JP4700929B2 - Antireflection film material, antireflection film using the same, and pattern forming method - Google Patents

Description

The present invention relates to an antireflective film material mainly composed of a compound containing a substituent containing silicon atoms, which is suitable as an antireflective film material used for microfabrication in a manufacturing process of a semiconductor element or the like, and far ultraviolet rays using the same , A resist pattern forming method suitable for ArF excimer laser light (193 nm), F ₂ laser light (157 nm), Kr ₂ laser light (146 nm), Ar ₂ laser light (126 nm) exposure, and an integrated circuit pattern forming method on a substrate Is.

  In recent years, with the increasing integration and speed of LSIs, there is a need for finer pattern rules. In lithography using light exposure, which is currently used as a general-purpose technology, the essence derived from the wavelength of the light source The resolution limit is approaching.

  As a light source for lithography used in forming a resist pattern, light exposure using a mercury lamp g-line (436 nm) or i-line (365 nm) as a light source is widely used, and as a means for further miniaturization, A method of shortening the wavelength of exposure light has been considered effective. For this reason, in the mass production process of the 64-Mbit DRAM processing method, a short wavelength KrF excimer laser (248 nm) is used as an exposure light source instead of i-line (365 nm). However, in order to manufacture a DRAM having a degree of integration of 1G or more, which requires a finer processing technique (processing dimension is 0.13 μm or less), a light source with a shorter wavelength is required, and in particular, an ArF excimer laser (193 nm) is used. Lithography has been studied.

  In the early stages of KrF lithography, steppers were developed that combine achromatic lenses or reflective optics with broadband light. However, since the accuracy of the achromatic lens or the aspherical reflecting optical system is not sufficient, a combination of a narrow-band laser beam and a refractive optical system lens has become mainstream. In general, in single wavelength exposure, it is a long-known phenomenon that incident light and reflected light from a substrate interfere to generate a standing wave. It is also known that a phenomenon called halation occurs due to light being condensed or scattered by the unevenness of the substrate. Both standing waves and halation cause dimensional fluctuations such as the line width of the pattern and shape collapse. The use of coherent monochromatic light further amplifies standing waves and halation with shorter wavelengths. For this reason, as a method for suppressing halation and standing waves, a method of putting a light-absorbing agent in the resist and a method of laying an antireflection film on the resist upper surface and the substrate surface have been proposed. However, the method of adding a light-absorbing agent has a problem that the resist pattern has a tapered shape. With the recent shortening of wavelengths and the progress of miniaturization, the problem that standing waves and halation have on pattern dimension fluctuations has become serious, and it has become impossible to cope with the method using a light absorber.

The upper-layer transmissive antireflection film is effective only in reducing standing waves in principle, and is not effective in halation. Further, the refractive index of the upper antireflection film for completely eliminating the standing wave is ideally the square root of the refractive index of the resist, so that the refractive index of the polyhydroxystyrene resist used in KrF is 1 .8, 1.34 is the ideal value. With an alicyclic acrylic resist refractive index of 1.6 used for ArF, the ideal value is 1.27. The material having such a low refractive index is limited to a perfluoro-based material, but the upper antireflection film is a water-soluble material because it is advantageous in terms of process that it can be peeled off during alkali development. is required. When a hydrophilic substituent is introduced to make a highly hydrophobic perfluoro-based material water-soluble, the refractive index is increased to a value of around 1.42 for KrF and around 1.5 for ArF. . For this reason, when patterning of 0.20 μm or less is performed by KrF lithography, it is impossible to suppress the influence of the standing wave only by the combination of the light absorber and the upper antireflection film. For ArF, the effect of the upper antireflection film can hardly be expected for the reasons described above, and even in KrF, when line width management becomes stricter due to further reduction of the line width in the future, an antireflection film is laid on the base of the resist. It has become necessary.

