JP2003175514A - Method for manufacturing mold for molding resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a mold (stamper) for forming a pattern having fine width and height on the surface of a resin. <P>SOLUTION: A metal is laminated on a substrate plate having a resist pattern formed on its surface to form a metal layer which is, in turn, peeled from the substrate plate having the resist pattern formed thereto to manufacture the mold for molding a resin. In this manufacturing method, the resist pattern is formed by forming a pattern on a resist film, which is obtained using a chemical amplifying type resist composition containing a resin and an acid generating agent, by an electron beam. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin molding die, and more specifically, a plastic lens,
A method for manufacturing a metal mold (stamper) for forming a pattern having a large pattern with fine pattern width and pattern space (line and space) on the surface of a resin molding such as a light guide plate or an optical recording medium. Regarding

[0002]

2. Description of the Related Art In recent years, resin moldings having irregularities of about several to 100 .mu.m on their surface have been widely used. For example, as optical components such as a diffraction grating and a pickup lens, those having irregularities such as a prism shape or a Fresnel lens shape on the surface are being used in order to improve the light-collecting property. Further, as a light guide plate of a liquid crystal display device, in order to have a light reflecting function, a light guide plate having irregularities such as V-shaped grooves formed on its surface is being used. Further, unevenness is formed on the surface of an information recording medium such as an optical disc for high density recording. In addition, also in electronic parts, injection molded circuit parts (MID) made of a thermoplastic resin molded body having a circuit formed on the surface and having high heat resistance have been used as injection molded electronic parts.

Such a resin molding having surface irregularities is generally formed by a hot melt molding method such as injection molding, compression molding or blow molding using a mold having a concavo-convex pattern (hereinafter sometimes referred to as a stamper). Being manufactured.
As a method of forming a stamper having a concavo-convex pattern used in such a molding method, currently, a metal thin film is formed on a substrate surface having a photoresist pattern to make it conductive, and then a metal is grown on the metal thin film by plating or the like. A method in which a metal layer having a target thickness is obtained and then the substrate is peeled to obtain a mold is widely adopted (Japanese Patent Laid-Open No. 9-222).
514, etc.). The photoresist pattern used to obtain a mold is obtained by forming a photoresist film on a substrate, exposing it to light such as ultraviolet rays, and then developing it.

In recent years, the uneven pattern of a stamper used for manufacturing an optical component such as a lens or a light guide plate has a difference in height of undulations of 10 μm or more, that is, a large uneven pattern having a step of 10 μm or more. Is required. While it is required to increase the unevenness in this way, the required pattern shape becomes complicated and fine lines
Microfabrication that requires and space (high resolution) has become important. Therefore, when manufacturing a die by the above-mentioned method, it is necessary to obtain high resolution with a thick photoresist film in order to meet these requirements.
However, in the pattern formation by light, the attenuation and distortion of the light beam incident on the photoresist film increases as it goes in the depth direction of the film. Therefore, even if the thick photoresist film is irradiated (exposed) with light, the pattern shape as designed cannot be obtained.

[0005]

In the semiconductor manufacturing, electron beams are widely used as a possible radiation source in a fine processing technique for obtaining a submicron order pattern. However, when a fine resist pattern for semiconductor production is obtained by drawing an electron beam, the thickness of the resist film used is usually as thin as 1 μm or less. Therefore, the electron beam resist composition is designed for use with a thin film thickness. Even if a resist film having a large film thickness is formed using such an electron beam resist composition, a good pattern shape may not be obtained in some cases. In fact, the inventors of the present invention have found that when a non-chemically amplified resist composition developed with a developer containing an organic solvent is used to form a resist film having a large film thickness, in the case of giving a negative pattern, the pattern swells. Occurs, and sufficient resolution cannot be obtained (that is,
It has been confirmed that, in the case of giving a positive pattern, fine resist cannot be finely processed), and a crack is formed in the resist film at the time of electron beam drawing or development, and a good pattern cannot be obtained.

Based on such knowledge, as a result of extensive studies to obtain a stamper having a pattern with large unevenness, when a chemically amplified resist composition is used to form a pattern by electron beam drawing, a good shape can be obtained even with a thick film thickness. It was found that a high-resolution resist pattern can be obtained by the above, and the present invention has been completed.

[0007]

Thus, according to the present invention, a metal is laminated on a substrate having a resist pattern formed on the surface to form a metal layer, and then the metal layer is formed with a resist pattern. A method for producing a resin molding die by peeling from a substrate, wherein the resist pattern is obtained by using a chemically amplified resist composition containing a resin and an acid generator to form a resist film with an electron beam. There is provided a method for producing a resin-molding die which is formed by drawing the above, and a resin-molding die produced by the method is provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present invention, the mold is a metal layer obtained by laminating a metal on a substrate on which a resist pattern is formed to form a metal layer, and then peeling off the substrate and the metal layer. The method of forming the mold is such that a resist pattern is formed on the substrate by the method described below, a metal is laminated on the substrate on which the resist pattern is formed to form a metal layer, and then a substrate on which the resist pattern is formed is used. It is a general method, for example, a method of peeling the metal layer by a physical force such as peeling. The thickness of the metal to be laminated on the substrate is not particularly limited as long as it is the thickness required for the target mold.

