TWI475029B - Low-dielectric imprinting material - Google Patents

Description

Low dielectric constant imprint material

The present invention relates to an embossing material and a film having a pattern transferred therefrom. More specifically, it relates to an imprint material for forming a film having a high transmittance and a high refractive index low dielectric constant, and a film having a pattern transferred by the material.

In 1995, Professor Joe and others of Princeton University now advocated a new technology called nanoimprint lithography (Patent Document 1). Nanoimprint lithography is to contact a mold having an arbitrary pattern with a substrate on which a resin film is formed, and pressurizing the resin film while using heat or light as an external stimulus to form the resin which hardens the target pattern. Membrane technology. The nanoimprint lithography has the advantages of simple and low-cost nanometer-level workability when compared with conventional photolithography for manufacturing a semiconductor device.

Further, nanoimprint lithography is expected to replace photolithography, and is suitable for use in manufacturing semiconductor devices, optical devices, display devices, memory media, biochips, and the like. From this, it is known that various reports on the curable composition for photon nanoimprint lithography used in nanoimprint lithography have been proposed (Patent Documents 2 and 3).

However, until now, various materials which are used as materials for nanoimprint lithography (hereinafter referred to as "imprint materials") have been disclosed, but no semiconductors which can be suitably or advantageously used for electric field effect transistors have been reported. The interlayer insulating film and/or the gate insulating film of the element, and the material of the optical member, specifically, a nanoimprint material having a film having a low dielectric constant, a high transmittance, and a high refractive index.

In the past, a compound having an anthracene skeleton has been conventionally used as one of the materials for forming an optical member. For example, when a surface uneven shape is formed on a substrate, a resin-forming component containing a monomer or an oligomer having an anthracene skeleton is reported. A coating material having a transmittance of a photopolymerization initiator of 60% or more (Patent Documents 4 to 6). However, in such conventional documents, not only the use as an imprint material but also a compound having a bisaryl fluorene skeleton is not taught as an imprint material.

In addition, a cross-linking property and a polymer composition for injection molding in the case of producing an optical article having a high refractive index have been reported using a quinone diacrylate as a monomer (Patent Document 7). However, the polymer having a ruthenium structure reported in this document is described as having an excellent property in terms of refractive index, thermal stability, abrasion resistance, and impact resistance, and there is no teaching in this document regarding the assignment. The polymer has a low dielectric constant property. In addition, it has been developed to use the polymer composition for the purpose of producing a plastic optical article such as a video recorder or an ophthalmic lens which must have a high refractive index, but does not necessarily have to have a low dielectric constant. Any possibility that the composition is suitable for use in semiconductor components, in particular imprinted materials.

[Practical Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 5772905

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-105414

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-202022

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-294800

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-182017

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2003-5368

[Patent Document 7] Japanese Patent Laid-Open No. Hei 7-2939

The present invention has been made in view of the above circumstances, and has been solved by providing an imprint material which forms a low dielectric constant film having high transmittance and high refractive index, and a film having a pattern transferred by the material.

Here, as apparent from the above, an object of the present invention is to provide an imprint material which forms a film having high transmittance, high refractive index, and low dielectric constant. Specifically, the transmittance is, for example, for the purpose of providing a material for forming a film having a high transmittance of 95% or more and preferably 98% or more, and the refractive index is, for example, provided to have a thickness of 1.57 or more, preferably 1.60 or more. The material of the high refractive index film is intended for the purpose of providing a material having a low dielectric constant of 2.0 or more, preferably 3.2 or less, for example.

In other words, the present invention is characterized in that an imprint material for forming a film having properties satisfying various characteristics such as total transmittance, refractive index, and dielectric constant is provided.

Moreover, the pattern size formed in the present specification is not affected by the nanometer scale, and the photon imprinting technique, for example, when it contains a micron scale, is called photoimprint processing. In addition, the "dielectric constant" in this specification means a specific dielectric constant.

The present inventors have found that a monomer having a compound having a bisaryl fluorene skeleton can impart a low dielectric constant to a film containing the compound in order to solve the above problems, and the present invention has been completed. .

In other words, the present invention relates to an imprint material comprising the component (A), the component (B), and the component (C), and based on 100 parts by mass of the total of the components (A) and (B). Each contains 50 to 95 parts by mass of the component (A) and 50 to 5 parts by mass of the component (B).

(A) component: a compound having a bisaryl fluorene skeleton represented by the following formula (1)

(B) component: a compound having at least one polymerizable group in a molecule

(C) component: photopolymerization initiator

[Chemical 1]

(In the formula, R represents an acrylonitrile group, a methacryloyl group or a vinyl group, A represents an alkylene group, and m and n each independently represent an integer of 0 to 3).

[Effect of the invention]

In the present invention, since the imprinted material contains a compound having a low dielectric constant of a bisaryl fluorene skeleton, the patterned transfer film made of the imprint material has a low dielectric constant, a high transmittance, and a high refraction. rate.

The embossing material of the present invention can be subjected to photohardening treatment, and since the cured film does not cause partial pattern peeling when the mold is peeled off, a film having a desired pattern can be formed correctly. Moreover, a good embossed pattern can be formed.

Further, the imprint material of the present invention can be formed on any substrate, and a film having a pattern formed by imprinting can be transferred, and it can be suitably used not only for an optical member but also for an electric field effect transistor or the like. An interlayer insulating film and/or a gate insulating film of a semiconductor element.

