JP4424630B2 - Chemically amplified resist composition and resist pattern forming method - Google Patents

Description

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【表２】

【００６３】
【表３】

【００６４】
【発明の効果】
本発明の化学増幅型レジスト組成物は、エッチング後のレジスト表面の荒れが発生せずドライエッチング耐性が良好であり、また感度および解像度も高く、高精度の微細なレジストパターンを安定して形成することができる。したがって、ＤＵＶエキシマレーザーリソグラフィーや電子線リソグラフィー用、特にＡｒＦエキシマレーザーを使用するリソグラフィーに好適に用いることができる。
【００６５】
また本発明のパターン形成方法を用いることにより、より高いドライエッチング耐性が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a chemically amplified resist composition and a resist pattern format method, and more particularly to a chemically amplified resist composition and a resist pattern format method suitable for fine processing using an excimer laser or an electron beam.
[0002]
[Prior art]
In recent years, in the field of microfabrication in the manufacture of semiconductor elements or liquid crystal elements, miniaturization has rapidly progressed due to advances in lithography technology. As the miniaturization technique, generally, the wavelength of an exposure light source is shortened, and specifically, the conventional ultraviolet ray typified by g-line and i-line is changed to DUV.
[0003]
At present, KrF excimer laser (248 nm) lithography technology has been introduced to the market, and ArF excimer laser (193 nm) lithography technology with a shorter wavelength is being introduced. The next generation technology is F ₂ excimer laser. Lithography technology is being studied (157 nm). In addition, an electron beam lithography technique has been energetically studied as a slightly different type of lithography technique.
[0004]
As a high-resolution resist for such short-wavelength light sources or electron beams, International Business Machines (IBM) has proposed “Chemically Amplified Resist”, and is currently energetically improving and developing this chemically amplified resist. Is underway.
[0005]
In addition, as the wavelength of the light source is shortened, the resin used for the resist is also forced to change its structure. In KrF excimer laser lithography, polyhydroxystyrene having high transparency with respect to 248 nm and its hydroxyl group are dissolved in an acid-dissociable manner. In the ArF excimer laser lithography, since the resin has insufficient transparency at 193 nm and is almost unusable, an acrylic resin or cycloolefin resin transparent at 193 nm is used. Attention has been paid. Examples of the acrylic resin include JP-A-4-39665 and JP-A-10-207069, and examples of the cycloolefin resin include JP-A-10-153864.
[0006]
However, even when these resins are used, the performance is still insufficient and higher dry etching resistance is required.
[0007]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a chemically amplified resist composition suitable for DUV excimer laser lithography or electron beam lithography having high dry etching resistance.
[0008]
[Means for Solving the Problems]
In view of the above problems, the present inventors have intensively studied for the purpose of improving the dry etching resistance of a chemically amplified resist composition, and as a result, by adding a block type isocyanate, the present invention can be applied to DUV excimer laser lithography or electron beam lithography. The present inventors have found that a suitable chemically amplified resist composition can be obtained and have reached the present invention.
[0009]
That is, the present invention provides a chemically amplified positive resist composition containing a resin that is soluble in an alkaline aqueous solution by an acid and a photoacid generator, wherein the isocyanate group of diisocyanate or an isocyanurate of diisocyanate is protected with a blocking agent look containing block-type polyisocyanate compound, the resin becoming soluble in an alkali aqueous solution by the acid, it has different alicyclic skeleton and a monomer unit having a lactone skeleton, a monomer unit having the lactone structure a chemical amplification type positive resist composition comprising a monomer unit.
[0010]
Further, the present invention includes a feature that the resist is formed using a chemically amplified resist composition, the heat treatment is performed by irradiation and / or far-infrared or heat source activity beam to resist before performing dry etching This is a resist pattern forming method.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The block-type polyisocyanate compound used in the present invention is obtained by protecting a diisocyanate such as an aliphatic diisocyanate or an alicyclic diisocyanate, and an isocyanate group of an isocyanurate polymer obtained by polymerizing the diisocyanate with a blocking agent. In the present invention, the block type polyisocyanate compound is used as a crosslinking agent. The block type polyisocyanate compound can be used alone or in combination of two or more as required.
[0012]
The inventors of the present application have found that the inclusion of block-type polyisocyanate in the resist composition can improve the dry etching resistance and reduce the roughness of the resist surface after dry etching.