The method for laminating the metal is not particularly limited. For example, a metal thin film layer is formed on the surface of a substrate having a resist pattern by a conventional method such as a sputtering method, an electroless plating method, a vacuum deposition method, and the like. A method of growing a plating on the metal thin film layer by an ordinary method such as electrolytic plating until the plating has an arbitrary thickness. According to this method, a die can be efficiently obtained, and a fine pattern can be accurately reflected on the die, which is preferable. The metal used as the material of the metal thin film and the metal used as the raw material for plating grown by electrolytic plating or the like may be the same or different. There are no special restrictions on either metal, but for example nickel, gold,
Platinum, palladium, silver, titanium, tantalum, chromium, copper, cobalt and other metals (preferably nickel)
, Nickel-copper, nickel-cobalt, nickel-
Examples include alloys of silver, nickel-gold, nickel-chromium, silver-silicon and the like. The thickness of the metal thin film layer may be any thickness as long as the metal thin film layer functions as a conductive layer necessary for electrolytic plating to be performed next, and is usually several Å to 10 μm.
The thickness of the plating grown on the metal thin film layer may be such that the sum of the thickness of the metal thin film and the thickness of the metal thin film corresponds to the required die thickness. After separating the substrate and the mold, the resist pattern remaining on the mold may be removed by washing with an organic solvent or the like capable of dissolving the resist pattern such as tetrahydrofuran.

The resist pattern used for forming the mold will be described in detail below. The resist pattern used in the present invention is obtained by using a chemically amplified resist composition (hereinafter sometimes simply referred to as a resist or a resist composition). The resist pattern is formed by drawing an electron beam.

The resist composition used for forming the resist pattern in the present invention is applied to the resist developing solution by an acid generator which is a compound which generates an acid upon irradiation with ionizing radiation and a catalytic reaction of the acid derived from the acid generator. It is a so-called chemically amplified resist composition containing a solvent that changes solubility. This resist composition contains a crosslinking agent, a dissolution inhibitor, and other components as necessary. A resist composition containing a resin, an acid generator, and a cross-linking agent is preferred because cracks are less likely to occur in the pattern.

The resin used in the resist composition is an alkali-soluble phenol resin having a phenolic hydroxyl group. As the alkali-soluble phenol resin, for example,
Novolac resin, which is a condensation reaction product of phenols with aldehydes and ketones; vinylphenol resin obtained by polymerization of vinylphenols, if necessary, together with other monomers copolymerizable with vinylphenols; And the like are preferable examples. The resin may be used alone or in combination of two or more.

Specific examples of phenols as raw materials for novolac resins include phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, and 2 , 5-dimethylphenol, 2,3
Examples include 5-trimethylphenol and 2,3,6-trimethylphenol. These may be used alone or in combination of two or more.

Specific examples of the aldehydes used as the raw material for the novolac resin include formalin, paraformaldehyde, hydroxybenzaldehyde and the like. These may be used alone or in combination of two or more. Specific examples of the ketones that are raw materials of the novolac resin include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, and the like. These may be used alone or in combination of two or more. The novolak resin can be obtained by a conventional method, for example, by reacting a phenol with an aldehyde or a ketone in the presence of an acidic catalyst such as oxalic acid.

Vinylphenols which are raw materials of vinylphenol resin include 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene and α-methyl-
4-hydroxystyrene, α-methyl-3-hydroxystyrene, α-methyl-2-hydroxystyrene, 4-
Hydroxy-3-methylstyrene, 2-hydroxy-4
-Methylstyrene and the like.

Other monomers copolymerizable with vinylphenols, which are raw materials for the vinylphenol resin, include styrene, α-methylstyrene, 2-methylstyrene and 4-methylstyrene.
Methylstyrene, 3-ethylstyrene, 4-propylstyrene, 3-isopropylstyrene, 4-chlorostyrene, 3-methyl-α-methylstyrene, 4-methyl-α
-Methylstyrene, 4-ethyl-α-methylstyrene,
Styrenes such as 3-chloro-α-methylstyrene, 2,4-dimethylstyrene, 2-methyl-4-ethylstyrene, 2-chloro-4-methylstyrene; acrylic acid,
(Meth) acrylic acids such as methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacryl Butyl acid, amyl methacrylate, 2-ethylhexyl methacrylate,
(Meth) acrylic acid esters such as hydroxypropyl methacrylate and lauryl methacrylate; acrylonitrile, methacrylonitrile; and the like. Among these, styrenes are preferable because they give a good pattern. The ratio of such other monomer used for copolymerization to vinylphenols is 50% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight from the viewpoint of ensuring proper solubility in a developing solution. It is less than or equal to weight%.

The vinylphenol resin can be obtained by copolymerizing vinylphenols and other monomers added as necessary in the presence of a polymerization initiator such as azobisisobutyronitrile according to a conventional method. In addition, vinylphenol, such as acetoxystyrene or t-butoxystyrene, whose phenolic hydroxyl group is protected by a group (protective group) whose bond is cleaved by an alkali or an acid is used as a monomer. It is used as a vinylphenol precursor protected with a group (protecting group) whose bond is cleaved with, and azobisisobutyronitrile or butyllithium is used as a polymerization initiator, and a homopolymer or other monomer is added according to a conventional method. It can also be synthesized by synthesizing the above copolymer and then deprotecting it with an aqueous alkaline solution such as aqueous ammonia or an aqueous sodium hydroxide solution or an acid such as hydrochloric acid. The vinylphenol resin may be, for example, a hydrogenated vinylphenol resin obtained by dissolving the above-mentioned phenol resin in an organic solvent and partially hydrogenating it in the presence of a homogeneous or heterogeneous catalyst.

