and silicone-based surfactants are added to the photocurable compositions for solvent-free photonanoimprint lithography to improve the wear and coating properties of protective films such as compact disks and magneto-optical disks. (Patent Documents 7 to 10). Similarly, Patent Document 11 discloses that a nonionic fluorosurfactant is added in order to improve the ink ejection stability of the inkjet composition. Furthermore, Patent Document 12 discloses that 1% of a polymerizable unsaturated double bond-containing surfactant is used when embossing a painting composition coated with a thick film with a brush, brush, bar coater or the like with a hologram processing mold. As described above, an example in which 3% or more is preferably added to improve the water swellability of the cured film is disclosed. As described above, a technique for adding a surfactant to a protective film such as a positive photoresist, a pigment-dispersed photoresist for producing a color filter, or a magneto-optical disk to improve the coating property is a known technique. In addition, as seen in the above examples of inkjet and painting compositions, there is also a technique for adding a surfactant to a solventless photocurable resin and adding the surfactant to improve the properties in each application. It is known. However, a method for improving the substrate coatability of a low-viscosity photocurable nanoimprint resist composition that does not contain pigments, dyes, and organic solvents as essential components has not been known so far.

  In the optical nanoimprint, it is necessary to improve the fluidity of the composition into the cavity of the mold recess and to improve the adhesion between the resist and the substrate. It has been difficult to achieve both fluidity, releasability and adhesion. In particular, for optical nanoimprint resist compositions, if the adhesion to the mold is strong, the number of repeated use of the mold decreases, and there is a problem that the productivity is remarkably reduced, but there are almost no techniques for reducing the adhesion to the mold. Not considered.

The prior art relating to optical nanoimprinting, which is an application range of the present invention, will be described in more detail. In photo nanoimprint lithography, a liquid photocurable composition for photonanoimprint lithography is dropped onto a substrate such as a silicone wafer, quartz, glass, film or other material such as a ceramic material, metal, or polymer, and is approximately several tens of nm. After coating with a film thickness of ˜several μm, pressing and pressing a mold having fine irregularities with a pattern size of about several tens of nanometers to several tens of μm, and curing the composition by light irradiation in the pressurized state In general, the mold is released from the coating film to obtain a transferred pattern. For this reason, in the case of optical nanoimprint lithography, at least one of the substrate and the mold needs to be transparent for the convenience of light irradiation. Usually, light is irradiated from the mold side, and an inorganic material such as quartz or sapphire, a light-transmitting resin, or the like is often used as the mold material.
The optical nanoimprint method is (1) no heating / cooling process is required and high throughput is expected compared to the thermal nanoimprint method. (2) Since the liquid composition is used, imprinting at low pressure is possible. Major advantages include (3) no dimensional change due to thermal expansion, (4) the mold is transparent and easy to align, and (5) a robust three-dimensional crosslinked body is obtained after curing. It is done. In particular, the present invention can be preferably applied to a field where alignment accuracy is required with a pattern width of about 50 nm to 50 μm, and is suitable for a fine processing application in the semiconductor fine processing field and the flat panel display field.

  Another feature of the optical nanoimprint method is that the resolution does not depend on the light source wavelength as compared with ordinary optical lithography. Therefore, expensive devices such as a stepper and an electron beam drawing device are also used for fine processing on the nanometer order. The feature is not required. On the other hand, the optical nanoimprint method requires an equal-magnification mold, and since the mold and the resin are in contact, there are concerns about the durability and cost of the mold. Furthermore, in the optical nanoimprint lithography process, a residual film (a portion where the mold convex portion is pressed against the photocurable composition for optical nanoimprint lithography) is likely to occur. The thinner the remaining film layer, the more preferable is a structure that can be formed using nanoimprint. Further, if there is a large amount of residual film, it tends to be a line width controllability during etching or etching residue.

 Thus, in order to apply a thermal and / or optical nanoimprint method and imprint a nanometer-sized pattern over a large area, only pressing pressure uniformity and flatness of the master (mold) are required. In addition, it is necessary to control the behavior of the resist that is pushed out and flows out. In the conventional semiconductor technology, a region not used as an element can be arbitrarily set on the wafer, so that a resist outflow portion can be provided outside the imprint portion using a small master. In semiconductors, imprint defects should not be used as defective elements. For example, the entire surface functions as a device in applications such as hard disks, so special measures are required to prevent imprint defects. It is.

Molds used in optical nanoimprint lithography can be manufactured from various materials such as metals, semiconductors, ceramics, SOG (Spin On Glass), or certain plastics. For example, a flexible polydimethylsiloxane mold having a desired microstructure described in Patent Document 13 has been proposed. In order to form a three-dimensional structure on one surface of the mold, various lithography methods can be used depending on the size of the structure and the specifications for its resolution. Electron beam and x-ray lithography are typically used for structure dimensions below 300 nm. Direct laser exposure and UV lithography are used for larger structures.
Regarding the photo nanoimprint method, it is important that the photocurable composition for photo nanoimprint lithography does not adhere to the mold. The mold and the surface treatment of the mold, specifically, hydrogenated silsesquioxane or fluorinated ethylene propylene Attempts have been made so far to solve adhesion problems using polymer molds.

  Here, the photocurable resin used for optical nanoimprint lithography will be described. Photocurable resins applied to nanoimprints are roughly classified into radical polymerization types and ionic polymerization types, or their hybrid types, depending on the reaction mechanism. Although any composition can be imprinted, a radical polymerization type having a wide selection range of materials is generally used (Non-Patent Document 4). As the radical polymerization type, a composition containing a monomer (monomer) or oligomer having a vinyl group or (meth) acryl group capable of radical polymerization and a photopolymerization initiator is generally used. When irradiated with light, radicals generated by the photopolymerization initiator attack the vinyl group, and chain polymerization proceeds to form a polymer. When a bifunctional or higher polyfunctional monomer or oligomer is used as a component, a crosslinked structure is obtained. Non-Patent Document 5 discloses a composition that can be imprinted at low pressure and room temperature by using a low-viscosity UV curable monomer.

The characteristics of the material used for optical nanoimprint lithography will be described in detail. The required characteristics of materials vary depending on the application to be applied, but the demands for process characteristics are common regardless of the application. For example, the main requirements shown in Non-Patent Document 6 are applicability, substrate adhesion, low viscosity (<5 mPa · s), releasability, low cure shrinkage, fast curability, and the like. It is known that there is a strong demand for low-viscosity materials especially in applications that require low-pressure imprinting and reduction of the residual film ratio. On the other hand, when the required characteristics are listed for each application, there are, for example, a refractive index and light transmittance for an optical member, and an etching resistance and a remaining film thickness reduction for an etching resist. The key to material design is how to control these required characteristics and balance them. At least the process material and the permanent film have different required characteristics, so the material must be developed according to the process and application. As a material applied to such optical nanoimprint lithography, Non-Patent Document 6 discloses a photocurable material having a viscosity of about 60 mPa · s (25 ° C.). Similarly, Non-Patent Document 7 discloses a fluorine-containing photosensitive resin with improved releasability having a viscosity of 14.4 mPa · s mainly composed of monomethacrylate.
As described above, regarding the composition used in optical nanoimprinting, although there is a description of a demand for viscosity, there has been no report on a material design guideline for adapting to each application.

  An example of a photocurable resin that has been applied to optical nanoimprint lithography will be described. Patent Documents 14 and 15 disclose examples of embossing using a photocurable resin containing a polymer having an isocyanate group for producing a relief hologram or a diffraction grating. Patent Document 16 discloses a photocurable composition for imprint optical nanoimprint lithography, which contains a polymer, a photopolymerization initiator, and a viscosity modifier.

  Non-Patent Document 9 describes a technique for improving problems such as peelability between a photocurable resin and a mold, film shrinkage after curing, and low sensitivity due to photopolymerization inhibition in the presence of oxygen (1). A photocurable composition for optical nanoimprint lithography comprising a functional acrylic monomer, (2) a functional acrylic monomer, a silicone-containing monofunctional acrylic monomer, and a photopolymerization initiator is disclosed.

  In Non-Patent Document 10, a photocurable composition for photo-nanoimprint lithography containing a monofunctional acrylic monomer, a silicone-containing monofunctional monomer, and a photopolymerization initiator is formed on a silicone substrate, and light is applied using a surface-treated mold. It is disclosed that defects after molding in nanoimprint lithography are reduced.

In Non-Patent Document 11, a photocurable composition for optical nanoimprint lithography containing a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is formed on a silicone substrate, and high resolution and coating can be achieved by SiO ₂ mold. A composition having excellent uniformity is disclosed.

  However, as shown in Non-Patent Documents 8 to 11, although various photocurable resins in which an acrylic monomer, an acrylic polymer, and a vinyl ether compound having different functional groups are applied to optical nanoimprint lithography have been disclosed, No guidance on material design such as preferred types, optimal monomer types, monomer combinations, optimal monomer or resist viscosities, preferred resist solution properties, improved resist coatability is disclosed. In particular, there is no guideline for reducing mold adhesion, which is the lifeline of productivity. Therefore, a preferable composition for widely applying the composition to optical nanoimprint lithography applications is not known, and a satisfactory optical nanoimprint resist composition has never been proposed so far.