[0013]
Regarding the block type polyisocyanate, “Thermosetting Resin” Vol. 13 No. 2 (1992), pages 47 to 59, or “Advanced Progress in Coating Technology” (author: Yuji Harasaki) published by the Technical Center, Inc., pages 191-198. The block type polyisocyanate is also called a blocked isocyanate or a blocked polyisocyanate, and is a compound that is stable at room temperature by reacting a compound (blocking agent) having a certain kind of active hydrogen with the polyisocyanate compound. When the block type polyisocyanate is heated under certain conditions, the blocking agent is dissociated to regenerate the original active isocyanate group.
[0014]
The diisocyanate compound and the isocyanurate form which is a trimer of diisocyanate are not particularly limited, but are preferably aliphatic such as 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, isophorone diisocyanate or the like. An alicyclic diisocyanate is mentioned.
[0015]
Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol, phenol, and O-nitrophenol. , P-chlorophenol, phenols such as o, m, p-cresol, 1-dodecantyl, thiols such as benzenethiol, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxy, benzophenone oxime, etc. Examples include oximes, active methylene compounds such as diethyl malonate, ethyl acetoacetate, and acetylacetone, and lactams such as ε-caprolactam.
[0016]
Specific examples of the block polyisocyanate include, for example, Coronate series manufactured by Nippon Polyurethane Industry Co., Ltd., Death Module Series manufactured by Sumitomo Bayer Urethane Co., Ltd., and the like.
[0017]
The amount of the block polyisocyanate compound to be used is appropriately selected depending on the kind thereof, but is usually 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin that is soluble in an alkaline aqueous solution by an acid. The more the block type polyisocyanate compound is, the more the dry etching resistance is improved.
[0018]
The structure of the block-type polyisocyanate compound is not particularly limited. However, when a wavelength of 200 nm or less is used as a light source in lithography, a compound having no aromatic ring is preferable.
[0019]
Next, a resin that is soluble in an alkaline aqueous solution by an acid will be described. This resin is not particularly limited as long as it has a property of being soluble in an alkaline aqueous solution by an acid, and those used so far for resins for chemically amplified resist compositions can be used. These are arbitrarily selected depending on the light source used for lithography.
[0020]
For example, when a KrF excimer laser or an electron beam is used as a light source, a resin obtained by copolymerizing p-hydroxystyrene or a derivative thereof is preferably used in consideration of its high etching resistance. In that case, in order to use as a chemically amplified resist composition, it is essential to have a functional group in the copolymer structure that is eliminated by an acid and becomes soluble in an alkaline developer.
[0021]
Specifically, the hydroxyl group of p-hydroxystyrene or the carboxyl group of the monomer to be copolymerized may be protected by an acetoxy group, t-butyl group, tetrahydropyranyl group or methyladamantyl group. Is preferred.
[0022]
When the light source is an ArF excimer laser, the wavelength is short, so that a resin copolymerized with p-hydroxystyrene or a derivative thereof cannot be used because of its low light transmittance. Therefore, considering the balance with etching resistance, a resin having an alicyclic skeleton is preferably used.
[0023]
Specific examples include acrylic resins described in JP-A-9-090637 or JP-A-10-207069, and olefin resins described in JP-A-10-207070 or JP-A-10-218941. It is done.
[0024]
Among them, an acrylic copolymer obtained by polymerizing a monomer having an alicyclic skeleton and a monomer having a lactone skeleton is particularly suitable as a resin for ArF excimer laser lithography.
[0025]
A monomer having an alicyclic skeleton imparts high dry etching resistance to a copolymer obtained by polymerization and a resin composition thereof, and particularly contains a protective group that is eliminated by an acid. Can also provide high sensitivity at 193 nm. Monomers having an alicyclic skeleton can be used alone or in combination of two or more as required.
[0026]
Monomers having an alicyclic skeleton include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and These monomers are preferably at least one selected from the group consisting of derivatives having substituents such as alkyl groups, hydroxyl groups, and carboxyl groups on the alicyclic rings of these monomers. Specific examples include 1-isobornyl methacrylate, 2-methacryloyloxy-2-methyladamantane, cyclohexyl methacrylate, adamantyl methacrylate, tricyclodecanyl methacrylate, and dicyclopentadienyl methacrylate.
[0027]