The hydrogen atom of the phenolic hydroxyl group of these resins and the hydrogen atom of the carboxylic acid are t-butyl groups,
t-amyl group, 1,1-dimethyl-2-propenyl group,
t-butoxycarbonyl group, t-amyloxycarbonyl group, t-butoxycarbonylmethyl group, t-amyloxycarbonylmethyl group, 1,1-dimethyl-2-propenyloxycarbonylmethyl group, 1-methyl-2-butenyl Substituted with an oxycarbonylmethyl group, a 3-methyl-2-butenyloxycarbonylmethyl group, etc., and introduced an acid labile group (a structure in which the bond is cleaved by an acid to cause solubility in an alkaline aqueous solution). It may be a resin having a dissolution inhibiting effect (Japanese Patent Application Laid-Open No. H8-211613).

The acid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with an electron beam, and may be a generally known acid generator used in a chemically amplified resist composition. For example, diaryl iodonium salts, triaryl sulfonium salts, onium salts such as phenyldiazonium salts, imide sulfonate derivatives, tosylate compounds,
Carbonate compounds of benzyl derivatives, organic halogen compounds such as halides of triazine derivatives, α, α '
Examples thereof include a bis (sulfonyl) diazomethane compound, an α-carbonyl-α-sulfonyldiazomethane compound, a quinonediazidesulfonic acid compound, a sulfone compound, an organic phosphorus ester compound, an organic acid amide compound, and an organic imide compound. Among these, onium salts such as triarylsulfonium salts such as triphenylsulfonium trifluoromethanesulfonate and organic halogen compounds are preferable, and 2- [2- (4-methoxyphenyl) ethenyl is particularly preferable when the resin is a novolac resin. ]-
Organic halogen compounds such as 4,6-bis (trichloromethyl) -S-triazine are preferred. The proportion of such an acid generator is usually 0.1 to 100 parts by weight of the resin.
50 parts by weight, preferably 0.5 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of the acid generator is too small, the resolution may be deteriorated, and conversely, if the amount of the acid generator is too large, the heat resistance may decrease.

The cross-linking agent used as necessary is one that reacts with the resin to form a cross-linking structure between the resins, and is specifically a compound having two or more reactive groups. Such reactive groups include, for example, amino groups, carboxyl groups, hydroxyl groups, epoxy groups, isocyanate groups,
Examples thereof include vinyl group. Specific examples of the cross-linking agent include:
Aliphatic polyamines such as hexamethylenediamine;
Aromatic polyamines such as 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, diaminodiphenylsulfone and phenyldiamine; 4 , 4'-diazidochalcone, 2,6
-Bis (4'-azidobenzal) 4-methylcyclohexanone, 4,4'-diazidodiphenylmethane, 2,
Bisazides such as 2′-diazidostilbene; polyamides such as polyhexamethylenediamine terephthalamide; PL-1170, PL-1174, UFR6
5, CYMEL300, CYMEL303 (above, Mitsui Cytec Co., Ltd.), BX-4000, Nikarac MW-
30, N-alkoxymethylated melamine or N- which is easily available as MX290 (above, manufactured by Sanwa Chemical Co., Ltd.)
Alkoxymethylated glycoluril; EH-100
1, ES-4004, EX-C101, EX-C10
6, EX-C300, EX-C501, EX-020
Epoxy acrylate resins easily available as 2, EX-0205, EX5000 (all manufactured by Kyoei Chemical Co., Ltd.); hexamethylene diisocyanate polyisocyanate; isophorone diisocyanate polyisocyanate; tolylene diisocyanate polyisocyanate;
Examples thereof include hydrogenated diphenylmethane diisocyanate-based polyisocyanate;

Such a crosslinking agent is usually used in an amount of 0.1 to 100 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of the resin.
The amount is 0 parts by weight, more preferably 2 to 30 parts by weight. When the cross-linking agent is in this range, the cross-linking reaction for binding the resins to each other proceeds efficiently, so that the sensitivity and the pattern of the pattern are good.

The dissolution inhibitor which is used as required is such that the hydrogen atom of the phenolic hydroxyl group of the phenol compound is substituted in the same manner as described above and an acid labile group is introduced.
Compounds such as -dimethyl-1,1-di (4-t-butoxycarbonyloxyphenyl) methane (JP-A-6-11)
849, JP-A-6-118650, etc.).

As another component, for example, a surfactant can be contained for the purpose of preventing striation (coating streaks after coating) and improving the pattern shape. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and other polyoxyethylene alkyl ethers; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as oxyethylene dilaurate and polyoxyethylene distearate; Ftop EF301, 303, 352 (manufactured by Shin-Akita Kasei Co.), Megafac F171, F172, Same F173
(Manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-43
0, FC-431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-10.
1, the same SC-102, the same SC-103, the same SC-10
4, fluorine-containing surfactants such as SC-105 and SC-106 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymer K
P341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 5
7 and 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and the like (meth) acrylic acid copolymer type surfactants. The surfactants may be used alone or in combination of two or more.