Further, in the imprint material of the present invention, the curing rate, the dynamic viscosity, and the film thickness can be controlled by changing the kind of the compound having at least two polymerizable groups in the molecule. Further, the embossing material of the present invention can be designed to correspond to the type of the device to be manufactured and the type of the exposure process and the firing process, and since it can enlarge the process range, it can be used for manufacturing an optical member.

[In order to implement the invention]

The present invention is characterized in that a monomer having a bisaryl fluorene skeleton is used to impart a low dielectric constant property to a film formed of an imprint material containing the material. In other words, the present invention relates to a pressure of a photopolymerization initiator containing a compound having a bisaryl fluorene skeleton as the component (A), a compound having at least one polymerizable group in the molecule, and a component (C) component of the component (C). Printed material. Further, in addition to the components (A), (B) and (C), an imprint material of a solvent of the component (D) may be contained.

The respective components are described in detail below.

<(A) component>

The compound having a bisaryl fluorene skeleton of the component (A) is represented by the following formula (1).

[Chemical 2]

(In the formula, R represents an acrylonitrile group, a methacryloyl group or a vinyl group, A represents an alkylene group, and m and n each independently represent an integer of 0 to 3).

The above alkyl group is, for example, an alkylene group having 1 to 3 carbon atoms. The aforementioned m and n are, for example, 1.

In the present invention, the compound having a bisaryl fluorene skeleton may be used alone, and may impart a low dielectric constant property to a film formed of an imprint material containing the article.

The above compound having a bisaryl fluorene skeleton can be easily obtained from a commercially available product, and is specifically, for example, OGSOL (registered trademark) EA-0200, EA-0500, EA-1000, EA-F5003, and EA-F5503 ( The above is Osaka Gas Chemical Co., Ltd.).

The compound having a bisaryl fluorene skeleton may be used singly or in combination of two or more kinds.

The content of the component (A) in the imprint material of the present invention is preferably 50 to 95 parts by mass, more preferably 70 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B) below. More than the mass. When the ratio is too small, the dielectric property is increased, and the physical properties of the object are not easily obtained.

<(B) component>

The "compound having at least one polymerizable group in the molecule" of the component (B) is a compound having one or more polymerizable groups in one molecule and having the polymerizable group at the molecular terminal. Then, the compound is a monomer, or an oligomer. Further, the polymerizable group means, for example, at least one organic group selected from the group consisting of an acryloxy group, a methacryloxy group, a vinyl group, and an allyl group. Here, the acryloxy group means an acryloxy group, and the methacryloxy group means a methacryloxy group. Further, the number of the polymerizable groups in one molecule of the compound of the component (B) is generally from 1 to 6, and may be more than six.

a compound having at least one polymerizable group of the component (B), for example, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, pentaerythritol tetraacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylol methane tetra Acrylate, tetramethylol methane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-tripropenyl hexahydro-S-three Pyrazine, 1,3,5-trimethylpropenyl hexahydro-S-triazine, cis (hydroxyethyl propylene fluorenyl) isocyanate, cis (hydroxyethyl methacryl oxime) isocyanate, tripropylene fluorenyl Formaldehyde, trimethyl propylene decyl formaldehyde, 1,6-hexane diol acrylate, 1,6-hexanediol methacrylate, neopentyl alcohol diacrylate, neopentyl alcohol dimethacrylate, ethylene Alcohol diacrylate, ethylene glycol II Methacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropyl glycol diacrylate, isopropyl glycol Methacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N, N'-bis(propylene decyl) hemiproline, N, N'-bis (methacryl oxime) Semi-proline, thiodiethylene glycol diacrylate, thiodiethylene glycol dimethacrylate, bisphenol A diacrylate, bisphenol A methacrylate, bisphenol F diacrylate , bisphenol F methacrylate, bisphenol S diacrylate, bisphenoxyethanol oxime dimethacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, maleic acid II Allyl ester, triallyl trimellitate, phenyl methacrylate, 2-phenoxyethyl acrylate, and the like.

The above compound may be taken from a commercially available product, and is specifically, for example, KAYARD (registered trademark) T-1420, the same DPHA, the same DPHA-2C, the same D-310, the same D-330, the same DPCA-20, the same DPCA-30, the same DPCA-60, same as DPCA-120, same DN-0075, same DN-2475, same R-526, same NPGDA, same PEG400DA, same MANDA, same R-167, same HX-220, same HX620, same R-551 , with R-712, with R-604, with R-684, with GPO-303, with TMPTA, with THE-330, with TPA-320, with TPA-330, with PET-30, with RP-1040 (above It is manufactured by Nippon Kayaku Co., Ltd.), ARONIX (registered trademark) M-210, the same M-240, the same M-6200, the same M-309, the same M-400, the same M-402, the same M-405, the same M-450, the same M-7100, the same M-8030, the same M-8060, the same M-1310, the same M-1600, the same M-1960, the same M-8100, the same M-8530, the same M-8560, the same M-9050 (the above is manufactured by Toagosei Co., Ltd.), VISCOSE295, the same 300, the same 360, the same GPT, the same 3PA, the same 400, the same 260, the same 312, the same 335HP (the above is made by Osaka Organic Chemical Industry Co., Ltd. )Wait.

The component (B) may be, for example, a mixture of a compound having five polymerizable groups in one molecule and a compound having six such polymerizable groups. Further, the above compounds may be used singly or in combination of two or more kinds.

