KR20090131648A - Curable composition for nanoimprint and patterning method - Google Patents

Abstract

PURPOSE: A curing composition for nanoimprint, and a method for forming a resist pattern by using the composition are provided to form a micropattern, to improve the adhesion to a substrate after photocuring process and the release of a resist. CONSTITUTION: A curing composition for nanoimprint comprises 87 mass % or more of a monofunctional polymerizable compound, and a photopolymerization initiator. A method for forming a resist pattern comprises the steps of coating the curing composition for nanoimprint; pressing a light permeable mold on the resist layer on a substrate to modify the curing composition for nanoimprint; and irradiating light from the backside of the mold or the substrate to cure the coat, and fitting it to the desired pattern.

Description

Curable composition for nanoimprint, pattern formation method {CURABLE COMPOSITION FOR NANOIMPRINT AND PATTERNING METHOD}

The present invention relates to a curable composition for nanoimprint. More specifically, semiconductor integrated circuits, flat screens, microelectromechanical systems (MEMS), sensor elements, optical disks, magnetic recording media such as high density memory disks, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, flats Optical film or polarizing element for panel display, thin film transistor of liquid crystal display, organic transistor, color filter, overcoat layer, pillar material, rib material for liquid crystal alignment, micro lens array, immunoassay chip, DNA separation chip, micro reactor The present invention relates to a curable composition for imprint for forming a fine pattern using light irradiation used in the production of nano bio devices, optical waveguides, optical filters, photonic liquid crystals, and the like. Moreover, this invention relates also to the pattern formation method using such a curable composition for nanoimprints.

The nanoimprint method develops an embossing technique that is well known in optical disc fabrication, presses a die body (commonly called a mold, a stamper, and a template) in which a pattern of irregularities is formed into a resist, and mechanically deforms the micro pattern by precisely deforming it. It is a technique to make a transfer. Once a mold has been produced, since it is economical and has a small amount of harmful wastes and discharges because it is possible to simply and repeatedly shape a microstructure such as a nanostructure, application to various fields is expected in recent years.

The nanoimprint method includes a thermal imprint method using a thermoplastic resin as a work material (see, for example, Non Patent Literature 1), and an optical imprint method using a photocurable composition (see, for example, Non Patent Literature 2). Two techniques are proposed. In the case of the thermal nanoimprinting method, a microstructure is transferred to a resin on a substrate by pressing a mold onto a polymer resin heated to a glass transition temperature or higher, and releasing the mold after cooling. Since this method is applicable also to various resin materials and glass materials, application to various aspects is anticipated. For example, Patent Documents 1 and 2 disclose methods of nanoimprint in which nanopatterns are inexpensively formed using thermoplastic resins.

On the other hand, in the optical nanoimprint method in which light is irradiated through a transparent mold or a transparent substrate to photocure the curable composition for optical nanoimprint, imprinting at room temperature is possible without heating the material to be transferred when the mold is pressed. . Recently, new developments have been reported, such as the nanocasting method combining these advantages and the reversal imprint method for producing a three-dimensional layered structure.

In such a nanoimprint method, the following application techniques are proposed.

As a 1st technique, it is a case where the shape (pattern) itself has a function, and is applicable as an element part or structural member of various nanotechnology. Examples include various micro-nano optical elements, high-density recording media, optical films, structural members in flat panel displays, and the like. The second technique is to construct a laminated structure by simultaneous integral molding of a micro structure and a nano structure or by simple interlayer positioning, and to apply it to the production of a micro-total analysis system (micro-TAS) or a biochip. As a 3rd technique, it is used for the use which uses the formed pattern as a mask and processes a board | substrate by methods, such as an etching. In such a technique, high precision positioning and high integration can be applied to fabrication of high density semiconductor integrated circuits, liquid crystal display transistors, and magnetic material processing of next-generation hard disks called patterned media, instead of conventional lithography techniques. . In addition to the above-described techniques, the approach to the practical use of the nanoimprint method for these applications has been actively promoted in recent years.

As an application example of the nanoimprint method, first, an application example for fabricating a high density semiconductor integrated circuit will be described. In recent years, semiconductor integrated circuits have progressed in miniaturization and integration, and high precision of photolithography apparatuses has been advanced as a pattern transfer technique for realizing the microfabrication. However, it is difficult to satisfy three kinds of fine pattern resolution, device cost, and throughput with respect to further refinement request. On the other hand, nanoimprint lithography (photo nanoimprint method) has been proposed as a technique for performing fine pattern formation at low cost. For example, Patent Documents 1 and 3 below disclose a nanoimprint technique for forming a fine structure of 25 nm or less by transfer using a silicon wafer as a stamper. In this application, pattern formation at the tens of nm level and high etching resistance for functioning as a mask during substrate processing are required.

The application of nano imprint to next generation hard disk drive (HDD) is described. HDD has a high performance of the head and high performance of the media, and has a history of large capacity and miniaturization. HDDs have achieved large capacities by increasing the surface recording density in terms of improving media performance. However, when increasing the recording density, so-called magnetic field expansion from the magnetic head side surface becomes a problem. Since the magnification of the magnetic field does not decrease below a certain value even if the head is made small, a phenomenon called side light occurs as a result. When side writes occur, writing to adjacent tracks occurs at the time of recording, and data already recorded is erased. In addition, due to the magnetic field expansion, a phenomenon such as reading an extra signal from an adjacent track during reproduction occurs. To solve such a problem, techniques such as discrete track media and bit patterned media have been proposed which are solved by filling between tracks with nonmagnetic material and physically and magnetically separating them. Application of nanoimprint has been proposed as a method of forming a magnetic or nonmagnetic pattern in producing these media. Also in this application, pattern formation of several tens of nm level and high etching tolerance for functioning as a mask at the time of processing a board | substrate are calculated | required.

Next, application examples of the nanoimprint method to flat displays such as liquid crystal displays (LCDs) and plasma displays (PDPs) will be described.

With the trend of larger and higher resolution LCD and PDP substrates, the photo nanoimprint method has recently attracted attention as an inexpensive lithography instead of the conventional photolithography method used in the manufacture of a thin film transistor (TFT) or an electrode plate. . Therefore, the development of the photocurable resist which replaces the etching photoresist used by the conventional photolithography method is needed.

Moreover, as structural members, such as LCD, the application of the optical nanoimprint method to the transparent protective film material of patent documents 4 and 5, the spacer, etc. which are described in patent document 5 is also being examined. Since the resist for such a structural member is finally left in the display unlike the etching resist, it may be referred to as "permanent resist" or "permanent film".

In addition, a spacer defining a cell gap in a liquid crystal display is also a permanent film, and in conventional photolithography, a photocurable composition composed of a resin, a photopolymerizable monomer and an initiator has generally been widely used (for example, See Patent Document 6). The spacer is generally coated with a photocurable composition after forming a color filter on the color filter substrate or after forming the protective film for the color filter, and forming a pattern having a size of about 10 μm to 20 μm by photolithography. It forms by heat-hardening by low post baking.

In addition, micro electromechanical systems (MEMS), sensor elements, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, optical films and polarizing elements for flat panel displays, thin film transistors of liquid crystal displays, organic transistors, Color filter, overcoat layer, pillar material, rib material for liquid crystal alignment, micro lens array, immunoassay chip, DNA separation chip, micro reactor, nano bio device, optical waveguide, optical filter, photonic liquid crystal Nanoimprint lithography is also useful in.

In these permanent film applications, since the formed pattern is finally left in the product, performance mainly on the durability and strength of the film, such as heat resistance, light resistance, solvent resistance, scratch resistance, high mechanical properties against external pressure, and hardness, is required.

As described above, most of the patterns formed by the conventional photolithography method can be formed by nanoimprint, and are attracting attention as a technique capable of forming fine patterns at low cost.

In the curable composition for nanoimprint used in such a nanoimprint method, it is necessary to have the property which can form a favorable pattern by simple operation. Specifically, it should be low in viscosity, cured at high reaction rate when irradiated with light, suitable for spin coating or slit coating, fine pattern formation is possible, adhesion to mold is suppressed, and after photocuring It is necessary to have high adhesion to the substrate, excellent etching, easy peeling of the resist, and the like.

[Patent Document 1] US Patent No. 5,772,905

[Patent Document 2] US Patent No. 5,956,216

[Patent Document 3] US Patent No. 5,259,926

[Patent Document 4] Japanese Unexamined Patent Publication No. 2005-197699

[Patent Document 5] Japanese Unexamined Patent Publication No. 2005-301289

[Patent Document 6] Japanese Unexamined Patent Publication No. 2004-240241

[Non-Patent Document 1] S. Chou et al., Appl. Phys. Lett. 67, 3114 (1995)

[Non-Patent Document 2] M. Colbun et al., Proc. SPIE, Vol. 3676, 379 (1999)

As mentioned above, although the curable composition for nanoimprints needs to have various properties, the composition proposed so far did not satisfy all of these conditions. An object of the present invention is suitable for spin coating or slit coating, enables fine pattern formation, high adhesion to a substrate after photocuring, easy peeling of resist, and particularly a curable composition for nanoimprint for an etching resist. And a pattern forming method using the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the subject of the prior art, the present inventors discovered that the said objective can be achieved by this invention which has the following means.

[1] The curable composition for nanoimprints containing 87% by mass or more of a monofunctional polymerizable compound and a photopolymerization initiator.

[2] The curable composition for nanoimprint according to [1], which contains two or more kinds of monofunctional polymerizable compounds.