  The application to an etching resist for substrate processing will be described in detail. The etching resist is not an element left as it is, but merely a copy of a semiconductor or transistor circuit pattern. In order to create a circuit pattern, it is necessary to transfer these resist patterns to various layers including devices. The method of transferring the pattern is performed by an etching process that selectively removes the uncovered portion of the resist. For example, TFT array substrates and PDP electrode plates are manufactured by applying an etching resist on a conductive base or insulating base sputtered on a glass or transparent plastic substrate, drying, pattern exposure, development, and etching. The resist peeling process is performed on the thin film of each layer. Conventionally, a positive type photoresist has been often used as an etching resist. In particular, resists containing alkali-soluble phenol novolac resin and 1,2-quinonediazide compound as main components and chemically amplified resists containing (poly) hydroxystyrene as a polymer have high etching resistance and are easy to peel off. So far, etching photoresists for semiconductors and TFT transistors have been widely used, and much knowledge has been accumulated. For etching, there are wet etching methods using various liquid etchants and dry etching methods that vaporize and remove the film on the substrate using ions and radicals (active species) generated by decomposing gas with plasma in a decompression device. is there. Etching is an important process that greatly affects device design accuracy, transistor characteristics, yield, and cost. Etching resist has material and process compatibility that can be applied to both dry etching and wet etching. is necessary. In order to apply the composition used for optical nanoimprint lithography to the resist field used in these conventional photolithography, etching properties similar to those of conventional photoresists are necessary, but etching has not been sufficiently studied. Various problems occurred in the process.

The main technical issues for etching resists are improvement of pattern processing dimensional accuracy, improvement of taper processing control (improvement of undercut shape), improvement of etching uniformity on large substrates, improvement of etching selectivity with the substrate, etching speed There are many problems such as improvement of the multi-layered film, ensuring safety of waste liquid, waste gas, etc., and improving defects on the film (particles, residues) after etching. When applying a photocurable composition for photonanoimprint lithography for photonanoimprint as an etching resist, as with conventional positive photoresists,
(1) etchant selected according to film type, suitability for etching gas,
(2) imparting adhesion between the pattern and the etched substrate so as not to cause an undercut;
(3) In order to bathe the dimensional controllability of the pattern before and after etching, it is important to impart wettability between the etchant and the resist.

However, the photocurable composition for nanoimprint photonanoimprint lithography has a higher technical difficulty in terms of the following (4), (5), and (6) in addition to the points (1) to (3).
(4) In order to improve the releasability from the mold, if the resist film is made hydrophobic, the wettability of the etchant and the resist will be further deteriorated, and etching residue will be easily generated.
(5) Since the photo-curable composition for optical nanoimprint lithography has a three-dimensional network structure, it is difficult to peel off compared to a positive resist, and the etching resistance is improved if the network structure is made stronger. The point that peeling becomes more difficult,
(6) Compared to conventional photolithography, optical nanoimprint lithography is likely to generate residues after etching because the residue is likely to be removed after the mold is peeled off.
Etc.
Although various materials are disclosed for photo-curable compositions for photo-nano-imprint lithography for nano-imprints, disclosure of nano-imprint materials that can be suitably used in any of the steps of photo-lithography, etching, and peeling of nano-imprints There has never been a guideline for material design. In addition, photo-curable compositions for optical nanoimprint lithography, which have been known for use in inkjet compositions and protective films for magneto-optical disks, have a common part in the photolithographic process, but an etching process and a peeling process. The absence of this is greatly different from the etching resist. Therefore, when the photocurable resin applied in these uses is applied as an etching resist as it is, problems often occur in the etching process and the peeling process.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 US Pat. No. 5,259,926 JP 2005-527110 Gazette Japanese Patent Laid-Open No. 7-230165 JP 2000-181055 A JP 2004-94241 A JP-A-4-149280 JP-A-7-62043 JP 2001-93192 A JP 2005-8759 A JP 2003-165930 A JP 2006-114882 A JP 2004-59820 A JP 2004-59822 A US Publication No. 2004/110856

S.Chou et al.:Appl.Phys.Lett.Vol.67,114,3314 (1995) M. Colbun et al ,: Proc. SPIE, Vol. 676, 78 (1999) Electronic Journal 121−123 No.8 (2002) F.Xu et al.:SPIE Microlithography Conference, 5374,232 (2004) D.J.Resnick et al .: J.Vac.Sci.Technol.B, Vol.21, No.6,2624 (2003) The latest resist material handbook, P1, 103-104 (2005, published by Information Organization) CM Publishing: Development and application of nanoimprint P159-160 (2006) N. Sakai et al .: J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005) M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005) T. Beiley et al .: J. Vac. Sci. Technol. B18 (6), 3572 (2000) B. Vratzov et al .: J. Vac. Sci. Technol. B21 (6), 2760 (2003) Polymer design, P117 (1992, published by Nikkan Kogyosha) J. Brandrup et al., Polymer Handbook, 3 rd Ed (JOHN WILEY & SONS) The first nanoimprint technology, P157 (2005, published by Industrial Research Council)

  The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a novel photocurable composition for photo-nanoimprint lithography. In particular, an object is to provide a material having good adhesion to a mold. In particular, it is an object of the present invention to provide a composition having excellent photocurability, pattern forming property, spin coating property, slit coating property, and etching property, and improved adhesion to a mold.

As a result of intensive studies by the inventors based on the above problems, it has been found that the above problems can be solved by the following means.
(A) A total of polymerizable compounds containing 10% by mass or more of polymerizable compounds having a positive polarity factor (e value) in the Qe scheme and 10% by mass or more of polymerizable compounds having a negative e value are 88 to 99% by mass,
(B) 0.1-10% by mass of a photopolymerization initiator,
(C) 0.0005 to 5.0 mass% of at least one surfactant,
A photocurable composition for optical nanoimprint lithography.
(2) The photocurable composition for optical nanoimprint lithography according to (1), wherein the viscosity at 25 ° C. is 3 to 18 mPa · s.
(3) A pattern forming method including a step of applying and curing the photocurable composition for optical nanoimprint lithography according to (1) or (2), wherein the film thickness of the composition after application is 0 A pattern forming method in optical nanoimprint lithography, wherein the pattern is 5 to 40 μm.
(4) The step of applying the photocurable composition for photo-nanoimprint lithography according to (1) or (2), pressurizing a light-transmitting mold onto a resist layer on a substrate, and the photocurable composition for photo-nanoimprint lithography A resist pattern forming method including a step of deforming an object, a step of irradiating light from the back of the mold or the back of the substrate, curing the coating film, and forming a resist pattern that fits into a desired pattern.

  According to the present invention, it is possible to obtain a photocurable composition for photo-nanoimprint lithography having excellent mold adhesion while maintaining good conditions such as coating properties and photocurability.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, meth (acrylate) represents acrylate and methacrylate, meth (acryl) represents acryl and methacryl, and meth (acryloyl) represents acryloyl and methacryloyl.
In the present specification, the “monomer” in the present invention refers to a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers.
The nanoimprint referred to in the present invention refers to pattern transfer having a size of about several μm to several tens of nm.

 The photocurable composition for optical nanoimprint lithography of the present invention has, for example, high light transmittance before curing, excellent ability to form a fine concavo-convex pattern, application suitability, and sensitivity (fast curing) after curing, Excellent film properties in terms of resolution, line edge roughness, film strength, mold release, mold adhesion, residual film properties, etching resistance, low curing shrinkage, substrate adhesion, and other aspects Can be widely used for optical nanoimprint lithography.

That is, when the photocurable composition for optical nanoimprint lithography of the present invention is used for optical nanoimprint lithography,
(1) Since the solution fluidity at room temperature is excellent, the composition is easy to flow into the cavity of the mold recess, and the air is difficult to be taken in, so that bubble defects are not caused. Since it is difficult to adhere after photocuring, the mold can be used repeatedly.
(2) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.
(3) Since the photocuring speed of the film is high, the productivity is high.
And the like.