The component (B) can achieve a viscosity-adjusting effect of a compound having a bisaryl fluorene skeleton of the component (A) having high viscosity.

In addition, the content of the component (B) in the imprint material of the present invention is preferably 50 to 5 parts by mass, more preferably 10 parts by weight based on 100 parts by mass of the total of the components (A) and (B). More than the mass. When the ratio is too large, the dielectric constant increases, and when the ratio is too small, the handleability is deteriorated.

<(C) component>

A photopolymerization initiator of the component (C), for example, 3-butylpentyloxy-isobutyrate, 2,5-dimethyl-2,5-bis(benzidinedioxo)hexane, 1 , 4-bis[α-(3-butyldioxo)-isopropoxy]benzene, di-tert 3-butyl, 2,5-dimethyl-2,5-bis (p. 3-butyldioxo)hexene hydroperoxide, α-(isopropylphenyl)-isopropyl hydroperoxide, 2,5-dimethylhexane, 3-butyl hydroperoxide, 1,1-bis(3-butyldioxo)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(3-butyldioxo)valerate , cyclohexanone peroxide, 2,2',5,5'-tetra (3-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra (3-butyl Peroxycarbonyl)benzophenone, 3,3',4,4'-tetra(3-pentylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra (3- Hexylperoxycarbonyl)benzophenone, 3,3'-bis(3-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, 3-butylperoxybenzoate , an organic peroxide such as di-tert-butyl diperoxyphthalate, or 9,10-fluorene, 1-pyridinium chloride, 2-barium chloride, octamethylguanidine醌, 1,2-benzopyrene, etc. Or a benzoin derivative such as benzoin methyl, benzoin ether, α-methyl benzoine, α-phenyl benzoine, etc., 2,2-dimethoxy-1,2-di Phenylethane-1-one, 1-hydroxy-cyclohexyl-benzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxyl) -Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propenyl)benzene Methyl}-phenyl]-2-methyl-propan-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-(methylthio)phenyl]-2-? Lolinylpropan-1-one, 2-benzyl-2-oxomethyl-1-(4-morpholinylphenyl)-butanone-1,2-dimethylamino-2-( 4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, bis(2,4,6-trimethylbenzylidene)- Phenylphosphine oxide, 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-2-(o -benzimidoxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-B醯肟), etc., as long as the light source used in photohardening has an absorber, there is no particular limitation.

The above compounds may be taken from commercially available products, and are specifically, for example, IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379 EG, 819, and 819DW, the same 1800, the same 1870, the same 784, the same OXE01, the same OXE02, the same 250, DAROCUR (registered trademark) 1173, the same MBF, the same TPO, the same 4265 (above is Chiba‧Japan Co., Ltd.), KAYACURE (registered Trademark) DETX, same MBP, same DMBI, same EPA, same OA (above is made by Nippon Kayaku Co., Ltd.), VICURE-10, same 55 (above is STAUFFER Co.LTD), ESACURE KIP150, same TZT, same 1001, same as KT046, the same KB1, the same KL200, the same KS300, the same EB3, triazine-PMS, triazine A, triazine B (above is made by Japan DKSH Co., Ltd.), ADEKA OPTOMER N-1717, the same N-1414 And N-1606 (made by ADEKA Co., Ltd. (made by the old Asahi Electronics Co., Ltd.)).

These photopolymerization initiators may be used singly or in combination of two or more kinds.

The content of the component (C) in the imprint material of the present invention is preferably 0.5 phr to 30 phr, more preferably 1 phr to 20 phr, based on the total mass of the component (A) and the component (B). When the ratio is 0.1 phr or less, sufficient hardenability cannot be obtained, and the pattern characteristics are deteriorated. Here, phr means the mass of the photopolymerization initiator with respect to 100 g of the total mass of (A) component and (B) component.

<(D) component>

In the present invention, a solvent may also be contained as the component (D).

The solvent of the component (D) can achieve the viscosity-adjusting effect of the compound having a bisaryl fluorene skeleton of the component (A).

The aforementioned solvent such as toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, Diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate , diethylene glycol, 1-octanol, ethylene glycol, hexanediol, diacetone alcohol, furanol, tetrahydrofuranol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropanone, diethyl ketone, methyl isobutyl ketone, methyl-n-butanone, cyclohexanone, 2-glycol Ketone, ethyl acetate, isoamyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, 3-butanol, allyl alcohol, n-propanol , 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol , 1-octanol, ethylene glycol, hexanediol, trimethyl glycol, 1-methoxy-2-butanol, diacetone alcohol, furanol, tetrahydrofuranol, propylene glycol, benzyl alcohol, isopropyl ether, 1, 4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl The hydrazine, N-cyclohexyl-2-pyrrolidone, and the like are not particularly limited as long as the viscosity of the component (A) can be adjusted.

However, in the case of a compound having a bisaryl fluorene skeleton, a compound having at least two polymerizable groups in the molecule, and a photopolymerization initiator, the solvent is propylene glycol monomethyl ether acetate or propylene glycol monomethyl ether. , γ-butyrolactone, N-methylpyrrolidone, methanol, ethanol, isopropanol, butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, propylene glycol, hexanediol , methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dicyclohexyl Ketone, methyl acetate, ethyl acetate, and the like.

These solvents may be used singly or in combination of two or more kinds.