  In the case where the underlying antireflection film of the resist is a highly reflective substrate such as polysilicon or aluminum, the material of optimum refractive index (n value) and extinction coefficient (k value) is set to an appropriate film thickness. As a result, reflection from the substrate can be reduced to 1% or less, and an extremely large effect can be exhibited. For example, at a wavelength of 193 nm, the refractive index of the resist is 1.8, the refractive index of the lower antireflection film (real part of the refractive index) n = 1.5, the extinction coefficient (imaginary part of the refractive index) k = 0.5 If the film thickness is 42 nm, the reflectance is 0.5% or less (see FIG. 3). However, when there is a step on the base, the thickness of the antireflection film varies greatly on the step. Since the antireflection effect of the base uses not only the light absorption but also the interference effect, the first base of 40 to 45 nm where the interference effect is strong also has a high antireflection effect. The rate fluctuates. A material has been proposed in which the molecular weight of the base resin used for the antireflection film material is increased to suppress the film thickness fluctuation on the step and the conformal property is improved (Patent Document 1). There are problems such as pinholes that tend to occur after coating, problems such as impossibility of filtration, changes in viscosity over time and changes in film thickness, problems such as precipitation of crystals at the tip of the nozzle, and Formality can be exhibited only at steps with relatively low height.

  Next, there can be considered a method of adopting a film thickness (170 nm or more) of the third base or more in which the reflectance variation due to the film thickness variation is relatively small. In this case, if the k value is between 0.2 and 0.3 and the film thickness is 170 nm or more, the change in reflectance with respect to the change in film thickness is small, and the reflectance can be suppressed to 1.5% or less. it can. When the base of the antireflection film is a transparent film such as an oxide film or a nitride film, and there is a step under the transparent film, the film thickness of the transparent film is not limited even if the surface of the transparent film is flattened by CMP or the like. Fluctuates. In this case, it is possible to make the film thickness of the antireflection film thereon constant, but when the film thickness of the base transparent film of the antireflection film varies, the thickness of the minimum reflection film in FIG. 3 becomes the film thickness of the transparent film. It shifts by a period of λ / 2n (λ: exposure wavelength, n: refractive index of the transparent film at the exposure wavelength). When the film thickness of the antireflection film is set to the minimum reflection film thickness of 55 nm when the base is a reflection film, a portion having a high reflectance appears due to the film thickness fluctuation of the transparent film. In this case, in order to stabilize the reflectance with respect to the change in the film thickness of the base transparent film, it is necessary to make the film thickness of the antireflection film 170 nm or more as described above.

Antireflection film materials can be broadly classified into inorganic and organic materials. An inorganic system is a SiON film. This is formed by CVD using a mixed gas of silane and ammonia, and has a large etching selection ratio with respect to the resist. Therefore, there is an advantage that the etching load on the resist is small. is there.
Since it is a basic substrate containing nitrogen atoms, there is also a drawback that it tends to have a footing in a positive resist and an undercut profile in a negative resist. The organic system can be spin-coated and does not require special equipment such as CVD or sputtering, can be peeled off simultaneously with the resist, has no tailing, has a straight shape, and has good adhesion to the resist Is an advantage, and many antireflection films based on organic materials have been proposed. For example, a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in Patent Document 2, an alkali-soluble resin and a light absorber, or a maleic anhydride copolymer and a diamine-type light absorber described in Patent Document 3. A reaction product, a resin binder described in Patent Document 4 and a methylolmelamine-based thermal crosslinking agent, an acrylic resin base type having a carboxylic acid group, an epoxy group, and a light-absorbing group in the same molecule, Patent Examples include those composed of methylolmelamine and a benzophenone-based light absorber described in Document 5, and those obtained by adding a low-molecular light absorber to the polyvinyl alcohol resin described in Patent Document 7. All of these employ a method in which a light absorber is added to the binder polymer or introduced as a substituent into the polymer. However, since many of the light-absorbing agents have aromatic groups or double bonds, the addition of the light-absorbing agent increases the dry etching resistance and has a drawback that the dry etching selectivity with the resist is not so high. As miniaturization progresses and the thinning of resists is spurred, and the next generation ArF exposure uses acrylic or alicyclic polymers as resist materials, resist etching resistance. Decreases. Further, as described above, there is a problem that the thickness of the antireflection film must be increased. For this reason, etching is a serious problem, and there is a demand for an antireflection film having a high etching selectivity with respect to a resist, that is, a high etching speed.