[3] Among the two or more kinds of monofunctional polymerizable compounds, the polymerizable functional group of one monofunctional polymerizable compound is different from the polymerizable functional group of the other monofunctional polymerizable compound. Curable composition for nanoimprint as described in [2].

[4] The above-mentioned two or more kinds of monofunctional polymerizable compounds, at least one of (1) acryl ester compounds and (2) acrylamide compound or N-vinyl compound. Curable composition for nanoimprints in any one of [4].

[5] The curable composition for nanoimprint according to any one of [1] to [4], further comprising a silicone resin.

[6] The curable composition for nanoimprint according to any one of [1] to [5], further comprising a long chain alkyl carboxylic acid or a metal salt thereof or a carboxylic acid long chain alkyl ester.

[7] The curable composition for nanoimprint according to any one of [1] to [6], further comprising a nonionic surfactant.

[8] The curable composition for nanoimprint according to any one of [1] to [7], wherein the viscosity at 25 ° C. is 2 to 40 mPa · s.

[9] a step of forming a film having a film thickness of 0.03 to 40 µm by applying and curing the curable composition for nanoimprint according to any one of [1] to [8], and a step of forming a pattern in the formed film. The pattern formation method in optical nanoimprint lithography characterized by the above-mentioned.

[10] A step of applying the curable composition for nanoimprint according to any one of [1] to [8], a step of pressing the light-transmissive mold to a resist layer on the substrate, and deforming the curable composition for nanoimprint, mold A method of forming a resist pattern, comprising the step of irradiating light from the back surface or the back surface of a substrate to cure the coating film and to form a resist pattern fitted to a desired pattern.

The curable composition for nanoimprint of the present invention is suitable for spin coating and slit coating, enables fine pattern formation, high adhesion to a substrate after photocuring, and easy peeling of a resist. Moreover, according to this invention, it is further possible to provide the curable composition for nanoimprint which has moderate viscosity, hardens | cures with high reaction rate at the time of light irradiation, adhesion to a mold is suppressed, and is excellent also in etching property. Moreover, according to the patterning method of this invention, a fine pattern can be formed by a simple method.

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. Although description of the element | module described below may be made | formed based on typical embodiment of this invention, this invention is not limited to such embodiment.

In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification. In addition, in this specification, "meth (acrylate)" shows an acrylate and a methacrylate, "meth (acryl)" shows an acryl and methacryl, and "meth (acryloyl)" acryloyl And methacryloyl. In addition, in this specification, a "polymerizable compound" distinguishes with an oligomer and a polymer, and means the compound whose mass mean molecular weight is 1,000 or less. In this specification, a "functional group" means group which participates in a polymerization reaction. In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent. In addition, the nanoimprint referred to in this invention means pattern transfer of about several micrometers to several tens of nm size.

[Curable composition for nanoimprint of the present invention]

(Characteristic of the composition)

The curable composition for nanoimprint of the present invention (hereinafter may be simply referred to as the "composition of the present invention") includes (a) 87 mass% or more of at least one monofunctional polymerizable compound, and (b) a photopolymerization initiator. It is to contain. Usually, the curable composition used for a photo nanoimprint method contains the polymeric compound which has a polymeric functional group, and the photoinitiator which starts the polymerization reaction of the said polymeric compound by light irradiation, and also surfactant and oxidation as needed. It consists of containing an inhibitor etc. In the curable composition for nanoimprints of the present invention, the monofunctional polymerizable compound contains 87% by mass or more, and is characterized by containing a photopolymerization initiator.

It is preferable that the curable composition for nanoimprints of this invention contains a silicone resin or long-chain alkylcarboxylic acid further, and it is especially preferable to contain a silicone resin.

Preferred compositions of the curable composition for nanoimprint of the present invention include (a) 87 to 99.8 mass% of monofunctional polymerizable compound, (b) 0.1 to 8 mass% of photopolymerization initiator, and (c) 0.008 to 5.0 mass% of silicone resin. to be. As for a more preferable composition, (a) monofunctional polymeric compound is 90-99 mass%, (b) 0.3-5 mass% of photoinitiators, and (c) silicone resin are 0.01-4 mass%. More preferable compositions are 95-98 mass% of (a) monofunctional polymerizable compounds, 0.5-3 mass% of (b) photoinitiators, and 0.02-3 mass% of (c) silicone resin. When containing 2 or more types of monofunctional polymeric compounds, it is preferable that a total amount satisfy | fills the said range. The same applies to the photopolymerization initiator and the silicone resin. In addition, although said preferable composition is described about the case where a silicone resin is used as (c), the preferable composition when the long-chain alkylcarboxylic acid is used as (c) is also the same.

The detail of each component contained in the curable composition for nanoimprints of this invention is demonstrated below.

(Component contained in composition)

Monofunctional polymerizable compound

The nanoimprint curable composition of this invention contains at least 1 sort (s) of monofunctional polymeric compound. The monofunctional polymerizable compound used for this invention is a compound which has one polymerizable functional group. Although the kind in particular of a polymerizable functional group is not restrict | limited, It is preferable that it is an ethylenically unsaturated bond.

-메톡시스티렌, m-브로모스티렌, m-클로로스티렌, m-메틸스테렌, p-브로모스티렌, p-클로로스티렌, p-시아 노스티렌, p-메톡시스티렌, p-메틸스티렌,

-메틸스티렌, p-1-(2-히드록시부틸)스티렌, p-1-(2-히드록시프로필)스티렌, p-2-(2-히드록시프로필)스티렌, N-비닐숙신이미드, 2-메틸-5-비닐테트라졸, 2-페닐-5-(4'-비닐)페닐테트라졸, N,N-메틸-비닐톨루엔술폰아미드, N-비닐-N'-에틸우레아, 비닐아세테이트, 비닐벤조에이트, 비닐부틸에테르, 비닐부틸레이트, 비닐클로로아세테이트, 비닐디클로로아세테이트, 비닐도데실에테르, 비닐에테르, 비닐에틸에테르, 비닐메틸옥살레이트, 비닐에틸술파이드, 비닐포르메이트, 비닐이소부틸에테르, 비닐이소부틸술파이드, 비닐이소프로필케톤, 비닐라우레이트, 비닐-m-크레딜에테르, 비닐메틸술파이드, 비닐메틸술폭사이드, 비닐-o-크레딜에테르, 비닐옥타데실에테르, 비닐옥틸에테르, 비닐-p-크레딜에테르, 비닐페닐에테르, 비닐페닐술파이드, 비닐프로피오네이트, 비닐스테아레이트, 비닐-tert-부틸술파이드, 비닐티올아세테이트, 비닐-4-클로로시클로헥실케톤, 비닐-2-클로로에틸에테르, 비닐-tris(트리메톡시실록시)실란, p-비닐벤질에틸카르비놀, p-비닐벤질메틸카르비놀, 비닐렌카르보네이트, 비닐이소시아네이트, N,N-디에틸아크릴아미드, 이미드아크릴레이트, N-비닐포름아미드, 에톡시페닐(메트)아크릴레이트, 시클로헥실 (메트)아크릴레이트, 디시클로펜타닐(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜테닐옥시에틸(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 옥세탄아크릴레이트, 1-아다만틸(메트)아크릴레이트, (2-에틸-2-메틸-1,3-디옥솔란-4-일)메틸(메트)아크릴레이트, 아크릴로일모르폴린, 아크릴산 다이머, 2-(메트)아크릴로일옥시에틸숙신산, 2-(메타)아크릴로일옥시에틸헥사히드로프탈산 등을 들 수 있다.As the monofunctional polymerizable compound which can be used in the present invention, acrylamide, methacrylate, acetoxy acrylate, benzyl acrylate, butyl acrylate, glycidyl acrylate, acrylonitrile, allyl benzene, crotonaldehyde, di Allylcyanamide, diethylfumarate, 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, fumaronitrile, maleic anhydride, maleimide, N-phenyl methacrylamide, butyl methacrylate , Glycidyl methacrylate, methyl methacrylate, phenyl methacrylate, N-methyl acrylamide, N-hydroxyethyl acrylamide, N, N-dimethylaminoethyl (meth) acrylate, diethylami Noethyl (meth) acrylate, 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 methacrylate, norbornadiene, N-vinyloxazoli Don, N-vinyl-2-pyrrolidone, N-vinylformamide, diallyl melamine, N, N'-divinylaniline, indene, isopropenyl acetate, methacryloylacetone, norbornadiene, 2 , 4-acryloxymethyl-2,4-dimethyloxazoline, 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,

-Methoxystyrene, m-bromostyrene, m-chlorostyrene, m-methylstyrene, p-bromostyrene, p-chlorostyrene, p-cyano nostyrene, p-methoxystyrene, p-methylstyrene,

Methyl styrene, p-1- (2-hydroxybutyl) styrene, p-1- (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 chloro acetate, vinyl dichloro acetate, 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-credyl ether, vinyl methyl sulfide, vinyl methyl sulfoxide, vinyl-o-credyl ether, vinyl octadecyl ether, vinyl octyl ether , Vinyl-p-credyl ether, vinyl phenyl ether, vinyl phenyl sulfide, vinyl propionate, vinyl Terarate, vinyl-tert-butylsulfide, vinylthiol acetate, vinyl-4-chlorocyclohexyl ketone, vinyl-2-chloroethyl ether, vinyl-tris (trimethoxysiloxy) silane, p-vinylbenzylethylcar Binol, p-vinylbenzylmethylcarbinol, vinylene carbonate, vinyl isocyanate, N, N-diethylacrylamide, imide acrylate, N-vinylformamide, ethoxyphenyl (meth) acrylate, cyclohexyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, oxetane acrylate , 1-adamantyl (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, acryloylmorpholine, acrylic acid dimer, 2- (Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrate Lofted acid etc. are mentioned.