The imprint material of the present invention may contain a photosensitizer, an ultraviolet absorber, an antioxidant, a surfactant, a adhesion aid, etc. as long as it does not impair the effects of the present invention.

The photo sensitizer is, for example, a thioxan system, a xanthene system, a ketone system, a thiopyranium salt, a basic styrene group, a phthalocyanine system, a 3-substituted coumarin system, and a 3,4-substituted coumarin system. , quinoline blue, acridine, thiazine, phenazine, anthraquinone, benzophenone, benzoxanthene, anthraquinone, ketocoumarin, lavender, boric acid ester, and the like.

These photosensitizers may be used singly or in combination of two or more kinds. The wavelength of the UV range can also be adjusted by using the photosensitizer.

The ultraviolet absorbers are, for example, TINUVIN (registered trademark) PS, the same 99-2, the same 109, the same 328, the same 384-2, the same 400, the same 405, the same 460, the same 477, the same 479, the same 900, the same 928, Same as 1130, the same 111FDL, the same 123, the same 144, the same 152, the same 292, the same 5100, the same 400-DW, the same 477-DW, the same 99-DW, the same 123-DW, the same 5050, the same 5060, the same 5151 ( The above is Chiba ‧ Japanese shares have companies) and so on.

These ultraviolet absorbers can be used alone or in combination of two or more. By using the ultraviolet absorber, the hardening speed of the outermost surface of the film at the time of photohardening can be controlled, and the mold release property can be improved.

The antioxidants are, for example, IRGANOX (registered trademark) 1010, 1035, 1076, 1135, and 1520L (above, Chiba‧ Japan Co., Ltd.).

These antioxidants may be used singly or in combination of two or more kinds. By using the antioxidant, it is possible to prevent yellowing of the film due to oxidation.

The above surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyethylene oxide acetophenone, polyoxyethylene ether ether, and the like, polyoxyethylene alkyl ethers, polyoxyethylene octyl phenol ether, polyethylene oxide Polyoxyethylene alkyl ether allyl ethers of polydecyl phenol ethers, polyethylene oxide ‧ propylene oxide block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan Sorbitan fatty acid esters such as monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan Monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan III A nonionic surfactant such as a polyoxyethylene sorbitan fatty acid ester such as stearate, and the trade name EFTOP (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronics Co., Ltd. (old JEMCO shares limited) Company system)), goods MEGAFAC (registered trademark) F171, F173, R-08, R-30 (made by DIC Corporation), FLUORAD FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade name ASASHIGUARD (registered trademark) AG710, SURFLON S- 382, fluorine-based surfactant such as SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), and organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302 , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by BYK‧JAPAN Co., Ltd.), etc.

The above surfactants may be used singly or in combination of two or more kinds. When the surfactant is used, the ratio thereof is preferably from 0.01 phr to 10 phr, more preferably from 0.01 phr to 5 phr, based on the total mass of the component (A) and the component (B).

The adhesion aid is, for example, 3-methacryloxypropyltrimethoxydecane or 3-propenyloxypropyltrimethoxydecane. By using the adhesion aid, the adhesion to the substrate can be improved. The content of the adhesion aid is preferably from 5 phr to 50 phr, and more preferably from 10 phr to 50 phr, based on the total mass of the component (A) and the component (B).

The preparation method of the imprint material of the present invention is not particularly limited as long as the components (A), (B), (C), and (D) are uniformly mixed. Further, the order of mixing the components (A) to (D) is not particularly limited as long as a uniform solution can be obtained. This preparation method is, for example, a method of mixing the component (B) and the component (C) in a specific ratio in the component (A). Further, for example, a method in which the component (D) is mixed and a uniform solution is formed. Further, in an appropriate stage of the preparation method, a method of mixing other additives may be added as needed.

In addition, when the solvent of the component (D) is used, at least one of the film before the light irradiation and the film after the light irradiation may be subjected to a baking treatment for the purpose of evaporating the solvent. The firing machine is not particularly limited. For example, a hot plate, an oven, or an oven can be used, and it can be baked in an appropriate gas atmosphere, that is, an inert gas such as air or nitrogen, or a vacuum. The firing temperature is not particularly limited as long as it evaporates the solvent, and can be carried out, for example, at 40 to 200 °C.

The embossing material of the present invention can be applied to a substrate to be photocured, and then heated as needed to obtain a desired film. The coating method is, for example, a conventional or well-known method such as a spin coating method, a dipping method, a flow coating method, a spray method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method. Method, transfer method, brush coating method, blade coating method, air knife coating method, and the like.

In order to apply the imprint material of the present invention, for example, a glass having tantalum, indium tin oxide (ITO) film (hereinafter referred to as "ITO substrate"), and a glass film formed with tantalum nitride (SiN), A film formed of indium zinc oxide (IZO) glass, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics or the like is formed. Further, a flexible substrate having flexibility can also be used.

The light source for hardening the imprint material of the present invention is not particularly limited, and is, for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a KrF excimer laser, an ArF excimer laser, an F ₂ excimer laser, an electron beam ( EB), extreme ultraviolet (EUV), etc. Further, in general, a wavelength of 436 nm G line, 405 nm H line, 365 nm I line, or GHI hybrid line can be used. Further, the exposure amount is preferably 30 to 2000 mJ/cm ^{2 and} preferably 30 to 1000 mJ/cm ² .