  A light absorbing agent for giving an optimum extinction coefficient in an antireflection film has been studied. In particular, an anthracene type is proposed for KrF, and a phenyl type is proposed for ArF. However, as described above, these are also substituents having excellent dry etching resistance, and even when the polymer backbone formed by pendating the die is made of a polymer having low etching resistance such as acrylic, there is a practical limit. is there. On the other hand, in general, it is known that a material containing silicon has a high etching rate and a high selectivity with respect to a resist under etching conditions using a fluorocarbon-based gas. It is considered that the etching selectivity can be dramatically increased by using. For example, Patent Document 8 proposes an antireflective film for KrF exposure having a polysilane having a phenyl group pendant as a skeleton, and a high etching selectivity is achieved.

In recent years, the resist film has been made thinner with higher resolution. Although there is a demand for improving the etching resistance of resists as the film thickness is reduced, it is not sufficient. A thin mask resist pattern transfer method includes a hard mask method. When the substrate to be processed is p-Si or the like, an SiO ₂ film is considered. When the substrate to be processed is an SiO ₂ film, SiN, W—Si, amorphous Si, or the like is being studied. The hard mask may be left or peeled off. In particular, when the base is an insulating film such as a SiO ₂ film, it is necessary to peel off the W-Si and amorphous Si films because they are good conducting films. Since the SiN film is an insulating film, it does not need to be peeled off depending on the case. However, since the constituent elements are similar to those of SiO ₂ , there is a drawback that the etching selectivity as an original function as a hard mask is low. Furthermore, a hard mask of a SiON film that also functions as an antireflection film has been proposed (Non-Patent Document 1).

  Here, in Patent Documents 9 to 14, a coating liquid for forming a silica-based insulating film is proposed. Many pattern forming methods using this technique and using a silicon-containing polymer as a resist underlayer have been proposed. For example, in Patent Documents 15 to 16, an organic film is formed on a substrate, silica glass is spin-coated thereon, a resist pattern thereon is transferred to a silica glass layer, and then patterned into an organic film layer by oxygen gas etching. A three-layer process has been proposed to transfer and finally process the substrate. Patent Documents 17 to 21 propose a silica glass layer and a silsesquioxane polymer material that also serve as an antireflection film. Further, Patent Document 22 proposes a material that combines the functions of an antireflection film based on a silsesquioxane polymer and a spin-on glass material and a hard mask in Patent Document 23. However, any silicon-containing polymer has a problem in storage stability, and has a fatal defect that the film thickness fluctuates during actual use.

Japanese Patent Laid-Open No. 10-69072 Japanese Patent Publication No. 7-69611 US Pat. No. 5,294,680 Japanese Patent Laid-Open No. 6-118631 JP-A-6-118656 JP-A-8-87115 JP-A-8-179509 Japanese Patent Laid-Open No. 11-60735 JP-A-57-83563 Japanese Unexamined Patent Publication No. 57-131250 JP-A-56-129261 Japanese Patent No. 3287119 JP 2001-22082 A JP 2001-22083 A Japanese Patent No. 3118887 JP 2000-356854 A Japanese Patent Laid-Open No. 5-27444 JP-A-6-138664 JP 2001-53068 A Japanese Patent Laid-Open No. 2001-92122 JP 2001-343752 A US Pat. No. 6420088 Special table 2003-502449 SPIE2000, Vol. 4226, p93 Proc. SPIE Vol. 2195, 225-229 (1994) Proc. SPIE Vol. 3678, 241-250 (1999) SPIE Vol. 3678, p702 (1999)

  The problem to be solved by the present invention is to provide a material for an antireflection film having a high etching selection ratio with respect to a resist, that is, a high etching speed with respect to the resist, and with little film thickness fluctuation even during long-term storage. A pattern forming method for forming an antireflection film layer on a substrate using an antireflection film material and a pattern forming method using the antireflection film as a hard mask for substrate processing are also provided.

  As one of the performance required for the antireflection film, there are no intermixing with a resist and no diffusion of low molecular components into the resist layer (Non-patent Document 2). In order to prevent these problems, a method is generally employed in which thermal crosslinking is performed by baking after spin coating of the antireflection film. Furthermore, it is desirable that the resist pattern on the antireflection film or the resist underlayer film has a vertical shape without skirting or undercut. This is because a dimensional conversion difference occurs after etching the antireflection film in the skirt shape, and the resist pattern collapses after development in the undercut shape.

  In Non-Patent Document 3, it is reported that cross-linking with an acid is effective in reducing the trailing edge of a positive resist. The method of adding a crosslinking agent and crosslinking with an acid is important in the antireflection film material. In Patent Document 20 and Patent Document 17, the addition of a crosslinking agent is effective.