A monomer having a lactone skeleton imparts adhesiveness to a substrate to a copolymer obtained by polymerization and a resin composition thereof, and particularly those containing a protective group that is eliminated by an acid are 193 nm. High sensitivity can be imparted. Monomers having a lactone skeleton can be used alone or in combination of two or more as required.
[0028]
Examples of the monomer having the lactone skeleton include (meth) acrylate having a δ-valerolactone ring, (meth) acrylate having a γ-butyrolactone ring, and an alkyl group on the lactone ring of these monomers, At least one selected from the group consisting of derivatives having a substituent such as a hydroxyl group or a carboxyl group is preferred.
[0029]
Specifically, β-methacryloyloxy-β-methyl-δ-valerolactone, β-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-β-methyl-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, Examples include 2- (1-methacryloyloxy) ethyl-4-butanolide, pantolactone methacrylate, and the like.
[0030]
The weight average molecular weight of the resin that is soluble in an alkaline aqueous solution by an acid is not particularly limited, but is preferably in the range of 1,000 to 100,000. The larger the weight average molecular weight, the better the dry etching resistance and the better the resist shape, and the smaller the weight average molecular weight, the better the solubility in the resist solvent and the better the resolution.
[0031]
As a method for producing a resin that is soluble in an alkaline aqueous solution with an acid, for example, a monomer solution obtained by dissolving a monomer and a polymerization initiator in an organic solvent in advance is dropped into an organic solvent kept at a constant temperature. The so-called drop polymerization method is simple and suitable.
[0032]
The organic solvent used in the dropping polymerization method is not particularly limited, but a solvent capable of dissolving both the monomer and the obtained copolymer is preferable, and examples thereof include 1,4-dioxane, isopropyl alcohol, acetone, tetrahydrofuran and the like. .
[0033]
The polymerization initiator used in the dropping polymerization method is not particularly limited, and examples thereof include azo compounds such as azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, and the like. An organic peroxide etc. are mentioned. Further, mercaptans such as n-butyl mercaptan and n-octyl mercaptan may be used in combination as a chain transfer agent.
[0034]
The polymerization temperature in the dropping polymerization method is not particularly limited, but is preferably in the range of 50 to 150 ° C. Although the dropping time is not particularly limited, it is preferably 6 hours or more, and it is preferable to hold the temperature for about 2 hours after completion of the dropping to complete the polymerization.
[0035]
A resin solution that is soluble in an alkaline aqueous solution by an acid produced by the dropping polymerization method is diluted to a suitable solution viscosity with a good solvent such as tetrahydrofuran or 1,4-dioxane, and then heptane, methanol, water, or the like. It is dropped and deposited in a large amount of poor solvent. Thereafter, the precipitate is filtered off and sufficiently dried. This step is called reprecipitation, and may be unnecessary depending on circumstances, but is very effective for removing unreacted monomers remaining in the polymerization solution, polymerization initiators, and the like. If these unreacted substances remain as they are, there is a possibility of adversely affecting the resist performance. Therefore, it is preferable to remove them if possible.
[0036]
Thereafter, the resin powder that is soluble in the alkaline aqueous solution by the dried acid is dissolved in the solvent. The solvent is arbitrarily selected according to the purpose, but the selection of the solvent is restricted by reasons other than the solubility of the resin, for example, the uniformity of the coating film, the appearance, or the safety.
[0037]
Examples of the solvent that satisfies these conditions include linear ketones such as 2-pentanone and 2-hexanone; cyclic ketones such as cyclopentanone and cyclohexanone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. Propylene glycol monoalkyl ether acetates; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Ethylene glycol such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Monoalkyl ethers; diethylene glycol alkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; esters such as ethyl acetate and ethyl lactate; alcohols such as cyclohexanol and 1-octanol; ethylene carbonate and γ-butyrolactone . These solvents can be used alone or in admixture of two or more.
[0038]
Next, the photoacid generator used in the present invention will be described.
The photoacid generator can be arbitrarily selected from those that can be used as the acid generator of the chemically amplified resist composition. Moreover, a photo-acid generator can be used individually or in combination of 2 or more types.
[0039]