The apparatus for performing photoimprinting is not particularly limited as long as it is a target pattern, and for example, ST50 of Toshiba Machine Co., Ltd., Sindre (registered trademark) 60 manufactured by Obducat, NM-0801HB manufactured by Mingchang Machinery Co., Ltd., etc. Commercially available device.

The mold material used in the photoimprint used in the present invention, for example, quartz, rhodium, nickel, carbonyl decane, glass graphite, or the like, is not particularly limited as long as it is a target image. Further, when the mold is used to improve the mold release property, a mold release treatment for forming a film of a fluorine-based compound or the like on the surface thereof can be performed. The release agent to be used for the release treatment, for example, OPTOOL (registered trademark) HD manufactured by DAIKIN INDUSTRIAL CO., LTD., is not particularly limited as long as it is a target pattern.

When the pattern of the optical embossing is selected and the pattern of the electronic device suitable for the purpose is selected, the pattern size is also used as a reference. The pattern size is, for example, nanometer and micrometer.

In the following, the invention will be described in more detail by way of examples and comparative examples, but the invention is not limited by the examples.

[Examples]

[Preparation of coating liquid for film formation]

<Example 1>

KAYARAD (registered trademark) neopentyl glycol diacrylate (Nippon Chemical Co., Ltd.) is added to 10g of OGSOL (registered trademark) EA-0200 (made by Osaka Gas Chemical Co., Ltd.) (hereinafter referred to as "OGSOL"). (hereinafter referred to as "NPGDA") 2.5g (25 parts by mass relative to 100 parts by mass of OGSOL), IRGACURE (registered trademark) OXE01 (manufactured by Chiba‧ Japan Co., Ltd.) (hereinafter referred to as "OXE01") 0.62g (The total mass of OGSOL and NPGDA is 5 phr), and the imprinting material PNI-1 was prepared.

<Example 2>

The imprint material PNI-2 was prepared in the same manner except that NPGDA of Example 1 was changed to pentaerythritol triacrylate (manufactured by ALDRICH Co., Ltd.) (hereinafter abbreviated as "PTA").

<Example 3>

To the PNI-1 obtained in Example 1, 13.1 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") was added to prepare an imprint material PNI-3.

<Example 4>

To the PNI-2 obtained in Example 2, 13.1 g of PGMEA was added to prepare an imprint material PNI-4.

<Comparative Example 1>

The imprint material PNI-a was prepared by adding 0.5 g of OXE01 (5 phr relative to NPGDA) to 10 g of NPGDA.

<Comparative Example 2>

The imprint material PNI-b was prepared in the same manner except that the NPGDA of Comparative Example 1 was changed to PTA.

<Comparative Example 3>

The imprint material PNI-c was similarly prepared except that the OGSOL of Example 1 was changed to PTA.

<Comparative Example 4>

To the PNI-a obtained in Comparative Example 1, 10.5 g of PGMEA was added to prepare an imprint material PNI-d.

<Comparative Example 5>

To the PNI-b obtained in Comparative Example 2, 10.5 g of PGMEA was added to prepare an imprint material PNI-e.

<Comparative Example 6>

To the PNI-c obtained in Comparative Example 3, 10.5 g of PGMEA was added to prepare an imprint material PNI-f.

[Production of film for photoimprint]

The PNI-1 obtained in Example 1 was spin-coated on a quartz substrate to prepare a film for photoimprint (PNI-1F).

The PNI-2 obtained in Example 2 was spin-coated on a quartz substrate to prepare a film for photoimprint (PNI-2F).

The PNI-3 obtained in Example 3 was spin-coated on a quartz substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute to obtain a film for photoimprint (PNI-3F).

The PNI-4 obtained in Example 4 was spin-coated on a quartz substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute to obtain a film for photoimprint (PNI-4F).

The PNI-a obtained in Comparative Example 1 was spin-coated on a quartz substrate to prepare a film for photoimprint (PNI-aF).

The PNI-b obtained in Comparative Example 2 was spin-coated on a quartz substrate to prepare a film for photoimprint (PNI-bF).

The PNI-c obtained in Comparative Example 3 was spin-coated on a quartz substrate to prepare a film for photoimprint (PNI-cF).

The PNI-d obtained in Comparative Example 4 was spin-coated on a quartz substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute to obtain a film for photoimprint (PNI-dF).

The PNI-e obtained in Comparative Example 5 was spin-coated on a quartz substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute to obtain a film for photoimprint (PNI-eF).

The PNI-f obtained in Comparative Example 6 was spin-coated on a quartz substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute to obtain a film for photoimprint (PNI-fF).

The nanoimprinting apparatus uses NM-0801HB (manufactured by Mingchang Machinery Co., Ltd.).

Each of the photoimprint coating films obtained in Examples 1 to 4 and Comparative Examples 1 to 6 was subjected to a patterning test. The mold used was tantalum and the pattern was 120 nm line and pitch. The mold was immersed in OPTOOL (registered trademark) HD (manufactured by DAIKIN Industrial Co., Ltd.) beforehand, and treated with a high-temperature and high-humidity apparatus having a temperature of 90 ° C and a humidity of 90 RH % for 2 hours, and rinsed with pure water to obtain air. Dryer.