Here, there is a problem that the cross-sectional pattern of the resist after development becomes an inversely tapered shape. This is because the acid used for the crosslinking reaction of the antireflection film moves to the resist layer, and the acid labile group of the resist is eliminated during baking, or the amine compound added in the resist is neutralized. This is thought to be the cause. In order not to move to the resist layer, there is a method of making the acid generated in the antireflection film bulky, but this is not preferable because the crosslinking reaction also hardly proceeds and causes intermixing with the resist. Here, Non-Patent Document 4 proposes a material using a ternary copolymer of hydroxyethyl methacrylate, methyl acrylate, and styrene as an organic antireflection film for ArF. As the crosslinking system, hydroxyethyl methacrylate and glycoluril-based crosslinking agents are used. What should be noted here is the presence of methyl acrylate, which is copolymerized to prevent reverse taper. Methyl acrylate is considered to have an effect of improving adhesion to the resist and suppressing acid diffusion. In order to prevent reverse taper shape, it is necessary to confine the acid in the antireflection film after crosslinking. For this purpose, carbon-oxygen single bonds such as carbonyl, ester, lactone, ether group and / or double bonds are required. It is effective to use a polymer having an organic group containing a bond, and it has been devised to use a siloxane polymer resin pendant with the functional group as an antireflection film.
Furthermore, in the present invention, when the cross-linking reaction mechanism has been intensively investigated, the silanol groups remaining in the polymer greatly contribute to the cross-linking reaction, and there is a certain specification without adding a cross-linking agent that has been essential in the past. It has been found that an antireflection film having substantially no problem can be obtained when the amount of silanol groups is present.

That is, the present invention includes an organic group having a carbon-oxygen single bond and / or a carbon-oxygen double bond, a light-absorbing group, and a silicon atom whose terminal is Si-OH and / or Si-OR. An antireflective modified silicone resin obtained by modifying a silicone resin is provided. Moreover, the anti-reflective film material containing this (A) silicone resin for anti-reflective films, (B) an organic solvent, and (C) an acid generator is provided.
The present invention is also a method for forming a pattern on a substrate by lithography, wherein at least an antireflection film material is applied on the substrate and baked to form an antireflection film, and a photoresist is formed on the antireflection film. Apply the film material, pre-bake to form a photoresist film, expose the pattern circuit area of the photoresist film, develop with a developer to form a resist pattern on the photoresist film, and form the resist pattern An antireflection film and a substrate are etched using the formed photoresist film as a mask, and a pattern is formed on the substrate .
The exposure is preferably performed using a high energy beam or an electron beam having a wavelength of 300 nm or less.
The present invention also provides an antireflection film obtained by applying the antireflection film material of the present invention on a substrate and baking it.

  When the antireflection film material of the present invention is used, it has an n value and a k value that can exhibit a sufficient antireflection effect, particularly for exposure at a short wavelength, and has a high etching selectivity, that is, a photoresist. It is possible to obtain an antireflection film having a sufficiently high etching rate with respect to the film and a sufficiently lower etching rate than the substrate to be processed. Further, the antireflection film material of the present invention has little film thickness fluctuation even during long-term storage. Therefore, this antireflection film has a high effect as a hard mask for the substrate to be processed. Furthermore, the resist pattern formed on the photoresist film on the antireflection film can also be formed into a vertical shape that does not cause reverse taper or tailing.

（上式中、Ｒ^１ａは炭素−酸素単結合及び／又は炭素−酸素二重結合を有する有機基であり、Ｒ^２は光吸収基を有する１価の有機基であってベンゼン環を含み、Ｘは同一又は異種のハロゲン原子、水素原子、ヒドロキシ基、炭素数１〜６のアルコキシ基、又は炭素数１〜６のアルキルカルボニルオキシ基であり、ｍとｎは各々０〜３の整数であって、０＜（４−ｍ−ｎ）≦４の関係を満足する。）
で示されるケイ素含有化合物の２種以上の混合物を加水分解、縮合して得ることができ、末端がＳｉ−ＯＨ及び／又はＳｉ−ＯＲになっているケイ素原子を含み、該Ｓｉ−ＯＨとＳｉ−ＯＲのモル比率が１００／０から２０／８０であるシリコーン樹脂のエポキシ環を変性して種類の異なる炭素−酸素結合を有する有機基に変換して得られ、
該反射防止用変性シリコーン樹脂の繰り返し単位が、
ｎ＝０に相当する下記一般式（２）