Among these, N-vinyl caprolactam, N-vinyl-2-pyrrolidone, acryloyl morpholine, benzyl acrylate, N-vinylformamide, isobornyl acrylate, phenoxyethyl acrylate, 2- ( (Meth) acryloyloxyethyl succinic acid and (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate are preferable, and N-vinyl caprolactam and acryloyl mor Pauline, benzyl acrylate, and isobornyl acrylate are more preferred in view of low viscosity, good compatibility, and good curability.

It is preferable to contain two or more types of monofunctional polymeric compound especially in the nanoimprint curable composition of this invention. At this time, it is preferable to select and combine two or more types of monofunctional polymeric compounds from a viewpoint of improving photocurability or improving adhesiveness with respect to a board | substrate from a polarity different from each other. Specifically, the monofunctional polymerizable compound which is a (meth) acryl group and the monofunctional polymeric compound which is an acrylamide group are combined, or the monofunctional polymeric compound which is a (meth) acryl group and the monofunctional polymeric compound which is N-vinyl group are combined. Etc. are preferable.

When using two or more types of monofunctional polymeric compounds, it is preferable that content of the most monofunctional polymeric compound contained most is 50-98 mass% of the whole composition, It is more preferable that it is 60-96 mass%, It is more preferable that it is 70-95 mass%.

Other polymerizable monomer

In this invention, a bifunctional or more than functional polymerizable compound can also be added as needed. Specific examples of the compound include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, di (meth) acrylate isocyanurate, 1,3-butylene glycol di (meth) acrylate , 1,4-butanedioldi (meth) acrylate, EO-modified 1,6-hexanedioldi (meth) acrylate, ECH-modified 1,6-hexanedioldi (meth) acrylate, aryloxypolyethylene glycol acrylate, 1,9-nonanedioldi (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (Meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxy pivalate neopentylglycol di (meth) acrylate, neopentylglycol di (meth) acrylate, EO modified neopentylglycol diacrylate, pro Len oxide (hereinafter referred to as "P0") modified neopentyl glycol diacrylate, caprolactone modified hydroxy pivalic acid ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid (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 glycol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylic Rate, tricyclodecane dimethanol (di) acrylate, neopentyl glycol modified trimethylolpropanedi (meth) acrylate, tri Propylene glycol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinyl ethylene urea, divinyl propylene urea , ECH modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, P0 modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO modified phosphate triacrylate, trimethylolpropane tree ( Meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, P0 modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocy Anurate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) a Relate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl modified dipentaerythritol tri (meth) Acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.

It is preferable that it is 0-10 mass% of the whole composition, as for content of a bifunctional or more functional compound, it is more preferable that it is 0-7 mass%, and it is still more preferable that it is 0-3 mass%.

Photopolymerization initiator

The nanoimprint curable composition of this invention contains a photoinitiator. Any photopolymerization initiator used in the present invention can be used as long as it is a compound that generates active species that polymerize the monofunctional polymerizable compound described above by light irradiation. As a photoinitiator, the radical polymerization initiator which generate | occur | produces a radical by light irradiation, and the cationic polymerization initiator which generate | occur | produce an acid by light irradiation are preferable, More preferably, it is a radical polymerization initiator, but the polymerizable group of the said polymeric compound It is appropriately determined according to the kind. That is, the photoinitiator in this invention mix | blends what has activity with respect to the wavelength of the light source to be used, and uses what generate | occur | produces suitable active species according to the difference of reaction format (for example, radical polymerization, cationic polymerization, etc.). There is a need. In addition, in this invention, a photoinitiator may use multiple types together.

Content of the photoinitiator used for this invention is 0.01-15 mass% with respect to all the polymerizable monomers contained in a composition, Preferably it is 0.1-12 mass%, More preferably, it is 0.2-7 mass%. to be. When using two or more types of photoinitiators, the total amount becomes said range.

When content of a photoinitiator is 0.01 mass% or more, since there exists a tendency for a sensitivity (fast curing property), resolution, line edge roughness property, and coating film strength to improve, it is preferable. On the other hand, when content of a photoinitiator is 15 mass% or less, since there exists a tendency for light transmittance, coloring property, handleability, etc. to improve, it is preferable. Until now, in the composition for inkjets and liquid crystal display color filters containing dyes and / or pigments, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied, but optical nanoimprints such as for nanoimprints have been studied. It is not clear about the addition amount of the preferable photoinitiator and / or the photo-acid generator with respect to the curable composition for]. That is, in systems containing dyes and / or pigments, these may act as radical trapping agents, affecting photopolymerization and sensitivity. In view of this, the addition amount of a photoinitiator is optimized in these uses. On the other hand, in the nanoimprint curable composition of this invention, dye and / or pigment are not an essential component, and the optimal range of a photoinitiator may differ from the thing of the field | areas, such as a composition for inkjets and a composition for liquid crystal display color filters.

As the radical photopolymerization initiator used in the present invention, a commercially available initiator can be generally used. An acyl phosphine type compound and an oxime ester type compound are preferable from a viewpoint of hardening sensitivity. Examples thereof include Irgacure (registered trademark) 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl1-propan-1-one, available from Ciba, Irgacure ( 184 (1-hydroxycyclohexylphenylketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexylphenylketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1 , 2-diphenylethan-1-one), Irgacure (registered trademark) 379 (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl -1-butanone]), Irgacure (registered trademark) 907 (2-methyl-1 [4-methylthiophenyl] -2-morpholinopropan-1-one, Irgacure (registered trademark) 819 (bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure (registered trademark) 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, 1-hydroxycyclo Hexyl-phenyl-ketone), Irgacure (registered trademark) 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, 2- Hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure (registered trademark) OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O -Benzoyloxime), Darocur (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242 (eta) Non, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6 available from BASF) -Trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO-L (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide), ESACURE 1001M (1- [4-benzoyl) available from Sieber Heguna, Japan Phenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propane-1-one, N-1414 Adeka Optoma (registered trademark) N-1414 available from Asahi Telephone Co., Ltd. Field system), Adeka Optoma (registered trademark) N-1717 (Acridin system), Adeka Optoma (registered trademark) N-1606 (triazine system), Sanwa TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine) from Chemicals, TME- from Chemicals Triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), MP-triazine from Sanwa Chemical (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), Midori Chemical Co., Ltd. TAZ-113 (2- [2- (3,4-dimethy) Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), Midori Chemical Co., Ltd. TAZ-108 (2- (3,4-dimethoxyphenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenyl Sulfide, 4-phenylbenzophenone, ethylmihilerketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl Thioxanthone, 1-chloro-4-propoxy thioxanthone, 2-methylthioke Ton, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1, 1-trichloroacetophenone, diethoxyacetophenone and dibenzosverone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenylether, 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-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1, 2'-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, butoxyethyl-4- (dimethylamino) benzoate Etc. can be mentioned.

In addition, in the present invention, "light" includes not only light of a wavelength in a region such as ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light, electromagnetic radiation, but also radiation. The radiation includes, for example, microwaves, electron beams, EUV, and X-rays. Moreover, laser beams, such as a 248 nm excimer laser, a 193 nm excimer laser, a 172 nm excimer laser, can also be used. These light may use the monochromatic light (single wavelength light) which passed the optical filter, and may be light (complex light) from which a some wavelength differs. Multiple exposure is also possible, and after forming a pattern for the purpose of raising film strength, etching resistance, etc., it is also possible to expose whole surface.

Although the photoinitiator used by this invention needs to be selected suitably with respect to the wavelength of the light source to be used, it is preferable not to generate gas during mold pressurization and exposure. When the gas is generated, the mold is contaminated, so it is necessary to frequently clean the mold, or the photocurable composition is deformed in the mold, causing problems such as deterioration of the transfer pattern accuracy.

It is preferable that the nanoimprint curable composition of this invention is a radically polymerizable composition whose polymeric compound (A) is a synthetic compound among radicals, and a photoinitiator (B) is a radical polymerization initiator which generate | occur | produces a radical by light irradiation.

Silicone resin

It is preferable that the nanoimprint curable composition of this invention contains a silicone resin. The silicone resin used in the present invention may be any compound or composition which is a silicone grease in which a solid silicone resin, silicone oil, or a silicone oil such as sodium stearate is added to the silicone oil, or a composition, but silicone oil is particularly preferred. Do. According to the present invention, by adding 87% by mass or more of a monofunctional polymerizable compound and a photopolymerization initiator, and further using a silicone resin, spin coating and slit coating can be improved to make fine pattern formation easier, and after photocuring The adhesiveness to a board | substrate can be improved and peeling of a resist can be made easy. Moreover, adhesion to a mold can be suppressed and etching property can be improved.

As the silicone resin, specifically, dimethylsilicone oil, methylphenylsilicone oil, methylhydrogensilicone oil, alkyl modified silicone oil, alkoxy modified silicone oil, polyethersilicone oil, mercapto modified silicone oil, amino modified silicone oil, epoxy modified silicone Oils, carboxyl-modified silicone oils, acrylate-modified silicone oils, methacrylate-modified silicone oils, fluorine-modified silicone oils, hydroxy-modified silicone oils, and the like, among which acrylic modified silicone oil, methacrylate-modified silicone oil and carboxyl group Modified silicone oils, alkoxy modified silicone oils, epoxy modified silicone oils are preferred, and acrylic modified silicone oils, methacrylate modified silicone oils, and carboxyl group modified silicone oils are more preferred. Moreover, a commercial item can also be used, for example, KF-105, X-22-163A, X-22-169AS, X-22-160AS, X-22-164A, and X-22- by Shin-Etsu Chemical Co., Ltd. make. 3710, X-22-167B, X-22-4272, etc. are mentioned.