After the electron beam drawing, a heat treatment (PEB treatment: Post Exposure Ba) described later is performed.
dimensional stability (P)
To obtain (ED resistance), a basic compound can be added to the resist composition. Examples of the basic compound include alkylamines such as ethylamine, propylamine, butylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tripropylamine and tributylamine; arylamines such as phenylamine, diphenylamine and triphenylamine; Alkanolamines such as ethanolamine, diethanolamine and triethanolamine; and the like. In addition, a sensitizer, a storage stabilizer, a dye and the like can be added.

The resist composition used in the present invention is usually
It is used as a solution dissolved in a solvent. The solvent is not particularly limited as long as it dissolves each of the components described above, for example, alcohols such as propanol and butanol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monoethyl ether (ethyl cellosolve), Glycol ethers such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether; ethylene glycol monoethyl ether acetate ( Ethyl cellosolve acetate),
Glycol ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol propyl ether acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl- Ketones such as 2-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3. -Methyl methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate,
Esters such as ethyl acetate, butyl acetate, ethyl lactate;
Examples of the aprotic polar solvent include N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, and N, N-dimethylacetamide. Among these, glycol ether acetates and ketones are preferable because the coated resist film has good uniformity.

The total solid content of the resist composition obtained by mixing the above-mentioned components is preferably adjusted to 5 to 40% by weight from the viewpoint of easiness of resist film formation. The resist composition may be used after removing foreign matters and the like by using a filter having a thickness of about 0.2 to 5 μm.

In order to obtain a resist pattern, first, the resist composition described above is applied to a substrate and dried to form a resist film. As the substrate, any substrate convenient for obtaining a desired resist pattern may be used, and examples thereof include a glass plate and a metal plate. The surface of the substrate may be polished to obtain a good resist pattern. The method of applying the resist to the substrate may be a general method, for example,
A spray method, a roll coating method, a spin coating method, etc. are mentioned. Then, the obtained coating film is heated (pre-baked: Pre.
-Bake) to obtain a resist film having no fluidity. The heating conditions can be arbitrarily set depending on the type of each component, the mixing ratio, the film thickness, etc.
It is 10-600 seconds at 200 degreeC. The thickness of the resist film formed here may be designed in consideration of the required height of the resist pattern. The height of the resist pattern can be determined according to the height of the unevenness required for the mold. Further, when the resist film having a desired thickness cannot be obtained by one application such as when the solid content concentration of the resist composition is low, the resist composition is further applied (overcoating) on the resist film having insufficient thickness. Then, the drying operation is repeated a necessary number of times to obtain a resist film having a desired film thickness.

A latent image pattern is formed on the obtained resist film by using an electron beam drawing apparatus. When the resist film has a large thickness (for example, 10 μm or more), it is preferable to set the electron beam accelerating voltage when irradiating the electron beam to 20 kV or more. After electron beam drawing, PEB processing is usually performed.
As a result, a cross-linking reaction or a deprotection reaction of an acid labile group is allowed to proceed at a position where the acid is generated in a pattern by being irradiated with an electron beam to form a negative or positive latent image pattern in the resist film. Then, the resist film having the latent image pattern is brought into contact with the developing solution, so that the latent image pattern is made visible (developed).

The developer is an aqueous solution in which an alkaline compound is dissolved in water, and examples of the alkaline compound include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water. Primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine, methyldiethylamine and N-methylpyrrolidone; dimethylethanol Alcohol amines such as amine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide,
Tetrabutylammonium hydroxide, quaternary ammonium salts such as choline; pyrrole, piperidine, 1,8-
Diazabicyclo [5.4.0] -7-undecene, 1,
Examples thereof include cyclic amines such as 5-diazabicyclo [4.3.0] -5-nonane. These alkaline compounds may be used alone or in combination of two or more.

The developing time can be arbitrarily set depending on the film thickness of the resist and the like, but is usually 30 to 600 seconds. The method of bringing the developing solution into contact with the resist film having the latent image pattern is not particularly limited, and may be, for example, a paddle method, a spray method, a dipping method, or the like. The developing temperature is not particularly limited, but is usually 15 to 35 ° C, preferably 20 to 30 ° C.

After forming a resist pattern by development, the substrate and the rinse solution are paddle-processed or spray-processed to remove unnecessary development residues remaining on the substrate, the back surface of the substrate, and the edges of the substrate, if necessary. Alternatively, they may be contacted by a dipping method or the like. The substrate that has been brought into contact with the rinse liquid is further
If necessary, it can be washed with water and then dried with compressed air or compressed nitrogen. The resist pattern formed on the substrate is heated (post-baked: Po
It can also be st Bake) and cured. The heating method is performed by a heating device such as a hot plate or an oven. The heating is usually performed at 100 to 250 ° C. for 5 to 90 minutes.

There is no particular limitation on the height of the resist pattern thus formed on the substrate, but it is usually 2 to 50.
μm, preferably 5 to 40 μm, more preferably 10
It is 30 μm. In particular, when a resist composition containing a crosslinking agent is used, a pattern having a height of 10 μm or more can be easily obtained without cracks.

[0033]

EXAMPLES The present invention will be described in more detail below with reference to synthesis examples and examples. Parts and% in each example are based on weight unless otherwise specified.