The photocurable composition for optical nanoimprint lithography of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is (a) polymerizable with a positive polarity factor (e value) in the Qe scheme. A total of 88 to 99% by mass of polymerizable compounds containing 10% by mass or more of compounds and 10% by mass or more of polymerizable compounds having a negative e value, and (b) 0.1 to 10% by mass of a photopolymerization initiator (C) At least one kind of surfactant is contained in an amount of 0.0005 to 5.0% by mass. Furthermore, (d) sensitizer 0-5.0 mass%, (e) adhesion promoter 0-5.0 mass%, etc. may be included. In particular, a composition in which the components (a) to (e) occupy 90% by mass or more of the whole is preferable. The polymerizable compound having a positive polarity factor (e value) and the polymerizable compound having a negative e value in the Qe scheme may each include two or more types, and when two or more types are included, The total amount is 10% by weight or more.
Here, the polar factor (e value) in the Qe scheme will be described. As described in Non-Patent Document 12, the reactivity of the monomer (polymerizable compound) in the copolymerization depends on the resonance stability of the monomer (polymerizable compound) and radicals generated therefrom, and the monomer (polymerizable compound). It is suggested that it is largely governed by the difference in polarity of the generated radicals. Alfredy and Price have empirically proposed the Qe scheme in consideration of the resonance term and the polarity term, and specifically expressed the reactivity of the monomer (polymerizable compound) in the copolymerization by the following formula.
r ¹ = k ¹¹ / k ¹² = (Q ¹ / Q ² ) exp [−e ¹ (e ¹ −e ² )]
r ² = k ²² / k ²¹ = (Q ² / Q ¹ ) exp [−e ² (e ² −e ¹ )]
Here, the subscripts 1 and 2 relate to the monomers (polymerizable compounds) 1 and 2 used in the polymerization reaction, Q is a term relating to the measure of conjugation of the monomer (polymerizable compound), and e is a polar term. .
The following formulas are derived from these two formulas, and it is shown that alternating growth is likely to occur in the copolymerization of the combination of monomers (polymerizable compounds) 1 and 2 having a large difference in polarity, and the alternation of the produced copolymer increases. Yes.
ln (r ¹ r ² ) = − (e ¹ −e ² ) ²
In the present invention, by using radically polymerizable compounds having different polar factors (e values), it is possible to remarkably improve mold adhesion while maintaining photoreactivity.
It is considered that this is because, as described above, the sign of the polar factor (e value) is different, so that the alternate growth is promoted and a firm cured film is formed, which makes it difficult to adhere to the mold.
In addition, about the code | symbol or value of the polar factor (e value) of the polymeric compound in connection with this invention, the thing of a nonpatent literature 13 was used.

The viscosity of the composition of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified.
The viscosity of the composition of the present invention is preferably in the range of 3 to 18 mPa · s at 25 ° C., more preferably 4 to 15 mPa · s.
By setting such a viscosity, it is possible to impart the ability to form a fine concavo-convex pattern before curing, coating suitability and other processing suitability. After curing, resolution, line edge roughness, residual film properties, substrate adhesion Alternatively, excellent coating film properties can be imparted in other respects. Here, the latest resist material handbook, pages 1, 103 to 104 (2005, published by Information Technology Corporation) describes that the viscosity is preferably 5 mPa · s or less.
However, as a result of intensive studies by the present inventors, the viscosity of the composition of the present invention is not simply low, but has a specific viscosity range, that is, a specific viscosity range of 3 to 18 mPa · s. Then, it has been found that the object of the present invention can be achieved more satisfactorily.
That is, by setting the viscosity of the composition of the present invention to 3 mPa · s or more, the substrate coating suitability tends to be more preferable, and the mechanical strength of the film tends to be improved. Specifically, by setting the viscosity to 3 mPa · s or more, the occurrence of unevenness on the surface during the application of the composition of the present invention tends to be suppressed, and the composition can be prevented from flowing out from the substrate during the application. It tends to be preferable.
On the other hand, by setting the viscosity of the composition of the present invention to 18 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition can easily flow into the cavity of the concave portion of the mold, Since it becomes difficult for air to be taken in, bubble defects are less likely to occur, and residues are less likely to remain after photocuring in the mold protrusions. Further, since the viscosity of the optical nanoimprint composition disclosed so far in the latest resist material handbook, pages 1, 103 to 104 (2005, published by Information Technology Corporation), is about 50 mPa · s, Since there was a problem that a residue was likely to remain in the concave portion of the mold after photocuring, it could be applied only to limited applications. For example, it has been difficult to develop into fine processing applications such as semiconductor integrated circuits and thin film transistors for liquid crystal displays.
The photocurable composition for optical nanoimprint lithography of the present invention can be suitably applied to these uses, and other uses such as a flat screen, a micro electro mechanical system (MEMS), a sensor element, an optical disk, a high-density memory disk, and the like. Magnetic recording media, optical components such as diffraction grating relief holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, microlens arrays, immunoassay chips, DNA separation chips, micros Widely applicable to the production of reactors, nanobiodevices, optical waveguides, optical filters, photonic liquid crystals, and the like.

(A) A polymerizable compound having a positive e value and a polymerizable compound having a negative e value The polymerizable compound having a positive e value and a polymerizable compound having a negative e value used in the present invention will be described. As described in Non-Patent Document 12, the e value represents the polarity of the radical of the generated polymerizable monomer. In the present invention, by appropriately combining polymerizable compounds having different e value polarities, the photocuring rate is obtained. Can be obtained. Surprisingly, by using a composition of such a combination, there is a tendency that an uncured product or a cured product hardly adheres after photocuring in both the mold convex portion and the concave portion. Such techniques and techniques have not been disclosed so far, and are particularly useful as optical compositions for optical nanoimprinting with high productivity.

As a specific example of the polymerizable compound having a positive e value, a radical polymerizable monomer having an ethylenically unsaturated bond-containing group is preferably used.
Specific examples of the radically polymerizable unsaturated monomer having a positive e value that can be used in the present invention include acrylamide, methacrylate, acetoxy acrylate, benzyl acrylate, butyl acrylate, glycidyl acrylate, acrylonitrile, allylbenzene, crotonaldehyde, diallyl cyanamide. , Diethyl fumarate, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1 , 3-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, fuma Nitrile, maleic anhydride, maleimide, N-phenylmethacrylamide, butyl methacrylate, glycidyl methacrylate, methyl methacrylate, phenyl methacrylate, N-methylacrylamide, N-hydroxyethylacrylamide, N, N-dimethylaminoethyl (meth) acrylate, diethylamino And monomers having one ethylenically unsaturated bond-containing group such as ethyl (meth) acrylate.
Furthermore, as the (meth) acrylate derivative, diethylene glycol monoethyl ether acrylate, dimethylol dicyclopentane di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Ethylene oxide (hereinafter referred to as “EO”) modified 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified (hereinafter referred to as “ECH”) modified 1,6-hexanediol di (meth) acrylate, allyloxy Polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, propylene oxide (hereinafter referred to as “PO”) modified bisphenol A di (meth) acrylate, modified vinyl Phenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol diacrylate, PO modified neo Pentyl glycol diacrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol, stearic acid-modified pentaerythritol di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) Di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Recall di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethanol (di) acrylate , Neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate 2-acryloyloxyethyl phthalate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, aliphatic epoxy (meth) acrylate, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate , Caprolactone (meth) acrylate, cetyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, Isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate Lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, Nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexa Ethylene glycol (meth) acrylate, phenoxytetraethylene glycol (Meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) Acrylate, tert-butylcyclohexyl (meth) acrylate, tridodecyl (meth) acrylate, trifluoroethyl (meth) acrylate, urethane mono (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified Limethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate , Dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. .

 Among these, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, EO-modified neopentyl glycol diacrylate, PO-modified neopentyl glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane Tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate Rate, and the like viscosity, excellent in such as volatile, preferably used in the compositions of the present invention.

On the other hand, as a specific example of the polymerizable compound having a negative e value that can be used in the present invention, a monomer having an ethylenically unsaturated bond-containing group is preferably used.
Specific examples of the monomer having an ethylenically unsaturated bond-containing group include N, N′-dimethylacrylamide, allyl acetate, allyl acrylate, allyl alcohol, vinyl mercaptobenzothiazole, N-vinyl caprolactam, vinyl carbazole, diallyl phthalate, 1 , 1'-diphenylethylene, 1-vinylimidazole, 1-vinyl-2-methylimidazole, indene, methacrylamide, 2-hydroxyethyl metallate, norbornadiene, N-vinyloxazolidone, N-vinyl-2-pyrrolidone, N- Vinyl formaldehyde, diallyl melamine, N, N'-divinylaniline, indene, isopropenyl acetate, methacryloyl acetone, norbornadiene, 2,4-acryloxymethyl-2,4-dimethyl Xazoline, 2,4-methacryloxymethyl-2,4-dimethyloxazoline, vinyldiethylphosphonate, vinyldimethylphosphonate, 2-methylpropenyl acetate, 3- (2-vinyl) -6-methyl-4,5-dihydropyridazinone 2-methyl-5-vinylpyridine, 2-vinylpyridine, 2-vinyl-5-ethylpyridine, 1-benzyl-3-methylene-5-methylpyrrolidone, 2-vinylquinoline, styrene, 2,4,6-trimethylstyrene, α- Methoxystyrene, m-bromostyrene, m-chlorostyrene, m-methylstyrene, p-bromostyrene, p-chlorostyrene, p-cyanostyrene, p-methoxystyrene, p-methylstyrene, α-methylstyrene, p- 1- (2-hydroxybutyl) styrene, p- -(2-hydroxypropyl) styrene, p-2- (2-hydroxypropyl) styrene, N-vinylsuccinimide, 2-methyl-5-vinyltetrazole, 2-phenyl-5- (4'-vinyl) phenyltetrazole, N , N-methyl-vinyltoluenesulfonamide, N-vinyl-N'-ethylurea, vinyl acetate, vinyl benzoate, vinyl butyl ether, vinyl butyrate, vinyl chloroacetate, vinyl dichloroacetate, vinyl dodecyl ether, vinyl ether, vinyl ethyl ether, vinyl Methyl oxalate, vinyl ethyl sulfide, vinyl formate, vinyl isobutyl ether, vinyl isobutyl sulfide, vinyl isopropyl ketone, vinyl laurate, vinyl m-cresyl ether , Vinyl methyl sulfide, vinyl methyl sulfoxide, vinyl-o-cresyl ether, vinyl octadecyl ether, vinyl octyl ether, vinyl p-cresyl ether, vinyl phenyl ether, vinyl phenyl sulfide, vinyl propionate, vinyl stearate, vinyl tert-butyl sulfide, vinyl thiol acetate, vinyl-4-chlorocyclohexyl ketone, vinyl-2-chloroethyl ether, vinyl-tris (trimethoxysiloxy) silane, p-vinylbenzylethylcarbinol, p-vinylbenzylmethylcarbinol, vinylenecarbo Nate, vinyl isocyanate, N, N-diethylacrylamide and the like.