300-20000 are preferable, as for the molecular weight of the silicone resin used by this invention, 400-15000 are more preferable, 500-12000 are still more preferable.

If the molecular weight of a silicone resin is more than the lower limit of the said preferable range, since photoresist exists in the tendency for a resist to peel easily in a mold, it is preferable. On the other hand, since the viscosity of a resist composition tends to fall that the molecular weight of a silicone resin is below the upper limit of the said preferable range, it is preferable.

Content of the silicone resin used for this invention is 0.008-5 mass% with respect to all the polymerizable monomers contained in a composition, Preferably it is 0.01-4 mass%, More preferably, it is 0.02-3 mass % to be. When using two or more types of silicone resins, the total amount becomes said range.

If content of a silicone resin is more than the lower limit of the said preferable range, a resist will peel easily in a mold after photocuring, and it exists in the tendency for defect generation | occurrence | production, such as a coating stripe, to be remarkably reduced at the time of application | coating of a slit coat etc., and it is preferable. On the other hand, when content of a silicone resin is below the upper limit of the said preferable range, generation | occurrence | production of defects, such as a crater, at the time of application | coating falls remarkably, and there exists a tendency for the adhesiveness with the board | substrate of a resist to improve, and it is preferable.

Long chain alkyl carboxylic acid, etc.

It is also preferable that the nanoimprint curable composition of this invention contains a long chain alkyl carboxylic acid, its metal salt, or a carboxylic acid long chain alkyl ester.

12-20 are preferable, as for carbon number of the alkyl part of the long-chain alkylcarboxylic acid used for this invention, and the alkyl part of the carboxylic acid long-chain alkylester used for this invention, 13-19 are more preferable. , 14-18 are more preferable. When carbon number is 12 or more, the effect by adding is easy to be acquired, and when carbon number is 20 or less, there exists a tendency for more favorable solubility to be obtained. Examples of the metal constituting the long chain alkyl carboxylic acid metal salt include sodium and potassium. The carboxylic acid portion of the carboxylic acid long chain alkyl ester is not particularly limited, and alkyl carboxylic acid or aryl carboxylic acid can be used.

As long-chain alkylcarboxylic acid or its metal salt, carboxylic acid long-chain alkylester which can be preferably used by this invention, For example, zinc stearate, zinc palmitate, butyl stearate, ethyl palmitate, etc. Can be mentioned.

According to the present invention, in addition to 87 mass% or more of a monofunctional polymerizable compound and a photopolymerization initiator, spin coating and slit coating are further performed by using a long chain alkyl carboxylic acid or a metal salt thereof or a carboxylic acid long chain alkyl ester. It is possible to improve the formation of fine patterns more easily, to improve the adhesion to the substrate after photocuring, and to facilitate the peeling of the resist. Moreover, adhesion to a mold can be suppressed and etching property can be improved.

(d) other ingredients

The nanoimprint curable composition of this invention has the effect of this invention according to various objectives other than the above-mentioned (a) monofunctional polymeric compound, (b) photoinitiator, (c) silicone resin, and long-chain alkylcarboxylic acid. Surfactants, antioxidants, solvents, polymer components, polymerization inhibitors, ultraviolet absorbers, light stabilizers, deterioration inhibitors, plasticizers, adhesion promoters, thermal polymerization initiators, colorants, elastomer particles, photoacid multipliers, light You may add a base generator, a basic compound, a flow regulator, an antifoamer, a dispersing agent, etc. It is preferable that especially the nanoimprint curable composition of this invention contains a nonionic surfactant.

-Surfactants-

It is preferable that the nanoimprint curable composition of this invention contains surfactant. Content of surfactant used for this invention is 0.001-5 mass% in the whole composition, Preferably it is 0.002-4 mass%, More preferably, it is 0.005-3 mass%. When using two or more types of surfactant, the total amount becomes said range. If the surfactant is in the range of 0.001 to 5% by mass in the composition, the effect of uniformity of the coating is good, it does not cause deterioration of mold transfer characteristics due to excessive surfactant, and does not cause poor substrate adhesion of the resist. There is an advantage.

By using such surfactant, a silicon wafer for semiconductor element manufacture, a square glass substrate for liquid crystal element manufacture, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, an amorphous silicon film, and an oxide In general, a striation occurs when a nanoimprint curable composition is applied onto a substrate on which various films such as an indium oxide (ITO) film doped with tin and a tin oxide film are formed, and a scaly shape (dry stain of a resist film), and the like. It becomes easier to solve the problem of coating failure. In addition, it is easier to improve the fluidity of the nanoimprint curable composition into the cavity of the mold recess, to improve the peelability between the mold and the resist, to improve the adhesion between the resist and the substrate, and to decrease the viscosity of the composition.

As an example of the nonionic surfactant which can be used by this invention, polyoxyalkylene polytyryl phenyl ether, such as brand name pionein D6112W (made by Takemoto fats and oils), is mentioned. Moreover, brand name Furodo FC-430, FC-431 (made by Sumitomo 3M), brand name Saffron S-382 (made by Asahi Glass, Inc.), EFTOP EF-122A, 122B, 122C, EF-121, EF -126, EF-127, MF-100 (manufactured by Tochem Products Co., Ltd.), trade names PF-636, PF-6320, PF-656, PF-6520 (all 0MN0VA Solutions, Inc.), trade name Futagent FT250, FT251 , DFX18 (all manufactured by Neos), brand names Udine DS-401, DS-403, DS-451 (all manufactured by Daikin Industries Co., Ltd.), brand names MegaPac 171, 172, 173, 178K, 178A, ( And fluorine-based surfactants such as Dainippon Ink Chemical Co., Ltd.). In these, polyoxyalkylene polytyryl phenyl ether, a perfluoro group containing oligomer, etc. are preferable.

Antioxidant

The nanoimprint curable composition of the present invention may contain a known antioxidant. Content of antioxidant used for this invention is 0.01-10 mass% with respect to the total amount of a polymeric compound, for example, Preferably it is 0.2-5 mass%. When using two or more types of antioxidant, the total amount becomes said range.

The oxidizing agent is to inhibit the fading of a variety of oxidizing gases such as fade and ozone, active oxygen, NO _x, SO _x (X is a positive number) by heat or light irradiation. In particular, in the present invention, by adding an antioxidant, there is an advantage that it is easy to prevent coloring of the cured film and to reduce film thickness reduction due to decomposition. Such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives and the like. Among these, especially a hindered phenol type antioxidant and a thioether type antioxidant are preferable from a viewpoint of coloring of a cured film, and a film thickness reduction.

As a commercial item of the said antioxidant, brand names Irganox 1010, 1035, 1076, 1222 (above, Chiba-Geigi Co., Ltd. make), brand names Antigene P, 3C, FR, Sumiraiza S, Sumiraiza GA80 (Sumitomo Chemical Co., Ltd.) (Trade name) Adekastab AO70, AO80, AO503 (made by ADEKA Corporation), etc. are mentioned. These may be used independently, or may mix and use them.

-solvent-

It is also possible to contain a solvent in the curable composition for nanoimprints of this invention as needed. It is preferable to use an organic solvent as a solvent. However, it is preferable that content of the organic solvent is 3 mass% or less in all the compositions. That is, since the curable composition for nanoimprint of this invention contains a monofunctional polymeric compound as a reactive diluent, it does not necessarily need to contain the organic solvent for dissolving the component of the curable composition for nanoimprint of this invention. In addition, if the organic solvent is not contained, the baking step for volatilization of the solvent becomes unnecessary, and thus the advantage of being effective in simplifying the process is great. Therefore, in the curable composition for nanoimprinting of this invention, content of the organic solvent becomes like this. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, It is especially preferable not to contain. As described above, the curable composition for nanoimprint of the present invention does not necessarily contain an organic solvent, but the case of dissolving a compound or the like that is insoluble in the reactive diluent as the curable composition for nanoimprint of the present invention or the viscosity may be finely adjusted. And the like, optionally. As a kind of organic solvent which can be used suitably for the curable composition for nanoimprints of this invention, it is a solvent generally used in the curable composition for nanoimprints and a photoresist, If it dissolves and disperse | distributes the compound used by this invention If it does not react with these components, it will not specifically limit.

As said organic solvent, For example, alcohol, 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; Ethylene glycol alkyl ether acetates such as methyl cellosolve 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 alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and 2-heptanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate Esters such as lactic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate Can be mentioned.

In addition, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyro High boiling point solvents, such as lactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate, can also be added. These may be used individually by 1 type and may use two or more types together.

Among these, methoxy propylene glycol acetate, ethyl 2-hydroxy propionate, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone, etc. are particularly preferable. Do.

In addition, although the curable composition for nanoimprints of this invention can be made to contain water, the content is in the whole composition, Preferably it is 2.0 mass% or less, More preferably, it is 1.5 mass%, More preferably, it is 1.0 mass% or less to be. By making the moisture content at the time of preparation into 2.0 mass% or less, the storage stability of the curable composition for nanoimprints of this invention can be made more stable.

-Sensitizer-

(d) sensitizers

A sensitizer can be added to the curable composition for nanoimprints of the present invention. By adding a sensitizer, the wavelength absorption of a UV range can be adjusted.