Specific examples include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, and diazomethane compounds. Of these, onium salt compounds are preferred, and examples thereof include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, and pyridinium salts.
[0040]
Specific examples include triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate. And diphenyliodonium hexafluoroantimonate.
[0041]
The amount of the photoacid generator used is appropriately determined depending on the type of photoacid generator to be used. 5 to 10 parts by weight. If the amount of the photoacid generator used is too small, it may be difficult to cause a chemical reaction due to the catalytic action of the acid generated by exposure, and if it is too large, the stability of the resist composition will decrease. Or coating unevenness when applying the composition, or scum or the like may occur during development.
[0042]
Furthermore, the chemical amplification resist composition of the present invention may be blended with various additives such as surfactants, quenchers, sensitizers, antihalation agents, storage stabilizers, antifoaming agents, etc., as necessary. it can.
[0043]
Examples of the surfactant include nonionic surfactants such as polyoxyethylene lauryl ether and polyethylene glycol dilaurate, and the following trade names: Polyflow No. 75 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Megafax F173 (manufactured by Dainippon Ink and Chemicals), Surflon SC-105 (manufactured by Asahi Glass), L-70001 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
[0044]
Next, a method for using the chemically amplified resist composition of the present invention will be described.
When pre-baking (soft baking) after resist coating or PEB (post-exposure baking) after exposure, the blocking agent comes off and the isocyanate is regenerated, which may cause a reduction in resolution. Therefore, when prebaking or PEB is performed, a block agent having a dissociation temperature higher than the heat treatment temperature is selected, or the heat treatment is preferably performed at a temperature lower than the dissociation temperature of the block agent.
[0045]
When pattern formation is performed using the chemically amplified resist composition of the present invention, the formed resist is irradiated with actinic rays such as UV, DUV, EB and / or far infrared rays or the like before dry etching. It is preferable to regenerate the polyisocyanate group by performing a heat treatment for a certain time with a heat source such as a hot plate to dissociate the blocking agent. Although the details of the mechanism of this treatment are unknown, hydroxyl groups and carboxyl groups generated by the generation of acid from the photoacid generator upon irradiation with actinic rays or electron beams, and removal of the protecting groups of the resist resin, and polyisocyanate It is presumed that it reacted with the group to form a three-dimensional cross-linked structure and improved dry etching resistance.
[0046]
Therefore, a method of performing a heat treatment by irradiating actinic rays again after forming a pattern by exposure, PEB and development is most preferable.
[0047]
【Example】
Hereinafter, the present invention will be specifically described based on examples. Here, “parts” means “parts by weight” unless otherwise specified.
The physical properties of the copolymer and the evaluation of the resist were performed by the following methods.
[0048]
<Weight average molecular weight>
It calculated | required in conversion of the polymethyl methacrylate by the gel permeation chromatography (GPC). As the solvent, chloroform or tetrahydrofuran was used.
[0049]
<Average copolymer composition of copolymer (mol%)>
^It calculated | required by the measurement of < ¹ > H-NMR. As the solvent, deuterated chloroform or deuterated acetone was used.
[0050]
<Sensitivity>
The resist film formed on the silicon wafer was exposed and immediately post-exposure baked, then developed with an alkaline developer, washed with water, and dried to form a resist pattern. The exposure amount for forming a line and space pattern (L / S = 1/1) with a line width of 1/1 was measured as sensitivity.
[0051]
<Resolution>
The minimum dimension (μm) of the resist pattern resolved when exposed with the above exposure amount was defined as the resolution.
[0052]
<Dry etching resistance>
The resist film formed on the silicon wafer was etched, and the etching rate of each resist (normalized with the novolac resin etching rate set to 1) was measured from the decrease in film thickness. Etching conditions were as follows: an etching machine manufactured by Tokyo Electron was used, and a C ₄ F ₈ / Ar / O ₂ mixed gas was used as the gas. The etching was performed at 2000 W and 50 mTorr for 50 seconds.
[0053]
In addition, the resist surface after etching was observed with an electron microscope, and the resist surface with no unevenness was evaluated as “◯”, and the resist surface with unevenness was evaluated as “x”.
[0054]
(Synthesis Example 1)