 Among these, N-vinylcaprolactam, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N-vinyl-2-pyrrolidone, N-vinylformaldehyde, etc. are excellent in viscosity, volatility, etc. Preferably used.

(B) Photopolymerization initiator A photopolymerization initiator is used in the composition of the present invention. The photoinitiator used for this invention contains 0.1-10 mass% by mass ratio in the whole composition, Preferably it is 0.2-8.5 mass%, More preferably, it is 0.3. -7.0 mass%. However, when using together with 2 or more types of photoinitiators, those total amount becomes the said range.
Therefore, the photocurable composition for optical nanoimprint lithography of the present invention is photocurable by radical polymerization.
If the ratio of the photopolymerization initiator is less than 0.1% by mass, the sensitivity (fast curability), resolution, line edge roughness, and coating film strength are inferior. On the other hand, if the photopolymerization initiator exceeds 15% by mass, the light transmittance, colorability, handleability and the like deteriorate, which is not preferable. So far, various addition amounts of preferred photopolymerization initiators have been studied for ink-jet compositions and dye- and / or pigment-containing liquid crystal display color filter compositions. There is no report about the preferable addition amount of the photopolymerization initiator for the curable composition. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the composition of the present invention, the dye and / or pigment is not an essential component, and the optimum range of the photopolymerization initiator is different from that in the field of an ink jet composition or a liquid crystal display color filter composition. There is.

  The photopolymerization initiator used in the present invention is formulated with an activity with respect to the wavelength of the light source to be used, and generates appropriate active species according to the difference in the reaction format (for example, radical polymerization or cationic polymerization). Use things. Moreover, only one type of photopolymerization initiator may be used, or two or more types may be used.

As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. Examples of these include Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure (available from Ciba). (Registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane- 1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholinop Lopan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 184 (1-hydroxy-cyclohexylphenyl ketone), 2-hydroxy-2-methyl-1-phenyl -1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), Darocur® 1173 (2-hydroxy-2-methyl- -Phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3) -Yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) available from BASF, Lucirin TPO-L (2,4,6-trimethylbenzoylphenylethoxy) Phosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, N-1414 Asahi available from ESACUR Nippon Scibel Hegner Adekaoptomer (registered trademark) N-1414 (carbazole phenone), Adekaoptomer (registered trademark) N-1717 (acridine), Adekaoptomer (registered trademark) N-1606 (triazine) System), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), manufactured by Sanwa Chemical, manufactured by Sanwa Chemical TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), MP-triazine manufactured by Sanwa Chemical (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-113 (2- [2- (3,4-dimethoxy) manufactured by Midori Chemical Cyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3,4-dimethoxyphenyl) -4,6-bis (trichloromethyl) manufactured by Midori Chemical ) -1,3,5-triazine), benzophenone, 4,4′-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2 -Chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4 ' -Jimee Xibenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone, methyl o-benzoylbenzoate, 2-benzoyl Naphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1,2′-biimidazole, 2,2-bis (o-chlorophene) Nyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl Benzoate, butoxyethyl-4- (dimethylamino) benzoate, p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3 Examples include 4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine.
In the composition of the present invention, in particular, a trihalomethyl group-containing compound such as 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, Irgacure® 184 (1 -Hydroxy-cyclohexyl ruphenyl-ketone), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO-L (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide) and the like are preferable.

(C) Surfactant The composition of the present invention contains a surfactant. Examples of the surfactant include nonionic surfactants, fluorine surfactants, silicone surfactants, and fluorine / silicone surfactants, and two or more of these may be used in combination.
In the composition of the present invention, the surfactant is contained in a total amount of 0.0005 to 5% by mass. In the composition of the present invention, the surfactant is preferably contained in the range of 0.001 to 2% by mass, and more preferably in the range of 0.05 to 1% by mass.
If the surfactant content is less than 0.0005% by weight, the effect of coating uniformity is insufficient. On the other hand, if it exceeds 5.0% by weight, mold transfer characteristics are deteriorated, which is not preferable.

Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
In the present invention, by using at least one of a nonionic surfactant, a fluorine surfactant, a silicone surfactant, and a fluorine / silicone surfactant, a more preferable photocurable composition for photo-nanoimprint lithography, can do. For example, the photocurable composition for optical nanoimprint lithography of the present invention is applied to a silicon wafer for semiconductor device production, a glass square substrate for liquid crystal device production, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, and a tantalum alloy film. Various types of films such as silicon nitride film, amorphous silicone film, tin oxide-doped indium oxide (ITO) film, tin oxide film, etc. The purpose is to solve the problem of coating defects such as uneven drying), and the fluidity of the composition into the cavity of the mold recess is improved, the releasability between the mold and the resist is improved, and the adhesion between the resist and the substrate is improved. And the viscosity of the composition of the present invention can be lowered. In particular, in the composition of the present invention, by adding a surfactant, coating uniformity can be greatly improved, and in coating using a spin coater or slit scan coater, good coating suitability can be obtained regardless of the substrate size. It is done.

  Examples of nonionic fluorosurfactants used in the present invention include trade names Florard FC-430 and FC-431 (Sumitomo 3M), trade names Surflon "S-382" (Asahi Glass), EFTOP "EF" -122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 "(manufactured by Tochem Products), trade names PF-636, PF-6320, PF-656, PF-6520 (any OMNOVA), product names aftergent FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), product names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), product Name megafuak 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.) Examples of silicon-based surfactants include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Paintad 31 (manufactured by Dainippon Ink & Chemicals), and KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned.

 Examples of fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.). Manufactured), and trade names Megafuk R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

  Examples of commercially available nonionic surfactants include polyoxy such as D-3110, D-3120, D-3412, D-3440, D-3510, and D-3605 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene alkyl ethers such as ethylene alkylamine, D-1305, D-1315, D-1405, D-1420, D-1504, D-1508, and D-1518 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene monofatty acid esters such as D-2112-A, D-2112-C and D-2123-C of the Pionein series manufactured by Takemoto Yushi Co., Ltd. D- of the Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene difatty acid esters such as 2405-A, D-2410-D, D-2110-D, etc., manufactured by Takemoto Yushi Co., Ltd. Onin series D-406, D-410, D-414, D-418 and other polyoxyethylene alkyl phenyl ethers, Nissin Chemical Industry's Surfinol series 104S, 420, 440, 465, 485, etc. And polystyryl phenyl ethers such as Pionein series D6112W manufactured by Takemoto Yushi Co., Ltd. Moreover, the reactive surfactant which has a polymerizable unsaturated group can also be used together with the surfactant used by this invention. For example, allyloxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PKE series), nonylphenoxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNE series), nonylphenoxy polypropylene glycol monometa. Acrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNP series), Nonylphenoxy poly (ethylene glycol-propylene glycol) monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNEP-600), Aqualon RN-10, RN- 20, RN-30, RN-50, RN-2025, HS-05, HS-10, HS-20 (Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

(D) Sensitizer It is preferable to add a sensitizer to the photocurable composition for optical nanoimprint lithography of the present invention. By adding a sensitizer, the wavelength in the UV region can be adjusted.
Typical sensitizers that can be preferably used in the present invention include those disclosed in Crivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], and specifically, pyrene. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

  The content of the sensitizer in the composition of the present invention is 0 to 5.0% by mass, preferably 0.1 to 5.0% by mass, and 0.2 to 2.0% by mass. More preferably. By setting the content of the sensitizer to 0.1% by mass or more, the effect of the sensitizer can be expressed more effectively. On the other hand, when the content of the sensitizer exceeds 5% by mass, poor dissolution or deterioration of liquid stability may occur.

(E) Adhesion promoter In the present invention, an adhesion promoter can be appropriately added for the purpose of improving the adhesion to the substrate. Specific examples include silicone compounds such as (meth) acryloyl-modified silicone, vinyl-modified silicone, and silicone hexaacrylate, commercially available silicone acrylate (trade name: Desolite Z7500 (manufactured by JSR), SHC200, SHC900, UVHC85XX series, UVHC11XX series (all manufactured by GE Toshiba Silicone), dimethylsiloxane monomethacrylate (FM0711, FM0721, FM0725 (all manufactured by Chisso Corporation)), dimethylsiloxane dimethacrylate (DMS-V22 (manufactured by Chisso Corporation)), Ebercryl-1360 (manufactured by Daicel Chemical Industries) can also be used. Similarly, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl (meth) acrylate, (perfluorohexyl) ethyl (meth) A compound having a fluorine atom such as acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, or the like can also be used. Also, ethyl (meth) acrylate acid phosphate, 3-chloro-2-acid phosphoroxypropyl (meth) acrylate, polyoxyethylene glycol (meth) acrylate acid phosphate, 2-hydroxyethyl (meth) acrylate acid phosphate, 2- (meta ) Phosphoric acid-containing (meth) acrylic monomers such as acryloyloxyethyl caproate acid phosphate can also be used in the present invention.