Typical sensitizers which can be preferably used in the present invention include Crivelo [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)], specifically, pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N- Vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives, and the like.

It is preferable that the content rate of the sensitizer in the curable composition for nanoimprints of this invention is 0-5.0 mass% of the whole composition, It is preferable that it is 0.1-5.0 mass%, It is more preferable that it is 0.2-2.0 mass%. By making the content of the sensitizer 0.1 mass% or more, the effect of the sensitizer can be expressed more effectively. Moreover, by making content of a sensitizer into 5 mass% or less, poor melt | dissolution and deterioration of liquid stability can be suppressed.

Organic Metal Coupling Agents

You may mix | blend an organometallic coupling agent with the curable composition for nanoimprints of this invention in order to improve the heat resistance of a surface structure which has a fine uneven | corrugated pattern, strength, or adhesiveness with a metal vapor deposition layer. In addition, the organometallic coupling agent is effective because it also has the effect of promoting the thermosetting reaction. As an organometallic coupling agent, various coupling agents, such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, a tin coupling agent, can be used, for example.

As a silane coupling agent used for the curable composition for nanoimprints of this invention, vinyl, such as vinyl trichlorosilane, vinyl tris ((beta) -methoxyethoxy) silane, vinyl triethoxysilane, and vinyl trimethoxysilane, for example. Silanes; acrylic silanes such as γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane; epoxy silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ Aminosilanes such as -aminopropyltrimethoxysilane; And γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, and the like as other silane coupling agents.

As a titanium coupling agent, for example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite Titanate, tetraoctylbis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate , Bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylic isostearoyl titanate, isopropyl isostaroyl diacryl titanate, isopropyl tri (dioctyl Phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, dicumylphenyl When there may be mentioned one ethylene titanate such as acetate titanate, di-isostearate.

Examples of the zirconium coupling agent include tetra-n-propoxy zirconium, tetra-butoxy zirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethylacetoacetate, zirconium butoxyacetyl Acetonate bis (ethylacetoacetate) etc. are mentioned.

As an aluminum coupling agent, for example, aluminum isopropylate, monosec-butoxy aluminum diisopropylate, aluminum sec-butylate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate) And alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetoacetate), and the like.

The said organometallic coupling agent can be mix | blended arbitrarily in the ratio of 0.001-10 mass% in solid content whole quantity of the curable composition for nanoimprints. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective for improving the provision of heat resistance, strength, and adhesion to the vapor deposition layer. On the other hand, since the ratio of an organometallic coupling agent is 10 mass% or less, there exists a tendency which can suppress the defect of stability of a composition, and film formation, and it is preferable.

Polymerization inhibitor

In order to improve storage stability etc., you may mix | blend a polymerization inhibitor with the curable composition for nanoimprints of this invention. As a polymerization inhibitor, For example, Phenols, such as hydroquinone, tert- butyl hydroquinone, a catechol, hydroquinone monomethyl ether; Quinones such as benzoquinone and diphenyl benzoquinone; Phenothiazines; Copper etc. can be used. It is preferable to mix | blend a polymerization inhibitor in the ratio of 0.001-10 mass% arbitrarily with respect to the whole amount of the curable composition for nanoimprints.

UV absorbers

You may mix | blend a ultraviolet absorber with the curable composition for nanoimprints of this invention.

As a commercial item of a ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 213 (above, Chiba Kaigi Co., Ltd. make), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350 , 400 (above, Sumitomo Chemical Co., Ltd. product) etc. are mentioned. It is preferable to mix | blend a ultraviolet absorber in the ratio of 0.01-10 mass% arbitrarily with respect to the whole amount of the curable composition for nanoimprints.

Light Stabilizer

You may mix | blend an optical stabilizer with the curable composition for nanoimprints of this invention.

As a commercial item of a light stabilizer, Tinuvin 292, 144, 622LD (above, Chiba-Geigi Co., Ltd.), Sanor LS-770, 765, 292, 2626, 1114, 744 (above, Sankyo Chemical Co., Ltd. make) Etc. can be mentioned. It is preferable to mix | blend an optical stabilizer in the ratio of 0.01-10 mass% with respect to the whole amount of a composition.

Deterioration inhibitor

You may mix | blend a deterioration inhibitor with the curable composition for nanoimprints of this invention.

As a commercial item of a deterioration inhibitor, Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, Sumitomo Chemical Co., Ltd. product) etc. are mentioned. It is preferable to mix | blend anti-aging agent in the ratio of 0.01-10 mass% with respect to the whole amount of a composition.

Plasticizer

You may mix | blend a plasticizer with the curable composition for nanoimprints of this invention.

It is possible to add a plasticizer to the curable composition for nanoimprint of the present invention in order to adjust the adhesiveness 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, tricredyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine, and dimethyl adipate. , Diethyl adipate, di (n-butyl) adipate, dimethyl suverate, diethyl suverate, di (n-butyl) suverate, and the like, and a 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 acquire the effect of adding a plasticizer, 0.1 mass% or more is preferable.

Adhesion Promoter

You may mix | blend an adhesion promoter with the curable composition for nanoimprints of this invention.

In order to adjust adhesiveness with a board | substrate, you may add an adhesion promoter to the curable composition for nanoimprints of this invention. Examples of adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxyptridine, 1,10-phenanthroline, 2,2'-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanol Amines, N-ethyldiethanolamine, N-ethylethanolamine and derivatives, benzothiazole derivatives and the like can be used. Adhesion promoter is 20 mass% or less in a composition, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain an effect.

Thermal polymerization initiator

You may mix | blend a thermal polymerization initiator with the curable composition for nanoimprints of this invention.

When hardening the curable composition for nanoimprints of this invention, a thermal polymerization initiator can also be added as needed. As a preferable thermal polymerization initiator, a peroxide and an azo compound are mentioned, for example. As a specific example, benzoyl peroxide, tert- butyl- peroxy benzoate, azobisisobutyronitrile, etc. are mentioned.

-coloring agent-

You may mix | blend a coloring agent with the curable composition for nanoimprints of this invention.

You may arbitrarily add a coloring agent to the curable composition for nanoimprints of this invention for the purpose of improving the visibility of a coating film. A coloring agent can use the pigment and dye used by UV inkjet composition, the composition for color filters, the composition for CCD image sensors, etc. in the range which does not impair the objective of this invention. As a pigment which can be used by this invention, the conventionally well-known various inorganic pigment or organic pigment can be used. Examples of the inorganic pigments are metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony and metal complex oxides are used. Can be mentioned. As an organic pigment, C.I. Pigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139, 151, 154, 167, C.I. Pigment Orange 36, 38, 43, C.I. Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, C.I. Pigment Violet 19, 23, 32, 39, C.I. Pigment Blue 1, 2, 15, 16, 22, 60, 66, C.I. Pigment Green 7, 36, 37, C.I. Pigment Brown 25, 28, C.I. Pigment Black 1, 7 and carbon black can be illustrated.

-filler-

You may mix | blend a filler with the curable composition for nanoimprints of this invention.

You may add a filler to the curable composition for nanoimprints of this invention as an arbitrary component for the purpose of improving heat resistance, mechanical strength, tackiness, etc. of a coating film. As the inorganic fine particles, those having ultra-fine particle size are used. The term "ultrafine particles" herein means particles having a submicron order, which are smaller in particle size than particles having a particle size of several micrometers to several 100 micrometers, which are generally called "fine particles". Although the specific size of the inorganic fine particle used in this invention differs also according to the use and grade of the optical article to which the curable composition for nanoimprints is applied, it is generally understood that the primary particle size is the range of 1 nm-300 nm. It is preferable to use. If primary particle size is 1 nm or more, the shaping | molding property, shape retention property, and mold releasability of the curable composition for nanoimprint can fully be improved, and if primary particle size is 300 nm or less, transparency required for hardening of resin can be maintained. It is preferable at the point of transparency.

Specific examples of the inorganic fine particles include metal oxide fine particles such as SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , Al ₂ O ₃ , and of these, colloidal dispersion is possible as described above, and particles of submicron order preferably used by selecting those having a size, and it is particularly preferred to use colloidal silica (SiO ₂₎ particles.

It is preferable to mix | blend an inorganic fine particle in the ratio of 1-70 mass% in solid content whole quantity of the curable composition for nanoimprints, and it is especially preferable to mix | blend in the ratio of 1-50 mass%. By setting the ratio of the inorganic fine particles to 1% by mass or more, the shaping, shape retention and release properties of the curable composition for nanoimprint of the present invention can be sufficiently improved, and the strength after exposure curing when the ratio of the inorganic fine particles is 70% by mass or less B is preferable at the point of surface hardness.

Elastomer Particles

You may mix | blend elastomer particle with the curable composition for nanoimprints of this invention.

Moreover, in the curable composition for nanoimprints of this invention, you may add an elastomer particle as an arbitrary component for the purpose of improving mechanical strength, flexibility, etc.