In the state in which the enamel mold was bonded to the PNI-1F produced by the PNI-1 obtained in Example 1, it was placed on a photoimprinting apparatus. The photoimprinting treatment is carried out under the conditions of 23 ° C at normal time, a) pressurization for 10 seconds until 1000 N, b) exposure with 500 mJ/cm ² using a high pressure mercury lamp, c) depressurization for 10 seconds, d) The mold is separated from the substrate and released from the substrate in this order. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that PNI-2F produced by PNI-2 obtained in Example 2 was used. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that PNI-3F produced by PNI-3 obtained in Example 3 was used. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that PNI-4F produced by PNI-4 obtained in Example 4 was used. The results of the photoimprint process are shown in Table 1.

The photoimprint treatment was carried out in the same manner as described above except that the PNI-aF produced by the PNI-a obtained in Comparative Example 1 was used. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that PNI-bF produced by PNI-b obtained in Comparative Example 2 was used. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that the PNI-cF produced by the PNI-c obtained in Comparative Example 3 was used. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that the PNI-dF produced by the PNI-d obtained in Comparative Example 4 was used. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that PNI-eF produced by PNI-e obtained in Comparative Example 5 was used. The results of the photoimprint process are shown in Table 1.

A photo imprint process was performed in the same manner as described above except that the PNI-fF produced by the PNI-f obtained in Comparative Example 6 was used. The results of the photoimprint process are shown in Table 1.

In Table 1, "photohardening treatment" refers to a case where it is evaluated whether or not the film is cured after exposure, "○" means hardened, and "x" means that it is not cured. "Peeling" means evaluating whether or not a part of the pattern is peeled off from the mold or the like due to mold release, and "○" means that it is not peeled off, and "X" means that it is peeled off. The "shape" means that the mold pattern on the film after demolding is evaluated to be well transferred, ○ indicates good transfer, and × indicates that it is not well transferred.

As is clear from the results of Table 1, in Examples 1 to 4, a pattern can be formed at the time of good photoimprint. Further, in Comparative Examples 1 to 6, although the film was cured by exposure, only part of the pattern was peeled off during demolding, and the pattern of the mold on the film after demolding was not well transferred.

From the above results, it is understood that the composition of the imprint material which forms a low dielectric constant film which is excellent in photoimprint treatment must have the component (A): a compound having a biaryl fluorene skeleton represented by the above formula (1). (B) component: a compound which has at least two polymerizable groups in a molecule, and (C) component: a photoinitiator is not clear. In addition, it may contain (D) component: solvent, and it is not clear.

[Measurement of dielectric constant]

The dielectric constant was measured by a vacuum of PROVA MJ-10 (manufactured by Measure Jig Co., Ltd.) and an AG-4311B LCR Meter (manufactured by Ando Electric Co., Ltd.) at a cycle number of 100 kHz.

The PNI-1 obtained in Example 1 was spin-coated on an ITO substrate, and the quartz substrate was coated thereon, and a) pressure was applied for 10 seconds to 1000 N at a constant temperature of 23 ° C, and b) using a high-pressure mercury lamp. Exposure at 500 mJ/cm ² , c) Depressurization for 10 seconds, d) Separating the mold from the substrate and releasing the mold, forming a photo-cured film on the ITO substrate, cutting a portion of the film, and peeling off the ITO. Then, aluminum was vapor-deposited on the ITO which was not peeled off and on the cured film with a diameter of 1 mm and a thickness of 0.1 μm, and was brought into contact with the probe to measure the dielectric constant. The results are shown in Table 2.

The dielectric constant was measured in the same manner as described above except that PNI-2 obtained in Example 2 was used. The results are shown in Table 2.

The PNI-3 obtained in Example 3 was spin-coated on an ITO substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute, and the quartz substrate was coated thereon, and a) was pressed in the order of 23 ° C at room temperature. 10 seconds up to 1000N, b) exposure of 500mJ/cm ² using a high-pressure mercury lamp, c) depressurization for 10 seconds, d) separating the mold from the substrate, and preparing a photo-cured film on the ITO substrate in this order, The pseudo-firing treatment was performed for 1 minute on a hot plate at 200 °C. A portion of the film was taken and the ITO was peeled off. Then, aluminum was vapor-deposited on the ITO which was not peeled off and on the cured film with a diameter of 1 mm and a thickness of 0.1 μm, and was brought into contact with the probe to measure the dielectric constant. The results are shown in Table 2.

The dielectric constant was measured in the same manner as described above except that PNI-4 obtained in Example 4 was used instead of PNI-3. The results are shown in Table 2.

The PNI-a obtained in Comparative Example 1 was spin-coated on the ITO substrate, and the quartz substrate was coated thereon, and was subjected to a) pressurization for 10 seconds to 1000 N in a normal condition of 23 ° C, and b) 500 mJ using a high pressure mercury lamp. /cm ² exposure, c) except for pressing for 10 seconds, d) separating the mold from the substrate, preparing a photo-cured film on the ITO substrate in this order, cutting a part of the film, and peeling off the ITO. Then, aluminum was vapor-deposited on the ITO which was not peeled off and on the cured film with a diameter of 1 mm and a thickness of 0.1 μm, and was brought into contact with the probe to measure the dielectric constant. The results are shown in Table 2.

The dielectric constant was measured in the same manner as described above except that PNI-b obtained in Comparative Example 2 was used. The results are shown in Table 2.

The dielectric constant was measured in the same manner as described above except that PNI-c obtained in Comparative Example 3 was used. The results are shown in Table 2.