Furthermore, an isocyanate-based (meth) acrylate compound can also be included in the photocurable composition for optical nanoimprint lithography of the present invention. Specific examples of the isocyanate-based (meth) acrylate compound include isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate n-propyl (meth) acrylate, isocyanate isopropyl (meth) acrylate, and isocyanate n-butyl (meth) ) Acrylate, isocyanate isobutyl (meth) acrylate, isocyanate sec-butyl (meth) acrylate, isocyanate alkyl (meth) acrylate such as isocyanate tert-butyl (meth) acrylate, (meth) acryloylmethyl isocyanate, (meth) acryloylethyl isocyanate, (Meth) acryloyl n-propyl isocyanate, (meth) acryloyl isopropyl isocyanate, (me ) Acryloyl n- butyl isocyanate, (meth) acryloyl Louis Seo-butyl isocyanate, (meth) acryloyl sec- butyl isocyanate, (meth) acryloyl tert- butyl isocyanate (meth) acryloyl alkyl isocyanate are exemplified.
Also, phosphoric acid-containing di (meth) acrylic monomers such as EO-modified phosphoric acid di (meth) acrylate can be used in the present invention.

 In the composition of the present invention, the addition amount of the adhesion promoter is 0 to 5% by mass, and more preferably 0.05 to 3.0% by mass. If it exceeds 5% by mass, the adhesion to the substrate becomes too strong, and a problem that the remaining film tends to remain may occur, or the liquid stability may deteriorate.

  When using one having two or more photopolymerizable functional groups in one molecule, a large amount of photopolymerizable functional groups are introduced into the composition of the present invention as described above. The crosslinking density becomes very large, and the effect of improving various physical properties after curing is high. Among the various physical properties after curing, heat resistance and durability (abrasion resistance, chemical resistance, water resistance) are improved by increasing the crosslink density, and even when exposed to high heat, friction or solvent, Deformation, disappearance, and damage are less likely to occur.

  In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer or polymer having a molecular weight higher than that of the polyfunctional monomer can be blended without departing from the spirit of the present invention. Polyfunctional oligomers having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, polyepoxy acrylate, oligomers having a bulky structure such as phosphazene skeleton, adamantane skeleton, cardo skeleton, norbornene skeleton, or Examples thereof include polymers.

Further, in the composition of the present invention, a compound having a dioxolane skeleton (meth) acrylate or an oxirane ring can be blended without departing from the gist of the present invention for the purpose of adjusting the viscosity and increasing the strength of the cured film.
Specific examples of the (meth) acrylate having a dioxolane skeleton include 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3. -Dioxolane, 4-acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-methacryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl -2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, and the like. .
Among them, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane and the like can be mentioned.

  Examples of the compound having an oxirane ring include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycol, and polyglycidyls of aromatic polyols. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Various polyol compounds can be further blended in the photocurable composition for photonanoimprint lithography of the present invention as required. Examples of polyols that can be suitably applied include ethylene glycol, glycerin, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, spiroglycol, various polyether polyols, various polyester polyols, and various caprolactone polyols. it can. The addition of such various polyols can improve the curing rate. Among these polyols, the hydroxyl group equivalent is small, and is excellent in compatibility with the epoxy compound and / or oxetane compound, which are the main reaction components of the photocationic curable composition, and the viscosity increase by addition is small, so ethylene glycol and trimethylolpropane Can be suitably applied in the present invention.

  The polyol preferably has 2 or more hydroxyl groups in one molecule, more preferably 2 to 6 hydroxyl groups in one molecule. When a polyol having two or more hydroxyl groups in one molecule is used, a sufficient effect of improving photocurability can be obtained, and mechanical properties of the resulting photocurable composition for photo-nanoimprint lithography are unlikely to deteriorate. Tend. On the other hand, the number of hydroxyl groups in one molecule of polyol is preferably 6 or less from the viewpoint of moisture resistance.

  Examples of such polyols include polyether polyols, polycaprolactone polyols, polyester polyols obtained by modification with a polyester composed of a dibasic acid and a diol.

  Of the above polyols, polyether polyols are preferred. For example, a polyether obtained by modifying a trihydric or higher polyhydric alcohol such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, and quadrol with a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Mention may be made of polyols. Specifically, EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, EO-modified glycerin, PO-modified glycerin, tetrahydrofuran-modified glycerin, EO-modified pentaerythritol, PO-modified pentaerythritol, tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified sucrose, EO-modified quadrole, polyoxyethylene diol, polyoxypropylene diol, polyoxytetramethylene diol, polyoxybutylene diol, polyoxybutylene-oxy Examples include ethylene copolymer diol. Of these, EO-modified trimethylolpropane, PO-modified trimethylolpropane, PO-modified glycerin, and PO-modified sorbitol are preferable.

  Commercially available polyether polyols include Sannix TP-400, Sannix GP-600, Sannix GP-1000, Sannix SP-750, Sannix GP-250, Sannix GP-400, Sannix GP-600 (Sanyo Kasei Co., Ltd.), TMP-3Glycol, PNT-4 Glycol, EDA-P-4, EDA-P-8 (Nippon Emulsifier Co., Ltd.), G-300, G-400, Examples thereof include G-700, T-400, EDP-450, SP-600, and SC-800 (manufactured by Asahi Denka Kogyo Co., Ltd.).

  Specific examples of the polycaprolactone polyol include caprolactone-modified trimethylolpropane, caprolactone-modified glycerin, caprolactone-modified pentaerythritol, and caprolactone-modified sorbitol.

  Examples of commercially available products of polycaprolactone polyol include TONE 0301, TONE 0305, and TONE 0310 (above, Union Carbide), and examples of polyester polyols that are available are Plaxel 303, Plaxel 305, Plaxel 308 (above, Daicel Chemical Industries, Ltd.), etc. Can be mentioned.

  Said polyol can be used individually by 1 type or in combination of 2 or more types. The molecular weight of the polyol used is preferably 100 to 50,000, more preferably 160 to 20,000. By using a polyol having a molecular weight in the above range, a photocurable composition for photo-nanoimprint lithography having better shape stability and physical property stability can be obtained, and the resulting photocurable composition for photo-nanoimprint lithography can be obtained. It tends to be possible to prevent the viscosity of the resin from becoming excessively high and the elastic modulus from decreasing.

  The photocurable composition for optical nanoimprint lithography of the present invention preferably has a water content of 2.0% by mass or less, more preferably 1.5% by mass, and even more preferably 1.0% by mass or less at the time of preparation. is there. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the photocurable composition for optical nanoimprint lithography of the present invention can be made more stable.

  Moreover, it is preferable that content of the organic solvent is 3 mass% or less in the whole composition in the photocurable composition for optical nanoimprint lithography of this invention. That is, since the photocurable composition for photo-nanoimprint lithography of the present invention preferably contains a specific monofunctional and / or bifunctional monomer as a reactive diluent, it is a component of the photocurable composition for photo-nanoimprint lithography of the present invention. It is not always necessary to contain an organic solvent for dissolving the. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the photocurable composition for optical nanoimprint lithography of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not contained. As described above, the photocurable composition for optical nanoimprint lithography of the present invention does not necessarily contain an organic solvent, but the reactive diluent does not dissolve a compound that does not dissolve in the photocurable composition for optical nanoimprint lithography of the present invention. When dissolving as a composition or when finely adjusting the viscosity, it can be optionally added. The organic solvent that can be preferably used in the photocurable composition for photonanoimprint lithography of the present invention is a solvent that is generally used in a photocurable composition for photonanoimprint lithography or a photoresist. Any compound may be used as long as it dissolves and uniformly disperses the compound to be used, and it is not particularly limited as long as it does not react with these components.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as rumethyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2- Ketones such as heptanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-methylbutane Acid methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, lactic acid And esters such as lactic esters chill and the like.
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These may be used alone or in combination of two or more.
Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable.

  The light for initiating polymerization of the present invention includes not only light having a wavelength in the region of ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light, or electromagnetic waves, but also radiation. For example, microwave, electron beam, EUV, and X-ray are included. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, a 172 nm excimer laser, or the like can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light). The exposure can be multiple exposure, and after the pattern is formed for the purpose of increasing the film strength and etching resistance, the entire surface can be further exposed.

  The photopolymerization initiator used in the present invention needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization / exposure. Those that do not generate gas are less likely to contaminate the mold, reduce the frequency of cleaning of the mold, and the photocurable composition for optical nanoimprint lithography is less likely to be deformed in the mold, so that the transfer pattern accuracy is less likely to deteriorate. preferable.

  The photocurable composition for optical nanoimprint lithography of the present invention includes a release agent, a silane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, and an anti-aging agent as necessary in addition to the above components. Agent, plasticizer, adhesion promoter, thermal polymerization initiator, colorant, inorganic particles, elastomer particles, antioxidant, photoacid growth agent, photobase generator, basic compound, flow regulator, antifoaming agent, dispersion An agent or the like may be added.