-올레핀계 공중합체, 에틸렌/

-올레핀/폴리엔 공중합체, 아크릴 고무, 부타디엔/(메트)아크릴산에스테르 공중합체, 스티렌/부타디엔 블록 공중합체, 스티렌/이소프렌 블록 공중합체 등의 엘라스토머의 입자이다. 또한, 이들 엘라스토머 입자를 메틸메타크릴레이트 폴리머, 메틸메타크릴레이트/글리시딜메타크릴레이트 공중합체 등으로 피복한 코어/쉘형의 입자를 사용할 수 있다. 엘라스토머 입자는 가교 구조를 취하고 있어도 된다As for the elastomer particle which can be added as an arbitrary component to the curable composition for nanoimprints of this invention, average particle size becomes like this. Preferably it is 10 nm-700 nm, More preferably, it is 30-300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene /

-Olefin copolymer, ethylene /

It is particle | grains of elastomer, such as an olefin / polyene copolymer, an acrylic rubber, butadiene / (meth) acrylic acid ester copolymer, a styrene / butadiene block copolymer, and a styrene / isoprene block copolymer. In addition, 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.

As a commercial item of an elastomer particle, Regina bond RKB (Regina Chemicals Co., Ltd. product), Techno MBS-61, MBS-69 (above, Technopolymer Co., Ltd. product) etc. are mentioned, for example.

These elastomer particles can be used alone or in combination of two or more thereof. Preferably the content rate of the elastomer component in the curable composition for nanoimprints of this invention is 1-35 mass%, More preferably, it is 2-30 mass%, Especially preferably, it is 3-20 mass%.

Basic compound

You may arbitrarily add a basic compound to the curable composition for nanoimprints of this invention for the purpose of suppressing hardening shrinkage, improving thermal stability, etc. Examples of the basic compound include an amine, a nitrogen-containing heterocyclic compound such as quinoline and quinolyzine, a basic alkali metal compound and a basic alkaline earth metal compound. Among these, an amine is preferable at the point of compatibility with a photopolymerizable monomer, For example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinu Clydine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, triethanolamine and the like.

(Preparation of composition)

The curable composition for nanoimprints of the present invention can be prepared by mixing the aforementioned components. Moreover, after mixing each said component, it can also be prepared as a solution, for example by filtering by the filter of 0.05 micrometer-5.0 micrometers of pore diameters. Mixing and dissolution of the curable composition for photo nanoimprint is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple steps, and may be repeated several times. The filtrate can also be filtered again. Although the material of the filter used for filtration can use polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, etc., It does not specifically limit.

In the curable composition for nanoimprints of the present invention, the viscosity at 25 ° C. of the component from which the solvent is removed is preferably 1 to 100 mPa · s. More preferably, it is 2-50 mPa * s, More preferably, it is 5-30 mPa * s. By making a viscosity into a suitable range, the rectangularness of a pattern improves and a residual film can be suppressed low.

The curable composition for nanoimprints of the present invention thus prepared has good applicability, and defects are less likely to occur in spin coat and slit coat. In addition, it has a low viscosity, high photoreaction rate and excellent pattern formation in nanoimprint lithography. For this reason, when an ITO film, a metal film, an insulation film, or a semiconductor (silicon wafer etc.) board | substrate is used, especially adhesiveness of the resist cured film / substrate after photocuring is excellent. In addition, the curable composition for nanoimprint of the present invention has good peelability between the resist and the mold after photocuring, and mold contamination does not occur. In addition, the wet etching property is good, and the resist can be easily peeled off after the etching, and there is no contamination of the substrate surface after the resist peeling.

[Pattern Forming Method]

Next, the formation method of the pattern (especially fine uneven | corrugated pattern) using the curable composition for nanoimprints of this invention is demonstrated. In the present invention, the curable composition is applied and cured to form a pattern. Specifically, at least a pattern forming layer made of the curable composition for nanoimprinting of the present invention is applied onto a substrate or support, and dried as necessary to form a layer (pattern forming layer) made of the curable composition for nanoimprinting to form a pattern receptor. Then, the mold is pressed against the surface of the pattern forming layer of the pattern receptor, and a process of transferring the mold pattern is performed, and the fine uneven pattern forming layer is exposed and cured. Optical imprint lithography according to the pattern forming method of the present invention can be laminated or multi-patterned, and can be used in combination with conventional thermal imprints.

Moreover, as an application of the curable composition for nanoimprints of this invention, apply | coating the curable composition for nanoimprints of this invention on a board | substrate or a support body, and exposing, hardening and drying (baking) the layer which consists of this composition as needed, Permanent films, such as an overcoat layer and an insulating film, can also be produced.

Below, the pattern formation method and pattern transfer method using the curable composition for nanoimprints of this invention are demonstrated.

The curable composition for nanoimprint of the present invention is generally well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spin It can form by apply | coating by a coating method, the slit scanning method, etc. Although the film thickness of the layer which consists of a photocurable composition of this invention changes with the use to use, it is 0.03 micrometer-40 micrometers normally, and it is preferable that they are 0.05 micrometer-30 micrometers. Moreover, you may apply | coat multiple curable compositions for nanoimprints of this invention.

The substrate or support for applying the curable composition for nanoimprint of the present invention may be quartz, glass, optical film, ceramic material, deposited film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG, poly Polymer substrates such as ester films, polycarbonate films, polyimide films, TFT array substrates, PDP electrode plates, glass or transparent plastic substrates, conductive substrates such as ITO or metals, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide And semiconductor fabrication substrates such as amorphous silicon are not particularly limited. The shape of the substrate may be a plate shape or a roll shape.

선, 중성자선, 양성자선 등의 방사선도 사용할 수 있다. 자외선원으로서는, 예를 들어 자외선 형광등, 저압 수은등, 고압 수은등, 초고압 수은 등, 크세논등, 탄소 아크등, 태양등 등을 들 수 있다. 방사선에는, 예를 들어 마이크로파, EUV 가 포함된다. 또한, LED, 반도체 레이저광 혹은 248㎚ 의 KrF 엑시머 레이저광이나 193㎚ ArF 엑시머 레이저 등의 반도체의 미세 가공에서 사용되고 있는 레이저광도 본 발명에 바람직하게 사용할 수 있다. 이들 광은 모노크로광을 이용해도 되고, 복수의 파장이 상이한 광 (믹스광) 이어도 된다.Although it does not specifically limit as light which hardens the curable composition for nanoimprints of this invention, Light or radiation of the wavelength of 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, electron beams accelerated by accelerators such as cockcroft accelerators, vender graph accelerators, linear accelerators, betatrons, cyclotrons, etc. are used industrially most conveniently and economically. Γ-rays, X-rays, etc. emitted from an element or reactor

Radiation such as ray, neutron beam or proton beam can also be used. As an ultraviolet source, 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, a solar lamp etc. are mentioned, for example. Radiation contains microwave and EUV, for example. Moreover, the laser beam used by the microfabrication of semiconductors, such as an LED, a semiconductor laser beam, or 248 nm KrF excimer laser beam, a 193 nm ArF excimer laser, can also be used suitably for this invention. Monochrome light may be used for these lights, and light (mixed light) in which a some wavelength differs may be sufficient.

Next, the mold material which can be used by this invention is demonstrated. In optical nanoimprint lithography using the curable composition for nanoimprint of the present invention, at least one of the mold material and or the substrate needs to select a light transmissive material. In the optical imprint lithography applied to this invention, the curable composition for nanoimprints is apply | coated on a board | substrate, a light-transmitting mold is pressed, light is irradiated from the back surface of a mold, and the curable composition for nanoimprints is hardened. Moreover, the curable composition for nanoimprints may be apply | coated on a transparent substrate, a mold may be pressed, light may be irradiated from the back surface of a mold, and the curable composition for nanoimprints may be hardened.

Although light irradiation may be performed in the state which stuck a mold, and may be performed after mold peeling, in this invention, it is preferable to carry out in the state which stuck a mold.

As the mold usable in the present invention, a mold having a pattern to be transferred is used. Although the mold can form a pattern according to desired processing precision, for example by photolithography, an electron beam drawing method, etc., in the present invention, the mold pattern forming method is not particularly limited.

Although the light transmissive mold material used in this invention is not specifically limited, What is necessary is just to have a certain intensity | strength and durability. Specifically, light transparent resins, such as glass, quartz, PMMA, and a polycarbonate resin, flexible films, such as a transparent metal vapor deposition film and polydimethylsiloxane, a photocuring film, a metal film, etc. are illustrated.

Although it does not specifically limit as a non-transmissive mold material used when the transparent substrate of this invention is used, What is necessary is just to have predetermined intensity | strength. Specifically, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, and the like are exemplified, It is not particularly limited. The shape may be any of a plate mold and a roll mold. Roll-shaped molds are particularly applied where continuous productivity of transfer is required.

The mold used in the present invention may be one that has been subjected to a release treatment in order to improve the peelability of the curable composition for nanoimprint and the mold. Commercially available mold release agents such as those treated with a silane coupling agent such as silicone or fluorine, for example, Daikin Industries, Inc .: trade name Optool DSX and Sumitomo 3M, trade name Novec EGC-1720, can be preferably used.

When performing optical imprint lithography using the present invention, it is usually preferable to carry out the pressure of the mold at 10 atmospheres or less. By setting the mold pressure to 10 atm or less, the mold and the substrate are not easily deformed, the pattern accuracy tends to be improved, and since the pressurization is low, the apparatus tends to be reduced, which is preferable. It is preferable to select the area | region which can ensure uniformity of mold transfer in the range in which the residual film of the curable composition for nanoimprinting of a mold convex part becomes small in the pressure of a mold.

In the present invention, the light irradiation in optical imprint lithography may be sufficiently larger than the irradiation amount required for curing. The irradiation amount required for curing is determined by examining the consumption amount of the unsaturated bonds in the curable composition for nanoimprint and the tackyness of the cured film.