<Synthesis Example 1> Production of Novolac Resin (R-1) In a 2 liter flask equipped with a cooling pipe and a stirrer,
350 g of m-cresol, 350 g of p-cresol, 3
350 g of 7% formalin, and oxalic acid dihydrate 2.4
g was added and the reaction was carried out for 2 hours while maintaining the temperature at 95 to 100 ° C. After that, water was distilled off at 100 to 105 ° C. for 2 hours, and the temperature was raised to 180 ° C. and 10 mmHg.
The pressure was reduced to 1, the unreacted monomer and water were removed, and then the temperature was returned to room temperature for recovery to obtain 420 g of novolac resin R-1. Two PL gel 5 μm Mix D columns manufactured by Polymer Lab Co., Ltd. were connected in series to the column, THF was used as an eluent, the column temperature was 40 ° C., the liquid feed rate was 1 ml / min, and the UV detector had a wavelength of 254 nm. Gel permeation chromatography (GPC) analysis,
The standard polystyrene reduced weight average molecular weight (Mw) of the obtained novolak resin was 3,000.

<Synthesis Example 2> Polyvinylphenol (R-
2) Synthesis 4-hydroxystyrene 72.1 g (0.60 mo
l), 10.0 g of azobisisobutyronitrile (0.0
61 mol) and 200 ml of dioxane were charged into a 1-liter flask, and the mixture was stirred at 80 ° C. for 4 hours under a nitrogen stream. The obtained reaction liquid was poured into 5 liters of hexane, and the generated precipitate was filtered. The obtained solid content was dissolved in 200 ml of tetrahydrofuran, poured into 3 liters of n-hexane, and the generated precipitate was filtered (reprecipitation operation). After repeating this reprecipitation operation three times, it is dried.
25.2 g of 4-hydroxystyrene homopolymer was obtained. As a result of the same GPC analysis as in Synthesis Example 1, the obtained polymer was Mw = 2300 in terms of standard polystyrene.

<Synthesis Example 3> Synthesis of 4-hydroxystyrene / styrene copolymer (R-3) 4-hydroxystyrene 72.1 g (0.60 mo)
l), styrene 10.4 g (0.10 mol), azobisisobutyronitrile 10.0 g (0.061 mol)
200 ml of dioxane and 200 ml of dioxane were charged into a 1-liter flask, and the mixture was stirred at 80 ° C. for 6 hours under a nitrogen stream. The obtained reaction liquid was poured into 5 liters of hexane, and the generated precipitate was filtered. Tetrahydrofuran 2 was obtained.
It was dissolved in 00 ml and poured into 3 liters of n-hexane, and the generated precipitate was filtered (reprecipitation operation). This reprecipitation operation was repeated 3 times and then dried to obtain 28.6 g of 4-hydroxystyrene / styrene copolymer. As a result of the same GPC analysis as in Synthesis Example 1, the obtained polymer was Mw = 3000 in terms of standard polystyrene. In addition, ¹ H-
As a result of NMR spectrum analysis, the structural unit ratio of 4-hydroxystyrene / styrene copolymer was a molar ratio of 84/16.
Met.

<Synthesis Example 4> Synthesis of 4- (t-butoxycarbonylmethyloxy) styrene / 4-hydroxystyrene copolymer (R-4) In 200 ml of anhydrous dimethylformamide, 20 g of poly (4-vinylphenol) was added with nitrogen. After dissolving under an atmosphere, 0.80 g of NaOH (purity 95%) was added to this solution and stirred for 30 minutes. Then, 5.4 g of t-butyl chloroacetate was added dropwise thereto, and heated at 70 ° C. for 18 hours. After cooling and filtering, the precipitate formed by adding the solution to 3 liters of water was collected by filtration, resuspended in water, refiltered, and dried to give 4- (t-butoxycarbonylmethyloxy) styrene / A 4-hydroxystyrene copolymer was obtained. As a result of the same GPC analysis as in Synthesis Example 1, this polymer was Mw = 6,000 in terms of standard polystyrene. In addition, as a result of ¹ H-NMR spectrum analysis, about 24 mol% of hydrogen atoms of the phenolic hydroxyl group of poly (4-vinylphenol) used as a raw material was substituted with t-butoxycarbonylmethyl group.

<Synthesis Example 5> 4-hydroxystyrene / t
-Synthesis of butyl acrylate copolymer (R-5) 4-hydroxystyrene 60.1 g (0.50 mo
l), t-butyl acrylate 64.1 g (0.50
mol), azobisisobutyronitrile 10.0 g
(0.061 mol) and 200 ml of dioxane were charged into a 1-liter flask, and the mixture was stirred at 80 ° C. for 8 hours under a nitrogen stream. The obtained reaction liquid was put into 5 liters of xylene, and the generated precipitate was filtered. The obtained solid content was dissolved in 200 ml of diethyl ether, and 3 liters of n was added.
-Adding to hexane, the precipitate formed was filtered (reprecipitation operation). After repeating this reprecipitation operation three times, it was dried and
2.3 g of 4-hydroxystyrene / t-butyl acrylate copolymer was obtained. The polymer obtained was Synthetic Example 1
As a result of GPC analysis similar to, M in terms of standard polystyrene
w = 8,900. Moreover, as a result of ¹ H-NMR spectrum analysis, 4-hydroxystyrene / t-butyl was obtained.
The structural unit ratio of the acrylate copolymer is a molar ratio of 52/4.
It was 8.