  For the purpose of further improving the releasability, a release agent can be arbitrarily blended in the photocurable composition for optical nanoimprint lithography of the present invention. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the photocurable composition for photo-nanoimprint lithography of the present invention to be peeled cleanly without causing the resin layer to become rough or plate-cut. Examples of the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used. Moreover, these mold release agents can be adhered to the mold.

  Silicone release agents have particularly good release properties from the mold when combined with the above-mentioned photocurable resin used in the present invention, and the phenomenon of taking a plate hardly occurs. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, and examples thereof include unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicic acid, and silicone acrylic resin.

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
Two or more of the above-described modification methods can be performed on one polysiloxane molecule.

  The modified silicone oil is preferably compatible with the composition components. In particular, when using a reactive silicone oil that is reactive with other coating-forming components blended as necessary in the composition, the photocurable composition for optical nanoimprint lithography of the present invention is cured. Since it is fixed in the cured film by chemical bonding, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone or vinyl-modified silicone, it crosslinks with the photocurable composition for photonanoimprint lithography of the present invention. Excellent characteristics.

Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeding out on the surface, and excellent adhesion to metal deposition and overcoat layer This is preferable.
The said mold release agent can be added only in 1 type or in combination of 2 or more types.

  When a release agent is added to the photocurable composition for photo-nanoimprint lithography of the present invention, it is preferably blended in a proportion of 0.001 to 10% by mass in the total amount of the composition, 0.01 to 5% by mass It is more preferable to add in the range. When the ratio of the release agent is 0.01% by mass or more, the effect of improving the release property between the mold and the photocurable composition layer for optical nanoimprint lithography is sufficient. On the other hand, if the ratio of the release agent is within the above range of 10% by mass, the problem of surface roughness of the coating film due to repelling during coating of the composition is unlikely to occur, and the substrate itself and adjacent layers in the product, for example, It is preferable in that it hardly inhibits the adhesion of the deposited layer and hardly causes film breakage or the like (film strength becomes too weak) during transfer.

  The photo-curable composition for optical nanoimprint lithography of the present invention is blended with an organic metal coupling agent in order to improve the heat resistance, strength, or adhesion to the metal vapor deposition layer of the surface structure having a fine uneven pattern. May be. In addition, the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction. As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

  Examples of the silane coupling agent used in the photocurable composition for optical nanoimprint lithography of the present invention include vinylsilanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; γ -Acrylic silane such as methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Epoxy silanes such as xylpropylmethyldiethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Aminosilanes such as trimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; and other silane coupling agents such as γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyl Examples include diethoxysilane.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, isop Pirutori (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis. (Ethyl acetoacetate) and the like.

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.

  The said organometallic coupling agent can be arbitrarily mix | blended in the ratio of 0.001-10 mass% in solid content whole quantity of the photocurable composition for optical nanoimprint lithography. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, it tends to be more effective in improving heat resistance, strength, and adhesion with the deposited layer. On the other hand, it is preferable that the ratio of the organometallic coupling agent is 10% by mass or less because the stability of the composition and the deficiency in film formability can be suppressed.

  A polymerization inhibitor may be blended in the photocurable composition for optical nanoimprint lithography of the present invention in order to improve storage stability and the like. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like. The polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the photocurable composition for optical nanoimprint lithography.

  Examples of commercially available antioxidants include Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), Antigene P, 3C, FR, Sumilyzer S (manufactured by Sumitomo Chemical Co., Ltd.), and the like. It is preferable to mix the antioxidant at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  As a commercial item of an ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350 400 (above, manufactured by Sumitomo Chemical Co., Ltd.). It is preferable to mix | blend an ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of the photocurable composition for optical nanoimprint lithography.

  Commercially available light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.) Etc. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  Examples of commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Co., Ltd.). The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  A plasticizer can be added to the photocurable composition for optical nanoimprint lithography of the present invention in order to adjust the adhesion to the substrate, the flexibility of the film, the hardness, and the like. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate, There are di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and the plasticizer can be optionally added at 30% by mass or less in the composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or more is preferable.

  An adhesion promoter may be added to the photocurable composition for optical nanoimprint lithography of the present invention in order to adjust the adhesion to the substrate and the like. Adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10-phenanthroline 2,2'-bipyridine derivatives, benzotriazoles, organic phosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanol Amines and derivatives, benzothiazole derivatives, and the like can be used. The adhesion promoter in the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain the effect.

  When hardening the photocurable composition for photo nanoimprint lithography of this invention, a thermal-polymerization initiator can also be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

  For the purpose of improving the visibility of the coating film, a colorant may be optionally added to the photocurable composition for optical nanoimprint lithography of the present invention. As the colorant, pigments and dyes used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like can be used as long as the object of the present invention is not impaired. As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And metal complex oxides. Organic pigments include CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139,151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, CIPigment Violet 19, 23, 32, 39, CIPigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36 37, CIPigment Brown 25, 28, CIPigment Black 1, 7 and carbon black.

  For the purpose of improving the heat resistance, mechanical strength, tackiness and the like of the coating film, a filler may be added as an optional component to the photocurable composition for optical nanoimprint lithography of the present invention. As the inorganic fine particles, those having an ultra fine particle size are used. Here, “ultrafine particle” means a particle of submicron order, and generally means a particle having a particle size smaller than a particle having a particle size of several μm to several 100 μm, which is generally called “fine particle”. ing. The specific size of the inorganic fine particles used in the present invention varies depending on the use and grade of the optical article to which the photocurable composition for optical nanoimprint lithography is applied, but generally the primary particle size is 1 nm to 300 nm. It is preferable to use the thing of the range. When the primary particle size is 1 nm or more, the moldability, shape maintaining property and releasability of the photocurable composition for optical nanoimprint lithography can be sufficiently improved. On the other hand, if the primary particle size is 300 nm or less, the resin Transparency required for curing the resin can be maintained, which is preferable in terms of transparency.

Specific examples of the inorganic fine particles include metal oxide fine particles such as SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , and Al ₂ O ₃ , among which colloidal dispersion is possible as described above. In addition, it is preferable to select and use a particle having a particle size on the order of submicron, and particularly, it is preferable to use colloidal silica (SiO ₂ ) fine particles.

  The inorganic fine particles are preferably blended in a proportion of 1 to 70% by mass and particularly preferably in a proportion of 1 to 50% by mass in the total solid content of the photocurable composition for optical nanoimprint lithography. By setting the ratio of the inorganic fine particles to 1% by mass or more, the moldability, shape maintaining property and releasability of the photocurable composition for optical nanoimprint lithography of the present invention can be sufficiently improved. When the ratio is 70% by mass or less, it is preferable in terms of strength after exposure and curing and surface hardness.

Moreover, in the photocurable composition for optical nanoimprint lithography of the present invention, elastomer particles may be added as an optional component for the purpose of improving mechanical strength, flexibility and the like.
The elastomer particles that can be added as an optional component to the photocurable composition for photonanoimprint lithography of the present invention preferably have an average particle size of 10 nm to 700 nm, more preferably 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / Particles of elastomer such as polyene copolymer, acrylic rubber, butadiene / (meth) acrylic ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer. Further, core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

  Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resinas Kasei Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.

  These elastomer particles can be used alone or in combination of two or more. The content ratio of the elastomer component in the photocurable composition for optical nanoimprint lithography of the present invention is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

The photocurable composition for optical nanoimprint lithography of the present invention can contain a known antioxidant. The antioxidant suppresses fading caused by light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). Such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.

  A basic compound may be optionally added to the photocurable composition for optical nanoimprint lithography of the present invention for the purpose of suppressing curing shrinkage and improving thermal stability. Examples of the basic compound include amines and nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like. Among these, amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, tributylamine, and the like. Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.

  Next, the formation method of the pattern (especially fine uneven | corrugated pattern) using the photocurable composition for optical nanoimprint lithography of this invention is demonstrated. In the present invention, a curable composition is applied and cured to form a pattern. Specifically, a photocurable composition for photo-nanoimprint lithography is applied on a substrate or a support by applying at least a pattern forming layer comprising the photocurable composition for photo-nanoimprint lithography of the present invention and drying as necessary. A pattern receiver is formed by forming a layer (pattern forming layer) made of the above, a mold is pressed against the surface of the pattern receiving layer of the pattern receiver, a process of transferring the mold pattern is performed, and the fine uneven pattern forming layer is exposed. And let it harden. The optical imprint lithography according to the pattern forming method of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

  As an application of the photocurable composition for photo-nanoimprint lithography of the present invention, a photocurable composition for photonanoimprint lithography of the present invention is applied onto a substrate or a support, and a layer comprising the composition is exposed, A permanent film such as an overcoat layer or an insulating film can be produced by curing and drying (baking) as necessary.

  Hereinafter, a pattern formation method and a pattern transfer method using the photocurable composition for optical nanoimprint lithography of the present invention will be described.

  The photocurable composition for optical nanoimprint lithography of the present invention is generally applied by a well-known coating method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, and extrusion coating. It can be formed by coating by a spin coating method, a slit scanning method or the like. The film thickness of the layer made of the photocurable composition of the present invention is 0.05 μm to 30 μm, although it varies depending on the intended use. Moreover, the photocurable composition for optical nanoimprint lithography of the present invention may be applied multiple times.