Moreover, in the optical imprint lithography applied to this invention, although the board | substrate temperature at the time of light irradiation is normally performed at room temperature, you may irradiate light while heating in order to improve reactivity. As a preliminary step of light irradiation, since it is effective in preventing bubble mixing, suppressing the reactivity decrease by oxygen mixing, and improving the adhesiveness of the mold and the curable composition for nanoimprint, you may perform light irradiation in a vacuum state. In the present invention, the preferred degree of vacuum is performed in the range of 10 ⁻¹ Pa to atmospheric pressure.

After mixing the curable composition for nanoimprints of this invention and each said component, it can be prepared as a solution, for example by filtering by the filter of 0.05 micrometer-5.0 micrometers of pore diameters. Mixing and dissolution of the curable composition for nanoimprint is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple steps, and may be repeated several times. The filtrate can also be filtered again. Although the material used for filtration can use polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, etc., It does not specifically limit.

The case where the curable composition for nanoimprints of the present invention is applied to an etching resist will be described. As an etching process, it can carry out by the method suitably selected from the well-known etching process methods, and in order to remove the base part which is not covered by a resist pattern, it obtains a thin film pattern. Either a treatment with an etchant (wet etching) or a treatment (dry etching) in which the reactive gas is activated by plasma discharge under reduced pressure is performed.

The etching treatment may be a batch method in which a suitable number of sheets is bundled and processed, or a sheet treatment may be performed for each sheet.

As the etching solution in the case of performing the wet etching, a large number of etching solutions have been developed and used as representative examples of ferric chloride / hydrochloric acid, hydrochloric acid / nitric acid, hydrobromic acid and the like. Cerium ammonium nitrate solution, cerium nitrate / hydrogen peroxide mixed solution for Cr, dilute hydrofluoric acid, hydrofluoric acid / nitric acid mixed solution for Ti, ammonium solution and hydrogen peroxide mixed solution for Ta, Mo for A mixture of hydrogen peroxide, ammonia water and hydrogen peroxide, a mixture of phosphoric acid and nitric acid, a mixture of phosphoric acid and nitric acid for MoW and Al, a mixture of hydrofluoric acid and nitric acid, a mixture of phosphoric acid, nitric acid and acetic acid, dilute aqua regia, chloride for ITO Ferric solution, hydrogen iodide solution, a mixture of buffered hydrofluoric acid, hydrofluoric acid and ammonium fluoride in SiNx or SiO ₂ , a mixture of hydrofluoric acid, nitric acid and acetic acid in Si, poly Si, a mixture of aqueous ammonia and hydrogen peroxide in W, A mixture of nitric acid and hydrofluoric acid is used for PSG, and a mixture of hydrofluoric acid and ammonium fluoride is used for BSG. All.

Although the wet etching may be a shower method or a dip method, the precision of etching rate, in-plane uniformity, and wiring width largely depends on processing temperature, and conditions need to be optimized according to substrate type, use, and line width. In addition, when performing the said wet etching, it is preferable to perform post-baking in order to prevent the undercut by the penetration of etching liquid. Usually, these postbaking is performed at about 90 to 140 degreeC, but it is not necessarily limited to this.

Dry etching basically has a pair of parallelly arranged electrodes in a vacuum apparatus, and a parallel flat type dry etching apparatus is used in which a substrate is provided on one electrode. Depending on whether the high-frequency power supply for generating plasma is connected to the electrode on the side of the substrate or the opposite electrode, the reactive ion etching (RIE) mode in which ions are mainly involved and the plasma etching (PE) in which radicals are mainly involved ) Mode.

As the etchant gas used in the dry etching, an etchant gas suitable for each film type is used. Carbon tetrafluoro (chlorine) + oxygen for a-Si / n ⁺ or s-Si, carbon tetrafluorocarbon (sulfur hexafluoride) + hydrogen chloride (chlorine), carbon tetrafluorocarbon + oxygen for a-SiNx, a- Carbon tetrafluoride + oxygen, trifluorocarbon + oxygen for SiOx, tetrafluorocarbon (sulfur hexafluoride) + oxygen for Ta, carbon tetrafluoride + oxygen for MoTa / MoW, chlorine + oxygen for Cr As for Al, boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide, etc. are mentioned. In the dry etching process, the structure of the resist may be greatly changed by ion bombardment or heat, and the peelability is also affected.

The method of peeling the resist used for pattern transfer with respect to a lower substrate after an etching is demonstrated. Peeling is removed by liquid (wet peeling), or oxidized by plasma discharge of oxygen gas under reduced pressure to form a gas (dry peeling / ashing), or oxidized by ozone and UV light to form a gas. Resist removal can be performed by several peeling methods, such as removal (dry peeling / 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 amine and dimethyl sulfoxide or N-methylpyrrolidone are generally known. As the latter example, a monoethanolamine / dimethylsulfoxide mixture (mass mixing ratio = 7/3) is well known.

The resist peeling rate is largely involved in temperature, liquid amount, time, pressure, and the like, and can be optimized according to the substrate type and application. In this invention, it is preferable to immerse a board | substrate in the temperature range of about room temperature to about 100 degreeC (minutes-several ten minutes), and to perform solvent rinsing, such as butyl acetate, and water washing. From the viewpoint of improving the rinsing property, the particle removal property and the corrosion resistance of the peeling solution itself, only the rinse may be performed. Preferable examples include water washing with pure shower and drying with air knife drying. In the case where amorphous silicon is exposed on the substrate, since an oxide film is formed in the presence of water and air, it is preferable to block the air. Moreover, you may also apply the method of using ashing (painting) and peeling with a chemical liquid together. Ashing includes plasma ashing, downflow ashing, ashing with ozone, UV / ozone ashing. For example, when processing an Al substrate by dry etching, although a chlorine-based gas is generally used, aluminum chloride or the like, which is a product of chlorine and Al, may corrode Al. In order to prevent these, you may use the peeling liquid containing a preservative.

There is no restriction | limiting in particular as said etching process, a peeling process, a rinse process, and other processes other than water washing, What is suitably selected from the process in well-known pattern formation is mentioned. For example, a hardening process process etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as a hardening process process, Although it can select suitably according to the objective, For example, whole surface heat processing, whole surface exposure processing, etc. are mentioned preferably.

As said whole surface heat processing method, the method of heating the formed pattern is mentioned, for example. By whole surface heating, the film strength of the surface of the said pattern can be raised. 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 by heat treatment tends to be more improved. When the temperature is 200 ° C. or lower, decomposition of components in the curable composition for nanoimprint occurs and the film quality becomes weak. It can be effectively suppressed. There is no restriction | limiting in particular as an apparatus which performs said whole surface heating, It can select suitably from a well-known apparatus according to the objective, For example, a dry oven, a hot plate, an IR heater, etc. are mentioned. In addition, when using a hot plate, in order to perform heating uniformly, it is preferable to float the base material in which the pattern was formed from the plate.

As said whole surface exposure processing method, the method of exposing the whole surface of the formed pattern is mentioned, for example. By whole surface exposure, hardening in the composition which forms the said photosensitive layer is accelerated | stimulated, and since the surface of the said pattern hardens, etching resistance can be improved. There is no restriction | limiting in particular as an apparatus which performs 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 preferably.

EXAMPLE

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below.

<Example 1>

(a) As a monofunctional polymerizable compound, 29.22 g of N-vinyl caprolactam (made by Aldrich) and 68.18 g of benzyl acrylate (Biscote # 160 by Osaka Organic Chemicals), (b) 2,4,6 as a photoinitiator 2.10 g of -trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) (P-1), (c) 0.50 g of reactive silicone (XX-22-164A manufactured by Shin-Etsu Chemical Co., Ltd.) After quantification, the mixture was mixed at room temperature for 2 hours to obtain a homogeneous solution. The viscosity of the composition was 3 mPa · s.

The prepared composition was spin-coated on a 4-inch glass substrate (0.7 mm thick) on which an aluminum (Al) film having a film thickness of 2000 angstroms was formed so as to have a thickness of 3 µm. The coated base film spin-coated was set in a nanoimprint apparatus using a high pressure mercury lamp (lamp power 2000 mW / cm 2) manufactured by ORC as a light source, and 100 mJ / cm 2 of the back side of the mold at a mold pressing force of 0.8 kN and a vacuum degree of 10 Torr during exposure. It exposed on condition. At this time, as the mold, a mold having a line / space pattern of 20 µm, a groove depth of 2.0 µm, and a surface treated with a plasma using a fluorine-based gas was used. After the exposure, the mold was separated to obtain a resist pattern. Subsequently, the aluminum (Al) part which is not coat | covered with the resist by the phosphate etchant was removed, and the electrode pattern made from aluminum (Al) was formed. Furthermore, mold peeling was performed by immersing for 10 minutes in 70 degreeC monoethanolamine / NMP (N-methylpyrrolidone) mixed peeling liquid.

<Examples 2-12, Comparative Examples 1-2>

As shown in Table 1, the composition was changed and the same process as Example 1 was implemented.

The following measurements and evaluation were performed about the curable compositions for nanoimprints of Examples 1 to 13 and Comparative Examples 1 and 2 described above.

<Viscosity measurement>

The viscosity was measured at 25 ± 0.2 ° C using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd.

The rotational speed at the time of measurement changed according to the viscosity of the measurement object. Namely, 100 rpm for 0.5 mPa · s or more and less than 5 mPa · s, 50 rpm for 5 mPa · s or more and less than 10 mPa · s, 20 rpm for 10 mPa · s or more and less than 30 mPa · s, 10 rpm, 60 mPa · s for 30 mPa · s or more and less than 60 mPa · s The above-mentioned less than 120 mPa * s measured at 5 rpm, respectively.