（上式（２）中、Ｙ、Ｚは、各々独立に、水素原子、炭素数１〜６のアルキル基、炭素数１〜８のアルキルカルボニル基、炭素数１〜６のアルコキシカルボニル基である。）
又は下記一般式（３）

（上式（３）中、Ｙは、炭素数１〜８のアルキルカルボニル基であり、Ｚは、水素原子である。）
で表される繰り返し単位と、ｍ＝０に相当する繰り返し単位とからなる。
一般式（１）で示されるケイ素含有化合物の重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィ）に基づく測定でポリスチレン換算で５００〜１００万、好ましくは１０００〜５０万である。 Hereinafter, the present invention will be described in more detail.
The modified silicone resin shown in the present invention has the following general formula (1)

(In the above formula, R ^1a is an organic group having a carbon-oxygen single bond and / or a carbon-oxygen double bond, R ² is a monovalent organic group having a light absorbing group and includes a benzene ring, X is the same or different halogen atom, hydrogen atom, hydroxy group, alkoxy group having 1 to 6 carbon atoms, or alkylcarbonyloxy group having 1 to 6 carbon atoms, and m and n are each an integer of 0 to 3. And 0 <(4-mn) ≦ 4 is satisfied.)
It can be obtained by hydrolyzing and condensing a mixture of two or more of the silicon-containing compounds represented by the formula (1), containing a silicon atom whose terminal is Si—OH and / or Si—OR, and the Si—OH and Si Obtained by modifying the epoxy ring of a silicone resin having a —OR molar ratio of 100/0 to 20/80 to convert it into organic groups having different types of carbon-oxygen bonds ,
The repeating unit of the modified silicone resin for antireflection is
The following general formula (2) corresponding to n = 0

(In the above formula (2), Y and Z are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. .)
Or the following general formula (3)

(In the above formula (3), Y is an alkylcarbonyl group having 1 to 8 carbon atoms , and Z is a hydrogen atom .)
And a repeating unit corresponding to m = 0.
The weight average molecular weight of the silicon-containing compound represented by the general formula (1) is 500 to 1,000,000, preferably 1000 to 500,000 in terms of polystyrene as measured based on GPC (gel permeation chromatography).

The organic group having a carbon-oxygen single bond and / or a carbon-oxygen double bond of the present invention or the reference invention preferably has 2 to 30 carbon atoms, and more preferably an epoxy group, an ester group, an alkoxy group, and a hydroxy group. One or more organic groups selected from the group. The organic group means a group containing carbon and may contain hydrogen, nitrogen, sulfur and the like . -Carbon - oxygen single bond and / or carbon - organic group having an oxygen double bond can be cited below as examples.
_{(P-Q 1 - (S} 1) v1 -Q 2 -) u - (T) v2 -Q 3 - (S 2) v3 -Q 4 -
In the above formula, P is a hydrogen atom, a hydroxyl group, an epoxy ring (OCH ₂ CH—), an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or an alkylcarbonyl having 1 to 6 carbon atoms. Q ₁ , Q ₂ , Q ₃ and Q ₄ are each independently —C _q H _2q-p P _p — (wherein P is the same as above, p is an integer of 0 to 3) And q is an integer of 0 to 10), u is an integer of 0 to 3, and S ₁ and S ₂ are each independently —O—, —CO—, —OCO—, —COO— or Represents OCOO. v1, v2, and v3 each independently represent 0 or 1. Along with these, examples of T are shown below. The position where Q ₂ and Q ₃ are bonded to each other in T is not particularly limited, but can be appropriately selected in consideration of reactivity due to steric factors, availability of commercially available reagents used in the reaction, and the like.

Preferable examples of the organic group having a carbon-oxygen single bond and / or a carbon-oxygen double bond of the reference invention include the following. In the chemical formula, (Si) is shown to indicate the bonding site with Si.