<Preparation of Resist Composition 1> 100 parts of Resin (R-1) obtained by Synthesis Example 1 and 2 as an acid generator
-[2- (4-Methoxyphenyl) ethenyl] -4,6
-Bis (trichloromethyl) -S-triazine (P-
1) 1.0 part, as a cross-linking agent, "Cymel 303" (trade name, manufactured by Mitsui Cytec, hexamethoxymethylmelamine) (C-1) 5.0 parts, silicon-based surfactant "KP"
-341 "(trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) with 0.1 part of propylene glycol monomethyl ether acetate 1
After being dissolved in 80 parts, a resist composition 1 was prepared by filtering with a 3 μm polytetrafluoroethylene filter.

<Preparation of Resist Compositions 2 to 7> The resist composition was prepared in the same manner as in the preparation of the resist composition 1 except that the type and the number of parts of each component in the composition were as shown in Table 1. Items 2 to 7 were prepared.

[0041]

[Table 1]

The types of each component in Table 1 are as follows. Acid generator: (P-1) / 2- [2- (4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine (P-2) / triphenylsulfonium trifluoromethanesulfonate. (P-3) / 2,4,6-tris (trichloromethyl)
-S-triazine crosslinking agent: (C-1) / Cymel 303 (trade name, manufactured by Mitsui Cytec, hexamethoxymethylmelamine) (C-2) / Cymel 1170 (trade name, manufactured by Mitsui Cytec, butylated glycoluril) ) Dissolution inhibitor: (I-1) / 1,1-dimethyl-1,1-di (4-t-
Butoxycarbonyloxyphenyl) methane basic compound: (B-1) / diphenylamine (B-2) / triethanolamine

<Evaluation 1 to 7> The resist composition obtained above was applied onto a silicon wafer using a pattern forming coater using the resist compositions 1 to 7, and then prebaked at 110 ° C. for 120 seconds. A resist film having a film thickness of 10 μm was formed.
When forming a resist film, a resist composition capable of forming a resist film having a thickness of 10 μm at a coater rotation speed of 500 rpm or more cannot be formed unless the coater rotation speed is less than 500 rpm for one coating film. A resist film having a thickness of 10 μm was obtained by coating twice. A pattern was drawn on the obtained wafer using an electron beam drawing apparatus (ELS5700 manufactured by Elionix). The acceleration voltage of the electron beam was 50 kV. The drawing pattern is a 1: 1 line-and-space pattern in which electron beam drawing parts and electron beam non-irradiating parts are alternately repeated with the same width, and the line width is 40 kinds of 1 to 40 μm in steps of 1 μm. The entire 40 types of drawing patterns were drawn with an irradiation energy amount of 30 levels of ¹ to 30 μC / cm ^{2 in} steps of 1 μC / cm ² . Bake after drawing at 110 ° C for 120 seconds (P
ost Exposure Baking) was performed.
Next, a resist pattern was formed by developing with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds by a paddle method.

<Evaluation 8> 100 parts of an equimolar copolymer (weight average molecular weight of about 300,000) of pattern-formed α-methyl methyl acrylate and α-methyl styrene was formed using a non-chemically amplified electron beam resist composition. It was dissolved in 900 parts of o-dichlorobenzene and filtered through a polytetrafluoroethylene filter having a pore size of 3 μm to obtain a resist composition. The resulting resist composition is a general non-chemically amplified electron beam resist composition. This resist composition was spin-coated on a silicon wafer and prebaked at 180 ° C. for 180 seconds to form a resist film having a film thickness of 2 μm. This operation was repeated 5 times to make the film thickness 10 μm. After electron beam drawing was performed in the same manner as in the evaluation of the resist compositions 1 to 7, the mixture was treated with a mixed solvent of diethyl malonate and diethyl ketone in a ratio of 1: 1 (weight ratio) to 23
It was developed by a dip method at 180 ° C. for 180 seconds and rinsed with methyl isobutyl ketone by a dip method at 23 ° C. for 20 seconds to form a positive pattern.

<Evaluation 9> Pattern formation using non-chemically amplified electron beam resist composition Copolymer of 4-chlorostyrene and 4-chloromethylstyrene (copolymerization ratio is 1: 1 by molar ratio, standard polystyrene equivalent weight) 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA)
It was dissolved in 800 parts and filtered through a polytetrafluoroethylene filter having a pore size of 3 μm to obtain a resist composition. The resulting resist composition is a general non-chemically amplified electron beam resist composition. This resist was spin-coated on a silicon wafer and prebaked at 135 ° C. for 120 seconds to form a resist film having a film thickness of 2 μm.
This operation was repeated 5 times to make the film thickness 10 μm. After electron beam drawing was performed in the same manner as in the evaluation of the resist compositions 1 to 7, the weight ratio of ethyl cellosolve to isoamyl acetate was 65:
It was developed by a dip method at 23 ° C. for 180 seconds in a mixed solvent of 35, and rinsed by a dip method at 23 ° C. for 20 seconds in 2-propanol to form a negative pattern.