  The substrate or support for applying the photocurable composition for optical nanoimprint lithography of the present invention is quartz, glass, optical film, ceramic material, deposited film, magnetic film, reflective film, Ni, Cu, Cr, Fe, etc. Metal substrate, polymer substrate such as paper, SOG, polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass or transparent plastic substrate, conductive substrate such as ITO or metal, insulating substrate There are no particular restrictions on semiconductor production substrates such as silicone, silicon nitride, polysilicon, silicone oxide, and amorphous silicone. The shape of the substrate may be a plate shape or a roll shape.

  Although it does not specifically limit as light which hardens the photocurable composition for optical nanoimprint lithography of this invention, The light or radiation of the wavelength of area | regions, such as high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, and infrared, is mentioned. . As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. The radiation includes, for example, microwaves and EUV. Also, laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention. These lights may be monochromatic light, or may be a plurality of lights having different wavelengths (mixed light).

Next, the molding material that can be used in the present invention will be described. In the optical nanoimprint lithography using the photocurable composition for optical nanoimprint lithography of the present invention, it is necessary to select a light transmissive material for at least one of the mold material and / or the substrate. In photoimprint lithography applied to the present invention, a photocurable composition for photonanoimprint lithography is applied onto a substrate, a light-transmissive mold is pressed, light is irradiated from the back of the mold, and photonimprint lithography is used. The photocurable composition is cured. Alternatively, a photocurable composition for photo nanoimprint lithography can be applied on a light transmissive substrate, pressed against the mold, and irradiated with light from the back side of the mold to cure the photocurable composition for photo nanoimprint lithography. .
The light irradiation may be performed in a state where the mold is attached, or may be performed after the mold is peeled off, but in the present invention, it is preferably performed in a state where the mold is adhered.

As the mold that can be used in the present invention, a mold having a pattern to be transferred is used. The mold can form a pattern according to the desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention.
The light-transmitting mold material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film are exemplified.

  The non-light transmissive mold material used in the case of using the transparent substrate of the present invention is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. There are no particular restrictions. The shape may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.

  The mold used in the present invention may be a mold that has been subjected to a release treatment in order to improve the peelability between the photocurable composition for photo-nanoimprint lithography and the mold. Products that have been treated with a silane coupling agent such as a silicone type or a fluorine type, for example, Daikin Industries, Ltd .: trade name: OPTOOL DSX, Sumitomo 3M: trade name: Novec EGC-1720 Can do.

  When performing photoimprint lithography using the present invention, it is usually preferred that the mold pressure be 10 atmospheres or less. It is preferable that the mold pressure is 10 atm or less because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and the apparatus can be reduced because the pressure is low. The mold pressure is preferably selected in such a range that the uniformity of mold transfer can be ensured within a range where the remaining film of the photocurable composition for photo-nanoimprint lithography on the mold convex portion is reduced.

In the present invention, the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the photocurable composition for photo-nanoimprint lithography and the tackiness of the cured film.
In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, a vacuum state is effective because it is effective in preventing bubble contamination, suppressing the decrease in reactivity due to oxygen contamination, and improving the adhesion between the mold and the photocurable composition for optical nanoimprint lithography. May be irradiated with light. In the present invention, the preferable degree of vacuum is 10 ⁻¹ Pa to normal pressure.

  The photocurable composition for optical nanoimprint lithography of the present invention can be prepared as a solution by mixing the above components and then filtering with a filter having a pore size of 0.05 μm to 5.0 μm, for example. Mixing and dissolution of the photocurable composition for photo-nanoimprint lithography is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. Materials used for filtration can be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.

The case where the photocurable composition for optical nanoimprint lithography of the present invention is applied to an etching resist will be described. The etching step can be performed by a method appropriately selected from known etching methods, and is performed to remove the underlying portion not covered with the resist pattern, thereby obtaining a thin film pattern. Either a treatment with an etching solution (wet etching) or a treatment in which a reactive gas is activated by plasma discharge under reduced pressure (dry etching) is performed.
The etching process may be a batch system in which an appropriate number of sheets are processed together, or a single wafer process in which each sheet is processed.

As etching solutions for performing the wet etching, many etching solutions have been developed and used, typically ferric chloride / hydrochloric acid, hydrochloric acid / nitric acid, hydrobromic acid, and the like. For Cr, mixed solution of cerium ammonium nitrate or cerium nitrate / hydrogen peroxide solution, for Ti, diluted hydrofluoric acid, hydrofluoric acid / nitric acid solution, for Ta, mixed solution of ammonium solution and hydrogen peroxide solution For Mo, hydrogen peroxide solution, a mixture of ammonia water and hydrogen peroxide solution, a mixture solution of phosphoric acid and nitric acid, and MoW and Al, a mixture solution of phosphoric acid and nitric acid, a mixture solution of hydrofluoric acid and nitric acid, phosphoric acid Nitric acid / acetic acid mixed solution For ITO, diluted aqua regia, ferric chloride solution, hydrogen iodide water, SiNx and SiO ₂ are buffered hydrofluoric acid, hydrofluoric acid / ammonium fluoride mixed solution, Si, poly Si Is a mixture of hydrofluoric acid, nitric acid and acetic acid, W is a mixture of ammonia water and hydrogen peroxide, PSG is a mixture of nitric acid and hydrofluoric acid, and BSG is a mixture of hydrofluoric acid and ammonium fluoride. used.
Wet etching may be either a shower method or a dip method, but the etching rate, in-plane uniformity, and wiring width accuracy largely depend on the processing temperature, so conditions are optimal according to the substrate type, application, and line width. It is necessary to make it. Further, when performing the wet etching, it is desirable to perform post-baking in order to prevent undercut due to the penetration of the etching solution. Usually, these post-baking is performed at about 90 ° C. to 140 ° C., but is not necessarily limited thereto.

The dry etching basically uses a parallel plate type dry etching apparatus having a pair of electrodes arranged in parallel in a vacuum apparatus and setting a substrate on one of the electrodes. Reactive ion etching (RIE) mode in which ions are mainly involved and radicals are mainly involved depending on whether the high-frequency power source for generating plasma is connected to the electrode on the side where the substrate is installed or to the opposite electrode The plasma etching (PE) mode is classified.
As an etchant gas used in the dry etching, an etchant gas suitable for each film type is used. Carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine) for a-Si / n ⁺ and s-Si, carbon tetrafluoride for a-SiNx + Oxygen, carbon tetrafluoride + oxygen for a-SiOx, carbon trifluoride + oxygen, carbon tetrafluoride (sulfur hexafluoride) + oxygen for Ta, carbon tetrafluoride for MoTa / MoW For chlorine + oxygen for + oxygen and Cr, boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide and the like for Al. In the dry etching process, the resist structure may be greatly altered by ion bombardment or heat, which also affects the peelability.

  A method for removing the resist used for pattern transfer to the lower substrate after etching will be described. Peeling can be removed with a liquid (wet peeling), or oxidized by plasma discharge of oxygen gas under reduced pressure and removed in a gaseous state (dry peeling / ashing), or oxidized with ozone and UV light. The resist can be removed by several stripping methods such as removing it in a gaseous state (dry stripping / UV ashing). As the stripping solution, an aqueous solution system such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and ozone-dissolved water and an organic solvent system such as a mixture of an amine and dimethyl sulfoxide or N-methylpyrrolidone are generally known. As an example of the latter, a monoethanolamine / dimethyl sulfoxide mixture (mass mixing ratio = 7/3) is well known.

 The resist stripping rate is greatly influenced by temperature, liquid amount, time, pressure, etc., and can be optimized depending on the substrate type and application. In the present invention, it is preferable to immerse the substrate (from several minutes to several tens of minutes) in the temperature range of room temperature to 100 ° C., and rinse with water such as butyl acetate and then rinse with water. From the viewpoint of improving the rinsing properties, particle removability, and corrosion resistance of the stripping solution itself, only water rinsing may be used. A preferable example is a pure water shower for washing and an air knife drying for drying. When the amorphous silicone is exposed on the substrate, an oxide film is formed in the presence of water and air. Therefore, it is preferable to block air. Moreover, you may apply the method of using together ashing (ashing) and peeling by a chemical | medical solution. Examples of ashing include plasma ashing, downflow ashing, ashing using ozone, and UV / ozone ashing. For example, when an Al substrate is processed by dry etching, a chlorine-based gas is generally used, but aluminum chloride, which is a product of chlorine and Al, may corrode Al. In order to prevent these, a stripping solution containing a preservative may be used.

  There is no restriction | limiting in particular as other processes other than the said etching process, peeling process, rinse process, and water washing, It can mention selecting from the process in well-known pattern formation suitably. For example, a hardening process process etc. are mentioned. These may be used alone or in combination of two or more. There is no restriction | limiting in particular as a hardening process, Although it can select suitably according to the objective, For example, a whole surface heat processing, a whole surface exposure process, etc. are mentioned suitably.