Next, the light-absorbing groups of the present invention or the reference invention is a group having absorption at a wavelength between 150 to 300 nm, A anthracene ring (Reference Invention), naphthalene ring (Reference Invention) or a benzene ring (the present invention), Alternatively, these rings may have one or more substituents, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, or 1 carbon atom. To 6 acetal groups are preferred, and more preferred are methyl, methoxy, t-butoxy, t-amyloxy, acetoxy, 1-ethoxyethoxy and the like. An example of this can be given below.

  The methoxy group, acetoxy group, and acetal group of the light absorbing group can be deprotected during polymerization or after polymerization to form a hydroxy group.

  In addition to the aromatic absorbing group, an absorbing group having a Si—Si bond can also be used. Specifically, the following can be mentioned.

As a method for synthesizing the polymer compound, the monomer represented by the general formula (1) is co-condensed by hydrolysis.
The amount of water in the hydrolysis reaction is preferably 0.2 to 10 moles per mole of monomer. At this time, a catalyst can also be used. Acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, nitric acid Acids such as sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, trimethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide , Bases such as choline hydroxide and tetrabutylammonium hydroxide, tetraalkoxytitanium, trialkoxymono (acetylacetonato) titanium, tetraalkoxyzirconium, trialkoxymono (acetylacetonato) zirconium Which metal chelate compound can be mentioned are, to avoid potential by ring-opening the epoxy during polymerization, an organic amine is preferably used in order not mixed with alkali and metal impurities.

  As a reaction operation, water and a catalyst may be dissolved in an organic solvent, and a monomer may be added thereto. At this time, the monomer may be diluted with an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 40 to 80 ° C. for aging is preferable.

  As an organic solvent, a water-soluble thing is preferable, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether and mixtures thereof are preferred.

  Thereafter, an organic solvent that is hardly soluble or insoluble in the above water is added, the organic solvent layer is separated and washed with water to remove the catalyst used for the hydrolytic condensation. At this time, the catalyst may be neutralized as necessary.

  As the organic solvent, those hardly soluble or insoluble in water are preferable, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, Ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate Butyl, tert-butyl propionate, propylene glycol mono tert Butyl ether acetate, γ- butyrolactone, and mixtures thereof.

  Thereafter, the organic solvent layer is separated and dehydrated. It is necessary to sufficiently perform the remaining of water in order to advance the condensation reaction of the remaining silanol. Preferable examples include an adsorption method using a salt such as magnesium sulfate and molecular sieve, and an azeotropic dehydration method while removing the solvent.

  As another operation method, an organic solvent that is hardly soluble or insoluble in water can also be used as the organic solvent used for the hydrolysis and condensation of the monomer. For example, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether Acetate, γ-butyl lactone and A mixture thereof are preferred.

The monomer is dissolved in the organic solvent, and water is added to initiate the hydrolysis reaction.
The catalyst may be added to water or may be added to an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 40 to 80 ° C. for aging is preferable.

By adjusting the reaction conditions at this time, a silicone resin in which the proportion of silicon atoms having a terminal end required in the present invention is Si—OH and / or Si—OR is 0.1 to 50 mol%. Obtainable. The terminal group at this time can be easily obtained by using 29Si-NMR. When the ratio of silicon atoms whose ends are Si—OH and / or Si—OR is A (mol%), the following formula is obtained.

  Here, Q1, Q2, Q3 and Q4 are the number of siloxane bonds formed by tetrafunctional Si atoms, T1, T2 and T3 are the number of siloxane bonds formed by trifunctional Si atoms, and D1 and D2 are 2 This represents the number of siloxane bonds formed by the functional Si atom. The amount of each bond is calculated by integrating the 29Si-NMR peak values.

  At this time, when A is 0.1 mol% or less, the number of terminal SiOH and SiOR used for crosslinking of the resin is too small, and the coating film cannot be sufficiently cured, and the resist is used in the next step. Mixing may occur and a resist pattern with good rectangularity may not be obtained. On the other hand, if A is 50 mol% or more, condensation may be insufficient, and only a coating film having a weak strength may be obtained, and a resist pattern may collapse, which may be undesirable.