<Evaluation 10> 100 parts of Resin (R-1) obtained by Synthesis Example 1 of pattern formation using a non-chemically amplified photoresist composition, 2,
1,4 of 3,4,4'-tetrahydroxybenzophenone
20 parts of 2-naphthoquinonediazide-5-sulfonic acid ester (esterified with 75 mol% of phenolic hydroxyl groups) and a silicone-based surfactant "KP-34"
0.1 "(trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) was dissolved in 200 parts of propylene glycol monomethyl ether acetate, and then filtered through a polytetrafluoroethylene filter having a pore size of 3 µm to obtain a resist composition. The obtained resist composition is a general non-chemically amplified photoresist composition. This resist was spin-coated on a silicon wafer and prebaked at 100 ° C. for 90 seconds to form a resist film having a film thickness of 5 μm. This operation was repeated twice to make the film thickness 10 μm. This wafer was pattern-exposed using a mask aligner (PLA501 Canon Inc.). The wavelength of the ultraviolet ray used for the exposure was set to be only 365 nm by using a filter. The mask pattern used for exposure was a 1: 1 line in which exposed and non-exposed areas were alternately repeated with the same width.
In the and space pattern, the line width was set to 1 to 40 μm in steps of 1 μm. 10 to 30 at intervals of 10 mJ / cm ^{2 for the} entire 40 types of drawing patterns
The exposure was performed with an irradiation energy amount of 30 levels of 0 mJ / cm ² . After exposure to ultraviolet light in the same pattern as in the evaluation of the resist compositions 1 to 7, the resist composition was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds by a paddle method, and then with ultrapure water. A pattern was formed by rinsing by a spin spray method at 20 ° C. for 20 seconds.

<Evaluation> The following evaluations were performed on each of the formed patterns. (1) The sensitivity pattern was observed with an electron microscope, and the irradiation energy amount at which the actual pattern size of the 1: 1 line & space pattern drawing portion with a line width of 40 μm was 1: 1 was defined as the sensitivity. (2) Limit resolution The minimum line width that can be resolved with the irradiation energy amount corresponding to the sensitivity of (1) was defined as the limit resolution. (3) Cracks after development The pattern after development was observed to check for the presence of cracks (cracks in the resist film). The evaluation results are summarized in Table 2.

[0048]

[Table 2]

As can be seen from these results, when resist compositions 1 to 7 were used, a pattern of 10 μm or less could be resolved at a film thickness of 10 μm without generating cracks after development. On the other hand, in Evaluation 8 using the non-chemically amplified electron beam resist composition provided with a positive pattern, severe cracks were generated after development and a good pattern could not be formed, and a negative pattern was formed. In Evaluation 9 using the given chemically amplified resist composition, cracks did not occur, but only a critical resolution of 30 μm could be obtained due to swelling of the pattern and scum after development. Further, when the non-chemically amplified photoresist composition was used, a desired pattern could be formed with a lesbian having a limiting resolution of 25 μm (evaluation 10). Furthermore, a small amount of cracks occurred after development.

From the above, when an electron beam is drawn on the resist film obtained by using the chemically amplified resist composition, fine processing is possible even when the film thickness is large, and a good resist pattern is obtained. It was found that it is possible to manufacture a stamper with large unevenness. An example of manufacturing a mold using the resist pattern obtained by such a method will be shown below.

Example 1 A resist composition 1 containing a cross-linking agent was applied on a silicon wafer, and then the composition was applied at 110 ° C. for 1 hour.
Pre-baking was performed for 20 seconds to form a resist film having a film thickness of 6.0 μm. An electron beam lithography system (ELS
5700 Elionix) was used to draw a pattern. The acceleration voltage of the electron beam was 50 kV. The drawing pattern is a rectangle of 50μm x 500μm, 1μC / cm
It is drawn by irradiation energy amount of 30 levels 1~30μC / cm ² at ² increments. After drawing for 120 seconds at 110 ° C., baking (Post Exposure Baking) was performed. Next, a pattern was formed by developing with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds by a paddle method. For the obtained pattern,
The remaining film thickness of the area where each electron beam is drawn is measured by the stylus type film thickness meter (P
-10 KLA-manufactured by Tencor Co., Ltd.) to determine the relationship between the amount of irradiation energy and the residual film thickness (residual film sensitivity curve). By utilizing this relationship, it becomes possible to form a pattern having a desired cross-sectional shape.

Separately from the above-mentioned residual film sensitivity curve, a resist film having a film thickness of 6.0 μm was newly formed by the same method as described above. A line pattern was drawn on the resist film while gradually changing the amount of electron beam drawing energy. Specifically, the residual film sensitivity curve obtained above indicates that the residual film thickness is 0.525 μm.
The first line pattern (pattern length 500 μm × width 0.02) with an energy amount (D1) μC / cm ² of m.
5 μm) was drawn, and a line pattern was drawn next to it with an energy amount (D2) μC / cm ^{2 such} that the residual film thickness was 0.550 μm. Similarly, while gradually increasing the amount of energy so that the remaining film thickness increases by 0.025 μm,
The residual film thickness is 5.500 μm (D200) μC / cm
Up to ² , a total of 200 line patterns were drawn. Next to the 200 line patterns, 200 new line patterns were formed by the following procedure. That is, (D20
0) Draw with μC / cm ² first and the residual film rate is 0.025
200 line patterns were drawn up to (D1) μC / cm ² while reducing the amount of energy such that the line amount decreased by μm. A set of 400 line patterns (length: 500 μm × width: 10 μm) thus obtained was set as one set, and 10 sets were drawn. The above-described series of drawing operations is summarized as a conceptual diagram in FIG. In the case of Example 1, the minimum energy amount (D1) is 0.80 μC / cm.
² and the maximum energy amount (D200) is 3.50μ
It was C / cm ² .