The PNI-d obtained in Comparative Example 4 was spin-coated on an ITO substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute, and the quartz substrate was coated thereon, and then subjected to a condition of 23 ° C at a constant pressure. 10 seconds up to 1000N, b) exposure of 500mJ/cm ² using a high-pressure mercury lamp, c) depressurization for 10 seconds, d) separating the mold from the substrate, and preparing a photo-cured film on the ITO substrate in this order, The pseudo-firing treatment was performed for 1 minute on a hot plate at 200 °C. A portion of the film was taken and the ITO was peeled off. Then, aluminum was vapor-deposited on the ITO which was not peeled off and on the cured film with a diameter of 1 mm and a thickness of 0.1 μm, and was brought into contact with the probe to measure the dielectric constant. The results are shown in Table 2.

The dielectric constant was measured in the same manner as described above except that PNI-e obtained in Comparative Example 5 was used instead of PNI-d. The results are shown in Table 2.

The dielectric constant was measured in the same manner as described above except that PNI-f obtained in Comparative Example 6 was used instead of PNI-d. The results are shown in Table 2.

As is clear from the results of Table 2, in Examples 1 to 4, a film having a low dielectric constant can be formed. Further, in Comparative Examples 1 to 6, as compared with Examples 1 to 4, the dielectric constant was high.

From the above results, it is understood that the film obtained by the imprint material of the present invention has a low dielectric constant of 3.0 or less.

[Measurement of transmittance]

For the measurement of the transmittance, UV-2550 UV-VISIBLE SPECTROPHOTOMETER (manufactured by Shimadzu Corporation) was used to obtain a transmittance of a sample having a wavelength of 400 nm and a film thickness of 1 μm.

The PNI-1 obtained in Example 1 was spin-coated on a quartz substrate, and the quartz substrate was coated thereon, followed by a) pressurization for 10 seconds up to 1000 N in a normal condition of 23 ° C, and b) 500 mJ using a high pressure mercury lamp. Exposure of /cm ² , c) Depressurization for 10 seconds, d) Separating and releasing the coated quartz substrate from the lower quartz substrate, and preparing a photocured film on the quartz substrate in this order, and measuring the transmittance. The results are shown in Table 3.

A photocured film was formed on a quartz substrate in the same manner as described above except that PNI-2 obtained in Example 2 was used, and the transmittance was measured. The results are shown in Table 3.

PNI-3 obtained in Example 3 was spin-coated on a quartz substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute. Then, the quartz substrate was coated thereon, and a) pressure was applied for 10 seconds up to 1000 N in a normal condition of 23 ° C, b) exposure was performed at 500 mJ/cm ² using a high pressure mercury lamp, c) depressurization was performed for 10 seconds, d The coated quartz substrate was separated and released from the quartz substrate on the lower side, and a photocured film was formed on the quartz substrate in this order, and then fired at a hot plate of 200 ° C to measure the transmittance. The results are shown in Table 3.

A photocured film was formed on a quartz substrate in the same manner as described above except that PNI-4 obtained in Example 4 was used instead of PNI-3, and the transmittance was measured. The results are shown in Table 3.

PNI-a obtained in Comparative Example 1 was spin-coated on a quartz substrate, and other quartz substrates were coated thereon, and a) pressure was applied for 10 seconds to 1000 N in a normal condition of 23 ° C, and b) a high-pressure mercury lamp was used. The exposure was performed at 500 mJ/cm ² , c) the pressure was removed for 10 seconds, d) the coated quartz substrate was separated and released from the quartz substrate on the lower side, and a photo-cured film was formed on the quartz substrate in this order to measure the transmittance. . The results are shown in Table 3.

A photocured film was formed on a quartz substrate in the same manner as described above except that PNI-b obtained in Comparative Example 2 was used, and the transmittance was measured. The results are shown in Table 3.

A photocured film was formed on a quartz substrate in the same manner as described above except that PNI-c obtained in Comparative Example 3 was used, and the transmittance was measured. The results are shown in Table 3.

The PNI-d obtained in Comparative Example 4 was spin-coated on a quartz substrate, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute. Then, the other quartz substrates were coated, and a) pressure was applied for 10 seconds to 1000 N in a normal condition of 23 ° C, b) exposure was performed at 500 mJ/cm ² using a high pressure mercury lamp, and c) depressurization was performed for 10 seconds, d) The coated quartz substrate was separated from the quartz substrate on the lower side to be released from the mold, and a photocured film was formed on the quartz substrate in this order, and then fired at a hot plate of 200 ° C to measure the transmittance. The results are shown in Table 3.

A photocured film was formed on a quartz substrate in the same manner as described above except that PNI-e obtained in Comparative Example 5 was used instead of PNI-d, and the transmittance was measured. The results are shown in Table 3.

A photocured film was formed on a quartz substrate in the same manner as described above except that PNI-f obtained in Comparative Example 6 was used instead of PNI-d, and the transmittance was measured.

The results are shown in Table 3.

As can be seen from the results of Table 3, high transmittances were achieved in all of Examples 1 to 4 and Comparative Examples 1 to 6.

[Measurement of Refractive Index]

The refractive index was measured by using n&k Technology 1512RT (manufactured by N&K Technology, Inc.) to measure the refractive index at a wavelength of 633 nm.