Under a nitrogen atmosphere, 20.0 parts of 1,4-dioxane was placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 22.0 parts of pt-butoxystyrene (abbreviation: PTBST, molecular weight = 176), 15.0 parts of p-hydroxystyrene (abbreviation: HS, molecular weight = 120), 62.5 parts of 1,4-dioxane, azobis A monomer solution mixed with 1.9 parts of isobutyronitrile was dropped into the flask at a constant rate over 6 hours, and then a temperature of 80 ° C. was maintained for 2 hours. Next, the obtained reaction solution was diluted about 2-fold with tetrahydrofuran and dropped into about 10-fold amount of water with stirring to obtain a white precipitate (copolymer A-1). The resulting precipitate was filtered off and dried under reduced pressure at 60 ° C. for about 40 hours.
[0055]
Subsequently, each physical property of the obtained copolymer A-1 was measured. The weight average molecular weight was 12,000, and the copolymer composition ratio was PTBST / HS = 51/49 mol%.
[0056]
(Synthesis Example 2)
Under a nitrogen atmosphere, 20.0 parts of 1,4-dioxane was placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 2-Methacryloyloxy-2-methyladamantane (abbreviation: MAdMA, molecular weight = 234) 29.3 parts, β-methacryloyloxy-γ-butyrolactone (abbreviation: HGBMA, molecular weight = 170) 21.2 parts, 1,4-dioxane A monomer solution in which 62.5 parts and 1.9 parts of azobisisobutyronitrile were mixed was dropped into the flask at a constant rate over 6 hours, and then a temperature of 80 ° C. was maintained for 2 hours. Next, the obtained reaction solution was diluted about 2-fold with tetrahydrofuran and dropped into about 10-fold amount of methanol with stirring to obtain a white precipitate (copolymer A-2). The resulting precipitate was filtered off and dried under reduced pressure at 60 ° C. for about 40 hours.
[0057]
Subsequently, each physical property of the obtained copolymer A-2 was measured. The weight average molecular weight was 11,000, and the copolymer composition ratio was MAdMA / HGBMA = 50/50 mol%.
[0058]
Examples 1-4 and Comparative Examples 1-2
Each component shown in Table 1 was mixed to obtain a uniform solution, followed by filtration with a membrane filter having a pore size of 0.1 μm to prepare a resist composition solution. Thereafter, each composition solution was spin-coated on a silicon wafer, and then pre-baked at 120 ° C. for 60 seconds using a hot plate to form a resist film having a thickness of 0.5 μm. Next, after exposure using a KrF excimer laser exposure machine or ArF excimer laser exposure machine, post-exposure baking was performed at 120 ° C. for 60 seconds using a hot plate. Next, development was performed at room temperature using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with pure water, and dried to form a resist pattern. The evaluation results of the obtained resist pattern are shown in Table 2 and Table 3.
[0059]
Next, ultraviolet rays of about 500 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp, and heat treatment was performed on a hot plate at 180 ° C. for 60 seconds. And the result of having measured the etching rate of each resist on the conditions mentioned above was shown in Table 2 and Table 3.
[0060]
As described above, in the examples, the dry etching resistance was improved without greatly reducing the sensitivity and resolution, and the resist surface was not roughened after etching. On the other hand, in the comparative example, the dry etching resistance was not sufficient, and the resist surface was roughened after etching.
[0061]
[Table 1]

[0062]
[Table 2]

[0063]
[Table 3]

[0064]
【The invention's effect】
The chemically amplified resist composition of the present invention does not cause roughness of the resist surface after etching, has good dry etching resistance, has high sensitivity and resolution, and stably forms a highly accurate fine resist pattern. be able to. Therefore, it can be suitably used for DUV excimer laser lithography and electron beam lithography, particularly for lithography using an ArF excimer laser.
[0065]
Further, by using the pattern forming method of the present invention, higher dry etching resistance can be obtained.

Claims (2)

A block type polyisocyanate compound in which a diisocyanate or an isocyanate group of an isocyanurate of diisocyanate is protected with a blocking agent in a positive chemically amplified resist composition containing a resin that is soluble in an alkaline aqueous solution by an acid and a photoacid generator look-containing resin becomes soluble in an alkali aqueous solution by the acid, the monomeric unit having a lactone skeleton, a monomer unit having a different alicyclic skeleton and a monomer unit having the lactone structure chemical amplification type positive resist composition comprising. A resist is formed using the chemically amplified positive resist composition according to claim 1, and the resist is irradiated with actinic rays and / or heat-treated with far infrared rays or a heat source before dry etching. Resist pattern forming method.