After drawing the electron beam in this way, 11
Bake after writing for 120 seconds at 0 ° C (Post Expos
ure baking). Then, with a 2.38% tetramethylammonium hydroxide aqueous solution,
When developed by the paddle method at 90 ° C for 90 seconds, the height is 5μ.
It was possible to obtain a concavo-convex pattern in which patterns having a triangular cross-sectional shape of m were continuous. The slope of this pattern was flat rather than stepped. A nickel thin film was formed on the substrate having a concavo-convex pattern on its surface by the sputtering method. Using the formed nickel thin film as a conductive layer, nickel is grown by electrolytic plating of nickel to a thickness of 50
A 0 μm nickel layer was obtained. The silicon wafer used as the substrate and the nickel layer are peeled off by physical force, the residue of the resist pattern attached to the nickel layer is washed off with tetrahydrofuran, and a stamper having a 5 μm uneven pattern corresponding to the resist pattern is obtained. Obtained. The surface of the obtained stamper that was in contact with the resist pattern (the resin molding surface of the mold) was laser microscope (VK-850).
It was confirmed to be flat by observing with 0 Keyence Corporation).

Example 2 Using resist composition 3 containing a crosslinking agent, the film thickness was set to 20 μm, and the minimum energy amount was set to 1.2 μC / qscm at which the residual film thickness becomes 1 μm in the residual film sensitivity curve. A stamper having a pattern with irregularities of 19 μm was manufactured in the same manner as in Example 1 except that the maximum amount of energy was 7.5 μC / qscm which gives a residual film thickness of 19 μm. The surface of the obtained stamper in contact with the resist pattern (the resin molding surface of the die) was also flat.

Example 3 Using the resist composition 5 containing no cross-linking agent, the film thickness was set to 10 μm, and the maximum energy amount was set to 5.3 μC / qscm at which the residual film thickness becomes 1 μm in the residual film sensitivity curve. A stamper having a pattern with unevenness of 8 μm was manufactured in the same manner as in Example 1 except that the minimum energy amount was 0.4 μC / qscm, which was an energy amount with which the residual film thickness was 9 μm. The surface that was in contact with the resist pattern of the obtained stamper (the resin molding surface of the mold)
Was also flat.

Example 4 A resist composition 6 containing no crosslinking agent was used, the film thickness was 10 μm, and the maximum energy amount was 4.2 μC / qscm at which the residual film thickness was 1 μm in the residual film sensitivity curve. A stamper having a pattern with unevenness of 8 μm was manufactured in the same manner as in Example 1 except that the minimum amount of energy was 0.3 μC / qscm that gives a residual film thickness of 9 μm. The surface that was in contact with the resist pattern of the obtained stamper (the resin molding surface of the mold)
Was also flat.

Example 5 Using Resist Composition 1 containing a cross-linking agent, a resist film having a thickness of 10 μm was formed.
The line pattern having a length of 500 μm is arranged and drawn while gradually changing the electron beam drawing energy amount, and the minimum energy amount is the energy amount that the residual film thickness becomes 1 μm in the residual film sensitivity curve obtained above. 0 μC / cm ²
The maximum energy amount was set to 6.2 μC / cm ^{2 so} that the remaining film thickness was 9 μm. The line of the minimum energy amount and the line of the maximum energy amount are separated by 8 μm, and in the meanwhile, while gradually increasing the irradiation energy amount so that the cross-sectional shape of the pattern becomes a fan-shaped arc having a central angle of 90 degrees, 198 lines were drawn at intervals of 0.025 μm. Similarly, from 6.2 μC / cm ² to 1.
While reducing the irradiation energy amount to 0 μC / cm ² smoothly, 200 lines were drawn right next to each other at intervals of 0.025 μm. Such drawing was repeated 10 sets. Then, a stamper was manufactured in the same manner as in Example 1. The obtained stamper had a pattern in which a semicircle having a cross-sectional shape with a radius of 8 μm was continuous, and the surface in contact with the resist pattern (the resin molding surface of the mold) was flat.

[Brief description of drawings]

FIG. 1 is an explanatory diagram related to a method for producing a resist pattern.

Claims (5)

[Claims] 1. A metal mold for resin molding, comprising: forming a metal layer by laminating a metal on a substrate having a resist pattern formed on its surface; and peeling the metal layer from the substrate having the resist pattern formed thereon. A method for producing a resin, wherein the resist pattern is formed by drawing an electron beam on a resist film obtained by using a chemically amplified resist composition containing a resin and an acid generator. A method for manufacturing a molding die. 2. The height of the resist pattern is 2 to 50 μm.
The method for producing the resin molding die according to claim 1. 3. The method for producing a resin molding die according to claim 1, wherein the chemically amplified resist composition further contains a crosslinking agent. 4. A method of forming a metal layer, which comprises first forming a metal thin film on the surface of a substrate having a resist pattern formed thereon,
Next, the method for producing a resin molding die according to claim 1, wherein the metal thin film is subjected to electrolytic plating. 5. A resin molding die manufactured by the method according to any one of claims 1 to 4.