Furthermore, even when A is between 0.1 mol% and 50 mol%, a sufficiently cured coating film may not be obtained unless the ratio of Si—OH and Si—OR is a predetermined ratio. . That is, more preferably, a ratio of Si—OH / Si—OR = (100/0) to (20/80) is necessary. At this time, the ratio of —SiOH / —SiOR can be determined using ¹³ CNMR, using the integrated intensity (B) per one carbon atom at the α-position of the Si atom as an internal standard. That is, the R of -SiOR -SiO When _{R x -CH 2 C H 2 -R} x , and the the use of integrated intensity of the carbon atoms of the underlined portion (C), it is possible to determine by the following equation.
-SiOH / -SiOR = (A / 100-C / B) / (C / B)
When the ratio of Si-OR is higher than Si-OH / Si-OR = 20/80, the Si-OR cannot condense with each other, so that formation of a siloxane bond for film hardening is small and a film with sufficient hardness is obtained. It may not be possible. On the other hand, when the ratio of Si-OR is lower than Si-OH / Si-OR = 20/80, condensation between Si-OH and condensation between Si-OH and Si-OR easily proceeds and sufficient strength is obtained. It is a feature of the present invention that a coating film free from intermixing can be obtained.

Furthermore, when an epoxy group is contained in an organic group containing a carbon-oxygen bond, a modified silicone resin having an organic group having a different type of carbon-oxygen bond is formed by a modification reaction after forming a silicone resin. Can be converted. Examples of the repeating unit of the modified silicone resin are given below. The first and second repeating units in the upper stage are examples of the present invention, and the others are examples of the reference invention.

  Here, Y and Z are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. Specifically, , Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-ethylbutyl group, 3-ethylbutyl Group, 2,2-diethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, cyclohexylcarbonyl group, methoxy group Examples include carbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, t-butoxycarbonyl group, etc. It can be.

  Conversion from the original silicone resin is possible by generally known methods. For example, it can be easily converted into a modified silicone resin by heating alcohols or carboxylic acids in the presence of an acid, alkali or quaternary ammonium catalyst. In the reaction with carboxylic acids, carboxylic acid itself becomes a catalyst, so there is no need to add a catalyst.

  Acid catalysts used at this time include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, oxalic acid, acetic acid, propionic acid Acids such as oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid can be used. Examples of the alkali catalyst include bases such as ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, triethylamine, triethanolamine, benzyldiethylamine, tetraethylammonium hydroxide, choline hydroxide, and tetrabutylammonium hydroxide. Examples of the quaternary ammonium catalyst include benzyltriethylammonium chloride and benzyltriethylammonium bromide.

  The original silicone resin and modified silicone resin thus obtained (hereinafter referred to as a silicone resin including both and a blend of both) can also be used by blending. Since the blend ratio at this time greatly affects the performance of the resulting composition, it can be blended at an arbitrary ratio so that the performance is maximized. In the obtained mixture, it is more preferable to make the polymer compound into a uniform composition by operations such as heating, stirring, ultrasonic irradiation, and kneading.

  The organic solvent of the component (B) used in the present invention may be any organic solvent that can dissolve a silicone resin, an acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and ethyl 2-n-amyl ketone, 3-methoxybutanol, 3-ethyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2- Alcohols such as propanol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol diethyl ether, ethers such as diethylene glycol diethyl ether, propylene glycol monoethyl ether acetate, Propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, ethyl 3-methoxypropionate, 3-ethoxypropyl Examples include esters such as ethyl pionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. One of these may be used alone or two or more may be used. Although it can be used in mixture, it is not limited to these. In the present invention, among these organic solvents, diethylene glycol diethyl ether, 1-ethoxy-2-propanol, propylene glycol monoethyl ether acetate and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used. Is done.

  The amount of the organic solvent used is preferably 500 to 2,000 parts by weight, particularly 400 to 3,000 parts by weight, based on 100 parts by weight of the silicone resin.

  In this invention, the acid generator shown by (C) component for further accelerating | stimulating the crosslinking reaction by a heat | fever can be added. The acid generator includes those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of them can be added.

As the acid generator used in the present invention,
i. An onium salt of the following general formula (P1a-1), (P1a-2), (P1a-3) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

(In the above formula, each of R ^101a , R ^101b and R ^101c is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and having 6 to 20 carbon atoms. An aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, part or all of hydrogen atoms of which may be substituted with an alkoxy group, etc. R ^101b and R ^101c and may form a ring, when they form a ring, R ^101b, .K indicating each is R ^101c alkylene group having 1 to 6 carbon atoms ^- .R ^101d is representative of a non-nucleophilic counter ion R ^101e , R ^101f and R ^101g are represented by adding a hydrogen atom to R ^101a , R ^101b and R ^101c , R ^101d and R ^101e , and R ^101d , R ^101e and R ^101f may form a ring. When forming a ring, R ^101d and R ^101e and R ^101d and R ^101e and R ^101f represent an alkylene group having 3 to 10 carbon atoms.)