The PNI-1 obtained in Example 1 was spin-coated on a ruthenium wafer, and the quartz substrate was coated thereon, and was sequentially subjected to a) pressurization for 10 seconds to 1000 N in a normal condition of 23 ° C, and b) using a high pressure mercury lamp. Exposure at 500 mJ/cm ₂ , c) Depressurization for 10 seconds, d) Separation and release of the quartz substrate from the tantalum wafer, fabrication of a photocured film on the tantalum wafer, and measurement of the refractive index. The results are shown in Table 4.

A photocured film was formed on a tantalum wafer in the same manner as described above except that PNI-2 obtained in Example 2 was used, and the refractive index was measured. The results are shown in Table 4.

The PNI-3 obtained in Example 3 was spin-coated on a crucible wafer, and subjected to a pseudo-firing treatment on a hot plate at 100 ° C for 1 minute. Then, the quartz substrate was coated thereon, and a) pressure was applied for 10 seconds up to 1000 N in a normal condition of 23 ° C, b) exposure was performed at 500 mJ/cm ² using a high pressure mercury lamp, c) depressurization was performed for 10 seconds, d The quartz substrate and the tantalum wafer were separated and released, and a photocured film was formed on the tantalum wafer in this order, and subjected to a firing treatment at a hot plate of 200 ° C to measure the refractive index. The results are shown in Table 4.

A photocured film was formed on a tantalum wafer in the same manner as described above except that PNI-4 obtained in Example 4 was used instead of PNI-3, and the refractive index was measured. The results are shown in Table 4.

The PNI-a obtained in Comparative Example 1 was spin-coated on a ruthenium wafer, and the quartz substrate was coated thereon, and a) pressure was applied for 10 seconds to 1000 N in a normal condition of 23 ° C, and b) using a high pressure mercury lamp. Exposure at 500 mJ/cm ² , c) Depressurization for 10 seconds, d) Separation and release of the quartz substrate from the tantalum wafer, fabrication of a photocured film on the tantalum wafer, and measurement of the refractive index. The results are shown in Table 4.

A photocured film was formed on a tantalum wafer in the same manner as described above except that PNI-b obtained in Comparative Example 2 was used, and the refractive index was measured. The results are shown in Table 4.

A photocured film was formed on a tantalum wafer in the same manner as described above except that PNI-c obtained in Comparative Example 3 was used, and the refractive index was measured. The results are shown in Table 4.

The PNI-d obtained in Comparative Example 4 was spin-coated on a tantalum wafer, and subjected to a pseudo-baking treatment on a hot plate at 100 ° C for 1 minute. Then, the quartz substrate was coated thereon, and a) pressure was applied for 10 seconds up to 1000 N in a normal condition of 23 ° C, b) exposure was performed at 500 mJ/cm ² using a high pressure mercury lamp, c) depressurization was performed for 10 seconds, d The quartz substrate and the tantalum wafer were separated and released, and a photo-cured film was formed on the tantalum wafer, and fired at a hot plate of 200 ° C to measure the refractive index. The results are shown in Table 4.

A photocured film was formed on a tantalum wafer in the same manner as described above except that PNI-d was replaced by PNI-e obtained in Comparative Example 5, and the refractive index was measured. The results are shown in Table 4.

A photocured film was formed on a tantalum wafer in the same manner as described above except that PNI-d was replaced by PNI-f obtained in Comparative Example 6, and the refractive index was measured. The results are shown in Table 4.

As is clear from the results of Table 4, in Examples 1 to 4, a film having a high refractive index can be formed. Further, in Comparative Examples 1 to 6, as compared with Examples 1 to 4, there was a result that the refractive index was poor.

From the above results, it is understood that the film obtained by the imprint material of the present invention is formed to have a high refractive index of more than 1.6.

From the above results, it is understood that the film obtained from the imprint material of the present invention has excellent optical embossability, and has a low dielectric constant, a high refractive index, and a high transmittance.

[Industry use value]

The film obtained by the imprint material of the present invention can be suitably used for an electronic device and an optical member such as an interlayer insulating film and/or a gate insulating film of a semiconductor element such as an electric field effect transistor.

Claims (8)

An embossing material comprising (A) component, (B) component, and (C) component, and containing 50 to 95 masses based on 100 parts by mass of the total of the components (A) and (B) (A) component, and 50 to 5 parts by mass of the component (B), (A) component: a compound (B) having a bisaryl fluorene skeleton represented by the following formula (1): at least in the molecule Compound (C) having one polymerizable group: photopolymerization initiator [Chemical Formula 1] (In the formula, R represents an acrylonitrile group, a methacryloyl group or a vinyl group, A represents an alkylene group, and m and n each independently represent an integer of 0 to 3). An imprint material as claimed in claim 1 further contains a solvent as the component (D). The imprinting material of the first aspect of the invention, wherein the component (A) is contained in an amount of 70 parts by mass or more based on 100 parts by mass of the total of the component (A) and the component (B). The embossing material according to any one of claims 1 to 3, wherein the component (B) has a group selected from the group consisting of acryloxy group, methacryloxy group, vinyl group and allyl group. At least one compound which is a polymerizable group. A film having a pattern transferred, which is produced by the imprint material of any one of claims 1 to 4. An optical member characterized by comprising a film having a pattern transferred as in the fifth aspect of the patent application. A semiconductor device characterized by comprising a film having a pattern transferred as in the fifth aspect of the patent application. An electronic device characterized by comprising a film having a pattern transferred as in claim 5 of the patent application.