 Examples of the method for the entire surface heat treatment include a method for heating the formed pattern. By heating the entire surface, the film strength on the surface of the pattern is increased. As heating temperature in whole surface heating, 80-200 degreeC is preferable and 90-180 degreeC is more preferable. When the heating temperature is 80 ° C. or higher, the film strength due to the heat treatment tends to be further improved. By setting the heating temperature to 200 ° C. or lower, decomposition of components in the photocurable composition for optical nanoimprint lithography occurs. The tendency of the film quality to become weak and brittle can be more effectively suppressed. There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned. Moreover, when using a hot plate, in order to heat uniformly, it is desirable to carry out by lifting the substrate on which the pattern is formed from the plate.

 Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed pattern. The entire surface exposure accelerates the curing in the composition forming the photosensitive layer and the surface of the pattern is cured, so that the etching resistance can be increased. There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Viscosity measurement>
The viscosity was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotational speed during the measurement is 100 rpm for 0.5 mPa · s to less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for less than 30 mPa · s for 10 mPa · s, and 60 mPa · s for 30 mPa · s to 60 mPa · s Less than 10 rpm, 60 mPa · s or more and less than 120 mPa · s was 5 rpm, and 120 mPa · s or more was 1 rpm or 0.5 rpm, respectively.

<Measurement of photocuring speed>
Photocurability is measured using a high-pressure mercury lamp as the light source, and the change in monomer absorption at 810 cm ⁻¹ is measured using a Fourier transform infrared spectrometer (FT-IR) to determine the curing reaction rate (monomer consumption rate) in real time. I went there. A represents the case where the curing reaction rate is 1.0 / second or more, and B represents the case where the curing reaction rate is less than 1.0 / second.

<Pattern formability>
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold. B: There is a portion that is partially different from the pattern shape of the original plate that is the basis of the pattern shape of the mold (the range of the original pattern is less than 20%). C: The pattern pattern of the mold is clearly different from the original pattern, or the film thickness of the pattern is 20% or more different from the original pattern.

<Adhesion to mold>
The adhesion to the mold is determined by repeating the photo imprinting 5 times, and when the mold is peeled off after the 5th photocuring, whether the cured film or uncured material remains in the mold, and visually check the mold shape change. And were observed with an optical microscope and evaluated as follows.
A: No residue, no change in shape of the mold B: A slight amount of residue is observed, but no change in the shape of the mold C: There is a residue, and further deformation of the mold such as warpage occurs

<Spin coating suitability>
Applicability (I)
The photocurable composition for optical nanoimprint lithography of the present invention is spin-coated so as to have a thickness of 6.0 μm on a 4-inch 0.7 mm-thick glass substrate on which an aluminum (Al) film having a thickness of 4000 Å is formed. After the coating, the glass substrate was allowed to stand for 1 minute, surface observation was performed, and evaluation was performed as follows.
A: No repelling and coating streaks (striation) observed B: Some coating streaks observed C: Repelling or coating streaks were observed strongly

<Slit application suitability>
Applicability (II)
Using a slit coater resist coating apparatus (a head coater system manufactured by Hirata Kiko Co., Ltd.) for coating a large substrate, the photocurable composition for optical nanoimprint lithography of the present invention is used to form an aluminum (Al) film having a thickness of 4000 angstroms. It is applied onto a 4 inch 0.7 mm thick glass substrate (550 mm × 650 mm) formed to form a resist film with a film thickness of 2.0 μm, and the presence or absence of streaky irregularities appearing vertically and horizontally is observed. It was evaluated as follows.
A: Streaky unevenness was not observed B: Streaky unevenness was observed to be weak C: Streaky unevenness was observed strongly or repellency was observed on the resist film

<Etching property>
The photocurable composition for optical nanoimprint lithography of the present invention is formed in a pattern on the aluminum (Al) formed on the glass substrate, and after curing, the aluminum thin film is etched with a phosphoric nitrate etchant to visually observe a 10 μm line / space. And were observed with a microscope and evaluated as follows.
A: An aluminum line having a line width of 10 ± 2.0 μm was obtained. B: Variation in line width of the line became a line exceeding ± 2.0 μm. C: A defective portion of the line existed or the space between the lines was Connected

Example 1
(A) As a polymerizable compound, 38.4 g of N-vinylpyrrolidone monomer, 38.4 g of tripropylene glycol diacrylate monomer, 19.2 g of propylene oxide-modified trimethylolpropane triacrylate, (b) 2, 2 as a photopolymerization initiator, 4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) (P-1) 4.00 g, (c) Megafac R08 (manufactured by Dainippon Ink & Chemicals) as surfactant. 1 g was precisely weighed and mixed at room temperature for 2 hours to obtain a uniform solution. The viscosity of the composition was 7 mPa · s.

This prepared composition was spin-coated on a 4-inch 0.7 mm thick glass substrate on which an aluminum (Al) film having a thickness of 4000 angstroms was formed so as to have a thickness of 6.0 μm. The spin-coated coated base film is set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power: 2000 mW / cm ² ) as a light source. / 100 mJ / cm ² from the back surface of a mold having a space pattern and a groove depth of 5.0 μm made of polydimethylsiloxane (made by Toray Dow Corning, SILPOT184 cured at 80 ° C. for 60 minutes) After exposure, the mold was released to obtain a resist pattern. Subsequently, the aluminum (Al) portion not covered with the resist was removed with a phosphoric nitrate etchant to form an aluminum (Al) electrode pattern. Further, the resist was stripped by dipping at 80 ° C. for 3 minutes using a mixed stripping solution of monoethanolamine / dimethyl sulfoxide. The results are shown in Table 2. From the results of Table 2, the composition of the present invention is satisfactory in all of photocurability, adhesion, releasability, remaining film properties, pattern shape, coatability (spin coatability, slit coatability), and etchability. It was possible.

Examples 2-9
In Example 1, it carried out similarly except having changed the mixing | blending of each main component as described in Table 1 below. The results are shown in Table 2. From the results shown in Table 2, the composition of the present invention was satisfactory in all of photocurability, pattern forming property, adhesion to a mold, spin coating suitability, slit coating suitability, and etching property.

Comparative Example 1 and Comparative Example 2
In Example 1, it carried out similarly except having changed the mixing | blending of each main component as described in Table 3 below. The polymerizable compound (e value is positive) used in this comparative example is described in JP-A-7-70472. The results are shown in Table 4.

Comparative Example 3 and Comparative Example 4
In Example 1, it carried out similarly except having changed the mixing | blending of each main component as described in Table 3 below. The polymerizable compound (e value is positive) used in this comparative example is described in JP-A-4-149280. The results are shown in Table 4.
Comparative Example 5
In Example 1, it carried out similarly except having changed the mixing | blending of each main component as described in Table 3 below. The polymerizable compound (e value is positive) used in this comparative example is described in JP-A-7-62043. The results are shown in Table 4.

Comparative Example 6 and Comparative Example 7
In Example 1, it carried out similarly except having changed the mixing | blending of each main component as described in Table 3 below. The polymerizable compound (e value is positive) used in this comparative example is described in JP-A No. 2001-93192. The results are shown in Table 4.

Comparative Example 8
In Example 1, it carried out similarly except having changed the mixing | blending of each main component as described in Table 3 below. The results are shown in Table 4.

Comparative Example 9
Regarding the examples using polymerizable compounds having different signs of e value described in Non-Patent Document 14, the composition of each component is shown in Table 3 below, and the results are shown in Table 4.

  As apparent from the above, when only a polymerizable compound having a positive e value or only a polymerizable compound having a negative e value was used, deterioration of adhesion to the mold was observed.

 The photocurable composition for optical nanoimprint lithography of the present invention is a semiconductor integrated circuit, a flat screen, a micro electro mechanical system (MEMS), a sensor element, an optical disk, a magnetic recording medium such as a high-density memory disk, a diffraction grating relief hologram, etc. Optical components, nanodevices, optical devices, optical films and polarizing elements for the production of flat panel displays, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, micro Use as an optical nanoimprint resist composition for the formation of fine patterns in the production of lens arrays, immunoassay chips, DNA separation chips, microreactors, nanobiodevices, optical waveguides, optical filters, photonic liquid crystals, etc. It can be.

Claims (4)

(A) A total of polymerizable compounds containing 10% by mass or more of polymerizable compounds having a positive polarity factor (e value) in the Qe scheme and 10% by mass or more of polymerizable compounds having a negative e value are 88 to 99% by mass,
(B) 0.1-10% by mass of a photopolymerization initiator,
(C) 0.0005 to 5.0 mass% of at least one surfactant,
A photocurable composition for optical nanoimprint lithography. The photocurable composition for optical nanoimprint lithography according to claim 1, wherein the viscosity at 25 ° C. is 3 to 18 mPa · s. It is a formation method of a pattern including the process of apply | coating and hardening the photocurable composition for optical nanoimprint lithography of Claim 1 or 2, Comprising: The film thickness of the composition after application | coating is 0.5-40 micrometers. There is provided a pattern forming method in optical nanoimprint lithography. The process of apply | coating the photocurable composition for optical nanoimprint lithography of Claim 1 or 2, the process of pressurizing the light-transmitting mold to the resist layer on a board | substrate, and deform | transforming the said photocurable composition for optical nanoimprint lithography The resist pattern formation method including the process of irradiating light from the mold back surface or the substrate back surface, curing the coating film, and forming a resist pattern that fits into a desired pattern.