<Photocurability>

By FT-IR, absorption of 810 cm <^-1> of a double bond by light irradiation in nitrogen atmosphere was measured, and the consumption rate of the double bond was made into the reaction rate. Photocurability was evaluated based on the following criteria.

A: Reaction rate is 70% or more, 100% or less

B: the reaction rate is 40% or more but less than 70%

C: reaction rate is less than 40%

<Spin coating suitability>

After spin coating a curable composition for nanoimprinting to a thickness of 3.0 μm on a 4 inch 0.7 mm thick glass substrate on which an aluminum (Al) film having a thickness of 2000 angstroms was formed, the glass substrate was allowed to stand for 1 minute. Viii), the surface shape was observed, and the following references | standards evaluated.

A: no cratering and no streaks

B: Slight application stripes were observed

C: cratering or application streaks were strongly observed

<Slit application suitability>

Slit coater resist coating device (Hirata Pore Co., Ltd.) for large-sized board | substrate application on the 4-inch 0.7-mm-thick glass substrate (550 mm x 650 mm) which formed the aluminum (Al) film of film thickness 2000 angstroms. The curable composition for nanoimprint was apply | coated using the head coater system), the resist film with a film thickness of 3.0 micrometers was formed, the presence or absence of the stripe-shaped unevenness coming out vertically and horizontally was evaluated, and the following references | standards evaluated.

A: No streaky stain was observed.

B: Stripe-like stains were weakly observed

C: Stripe-shaped unevenness was strongly observed, or cratering was observed in the resist film.

<Pattern formability>

An aluminum (Al) film having a thickness of 2000 Angstroms was formed by using a mold made of glass having a line / space pattern of 20 µm, a groove depth of 2.0 µm, and surface-treated with a plasma using a fluorine-based gas. A 3 micrometers resist was apply | coated and formed into the glass substrate (0.7 mm thickness) of 4 inch, and photoimprint was performed on the conditions of 300 mJ / cm <2> of exposure amount. Then, the mold was removed and the pattern on the substrate was observed by an optical microscope and a scanning electron microscope. Evaluation criteria are as follows.

A: It is almost the same as the pattern of the original plate which is the source of the pattern shape of the mold.

B: There is a part (parts less than 20% of the pattern of the disc) that is different from the pattern shape of the disc which is the source of the pattern shape of the mold.

C: Clearly different from the original pattern which is the source of the pattern shape of the mold, or the film thickness of the pattern is 20% or more different from the original pattern

D: The evaluation of the photoreaction rate or coating aptitude is C, and the pattern formation property cannot be evaluated.

<Adhesion to Mold>

An aluminum (Al) film having a thickness of 2000 Angstroms was formed by using a mold made of glass having a line / space pattern of 20 µm, a groove depth of 2.0 µm, and surface-treated with a plasma using a fluorine-based gas. A 3 micrometers resist was apply | coated and formed on the 4-inch glass substrate (0.7 mm thickness), and the optical imprint was repeated 100 times. When the mold was removed after the 100th photocuring, whether the cured film or the uncured product remained in the mold and the shape change of the mold were visually observed with an optical microscope and evaluated according to the following criteria. In addition, the exposure amount at the time of optical imprint was 300 mJ / cm <2>.

A: no residue, and no shape change of the mold

B: Residue is slightly observed but no shape change of mold

C: There is a residue, and shape deformation such as warping occurs in the mold.

D: Evaluation of photocurability or coating aptitude is C, and evaluation of adhesiveness to a mold is impossible

<Substrate adhesiveness after photocuring>

The substrate adhesiveness was evaluated with reference to JIS K 5600-5-6 (crosscut method). After apply | coating a resist so that the film thickness after hardening may be set to 3 micrometers on a Si wafer, it exposed in the exposure amount 300mJ / cm <2> in nitrogen atmosphere, without pressing a mold, and obtained the cured film. 10x10 masses of lattice lancing patterns orthogonal to 1 mm x 1 mm were produced in this cured film. A tape was attached to the grid pattern to remove the tape at an angle of 60 degrees. The number of mass scales which showed peeling of the pattern visually was measured and evaluated based on the following criteria. It shows that the base material adhesiveness is so favorable that the number of the mass scales with which peeling of the pattern was seen is small.

A: The number of mass scales from which peeling was seen is less than 0-5

B: Number of mass scales from which peeling was seen 5 or more and less than 50

C: Number of mass scales from which peeling was seen 50 or more

D: Evaluation of the photoreaction rate or coating aptitude is C, and evaluation of the board | substrate adhesiveness after photocuring is impossible

<Etchability>

The curable composition for nanoimprint was formed in a pattern shape on the aluminum (Al) formed on the glass substrate, and after curing, the aluminum thin film was etched with a phosphate etchant, and the line / space of 20 µm was visually observed and optical microscope It evaluated by the following references | standards.

A: A line of aluminum having a line width of 20 ± 2.0 μm was obtained.

B: The deviation of the line width of the line became a line exceeding ± 2.0 μm.

C: A missing part of the line exists or is connected between the lines

D: Evaluation of the photoreaction rate or coating aptitude is C, and evaluation of etching property is impossible

<Resist Peelability>

The curable composition for nanoimprint was formed on the aluminum (Al) formed on the glass substrate at a film thickness of 3 μm, and photocured at 300 mJ / cm 2 under a nitrogen atmosphere, followed by 10 minutes in 50 ° C. of N-methylpyrrolidone. After immersion, washing with water and drying, the surface of the substrate was visually observed with an optical microscope, and evaluated according to the following criteria.

A: No resist residue is observed on the substrate

B: Slight residue of resist was observed on the substrate

C: resist is not completely removed

D: Evaluation of the photoreaction rate or coating aptitude is C, and evaluation of resist peelability is impossible

The above measurement and evaluation results are collectively shown in Table 1.

(Note) The unit of a monomer, a photoinitiator, a peeling agent, and surfactant is g. In addition, the blank indicates that no addition was made.

From the results of Table 1, the curable composition for nanoimprint of the present invention has a low viscosity, is cured at a high reaction rate at the time of light irradiation, is suitable for spin coating or slit coating, enables fine pattern formation, and adheres to a mold This was suppressed, the adhesiveness to the board | substrate after photocuring was high, the etching property was excellent, and the peeling of the resist was easy.

In addition, as a result of manufacturing and evaluating a composition in which only the silicone resin was removed from the curable compositions for nanoimprints of Examples 3, 5, and 6, all of the spin coating aptitudes, the slit coating aptitudes, the pattern forming properties, and the molds were compared with those of the corresponding examples. Inferior adhesiveness, etching property, and resist peelability were obtained. The composition corresponding to Example 5 further had poor substrate adhesiveness. As mentioned above, it was confirmed that a more favorable curable composition for nanoimprints is obtained by using a silicone resin.

In addition, as an example of a compound containing a long-chain alkyl carboxylic acid or a metal salt thereof, zinc stearate was substituted with silicon of Example 6 to prepare and evaluate a curable composition for nanoimprint, and the same results as in Example 6 were obtained. Obtained.

The curable composition for nanoimprint of the present invention is a semiconductor integrated circuit, a flat screen, a microelectromechanical system (MEMS), a sensor element, an optical disc, an optical component such as a high density memory disk, an optical component such as a diffraction grating or a relief hologram, nano Devices, optical devices, optical films and polarizers for flat panel displays, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunoassay chips As a photo nanoimprint resist composition for fine pattern formation at the time of manufacture of a DNA separation chip, a micro reactor, a nano bio device, an optical waveguide, an optical filter, a photonic liquid crystal, etc., it can be used widely for various uses.

Claims (10)

Curable composition for nanoimprints containing 87 mass% or more of monofunctional polymeric compounds and a photoinitiator. The method of claim 1, Curable composition for nanoimprints containing 2 or more types of monofunctional polymeric compounds. The method of claim 2, Among the two or more kinds of monofunctional polymerizable compounds, the polymerizable functional group of one monofunctional polymerizable compound is different from the polymerizable functional group of another monofunctional polymerizable compound. Curable composition for imprints. The method of claim 2 or 3, As said 2 or more types of monofunctional polymeric compound, the curable composition for nanoimprints containing at least 1 type of (1) acryl ester compound, and (2) acrylamide compound or N-vinyl compound. The method according to any one of claims 1 to 4, Furthermore, the curable composition for nanoimprints containing silicone resin. The method according to any one of claims 1 to 5, Furthermore, the curable composition for nanoimprints containing long-chain alkylcarboxylic acid or its metal salt, or carboxylic acid long-chain alkylester. The method according to any one of claims 1 to 6, A nonionic surfactant is further contained, The curable composition for nanoimprint characterized by the above-mentioned. The method according to any one of claims 1 to 7, The viscosity in 25 degreeC is 2-40 mPa * s, The curable composition for nanoimprints characterized by the above-mentioned.  The process of forming the film | membrane whose film thickness is 0.03-40 micrometers by apply | coating and hardening the curable composition for nanoimprints in any one of Claims 1-8, The process of forming a pattern in the formed film is characterized by the above-mentioned. The pattern formation method in optical nanoimprint lithography. The process of apply | coating the curable composition for nanoimprints in any one of Claims 1-8, Pressing the light-transmissive mold to the resist layer on the substrate to deform the curable composition for nanoimprint, A method of forming a resist pattern, comprising the step of irradiating light from the back of the mold or from the back of the substrate to cure the coating film and to form a resist pattern fitted to a desired pattern.