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f and R ^101g may be the same as or different from each other. Specifically, as the alkyl group, a methyl group, an ethyl group, Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylethyl, 4- Examples thereof include an ethylcyclohexyl group, a cyclohexylethyl group, a norbornyl group, an adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Ethylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, diethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like.

Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, tosylate, and benzene. Examples thereof include aryl sulfonates such as sulfonate, 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

  (P1a-1) and (P1a-2) have the effects of both a photoacid generator and a thermal acid generator, while (P1a-3) acts as a thermal acid generator.

(In the above formula, R ^102a and R ^102b each independently represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear or branched alkyl group having 1 to 10 carbon atoms. R ^104a and R ^104b each independently represents a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.

Specific examples of R ^102a and R ^102b include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylethyl group, 4-ethylcyclohexyl group, cyclohexylethyl group and the like.

R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like.

^Examples of R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group.

Examples of K ⁻ are the same as those described in the formulas (P1a-1), (P1a-2), and (P1a-3).

(In the above formula, R ¹⁰⁵ and R ¹⁰⁶ are each independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, aryl group or halogenated aryl group having 6 to 20 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Examples include amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like.

Examples of the halogenated alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a trifluoroethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, methylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and diethylphenyl group.

Examples of the halogenated aryl group for R ¹⁰⁵ and R ¹⁰⁶ include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group.
^Examples of the aralkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a benzyl group and a phenethyl group.

(In the above formula, R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, aryl group or halogen having 6 to 20 carbon atoms. An aryl group or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ are each independently And represents a linear or branched alkylene group having 1 to 6 carbon atoms.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

（上式中、Ｒ^101a、Ｒ^101bは上記と同様である。）

(In the above formula, R ^101a and R ^101b are the same as above.)

(In the above formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further It may be substituted with a linear or branched alkyl or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a linear or branched group having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or an alkoxy group having 1 to 4 carbon atoms; A phenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or substituted with a chlorine atom or a fluorine atom Is There may be.)

^Examples of the arylene group for R ¹¹⁰ include a 1,2-phenylene group and a 1,8-naphthylene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a phenylethylene group, and a norbornane- 2,3-diyl group etc. are mentioned, As the alkenylene group, 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like can be mentioned.

^Examples of the alkyl group of R ¹¹¹ include the same groups as R ^{101a to} R ^101c, and examples of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl group, 4-pentenyl group, diethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7 -Octenyl group and the like, and as the alkoxyalkyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, heptyloxyethyl group, methoxyethyl group, Ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl , Methoxypropyl, ethoxypropyl, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

Examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Examples of the alkoxy group having 1 to 4 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
Examples of the phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or an acetyl group include a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, p -Acetylphenyl group, p-nitrophenyl group, etc. are mentioned, As a C3-C5 heteroaromatic group, a pyridyl group, a furyl group, etc. are mentioned.

  Specific examples of onium salts include tetraethylammonium trifluoromethanesulfonate, tetraethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, and p-toluenesulfonic acid. Tetraethylammonium, trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoro Triphenylsulfonium lomethanesulfonate, trifluoromethanesulfonic acid (p-tert-butyl) Xylphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (P-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid tri Phenylsulfonium, butanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid triethylsulfonium, p-toluenesulfonic acid Liethylsulfonium, cyclohexylethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, diethylphenylsulfonium trifluoromethanesulfonate, diethylphenylsulfonium p-toluenesulfonate, Dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethyl (2-norbornyl) sulfonate trifluoromethanesulfonate ( 2-Oxocyclohexyl) sulfoniu And ethylene bis [ethyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylethyltetrahydrothiophenium triflate, and the like.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane Bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfur) Nyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Etc.

  Examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-diethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-ethyl3,4-pentanedione glyoxime, bis -O- (n-butanesulfonyl) -α-diethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n Butanesulfonyl) -2-ethyl 3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-diethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-diethylglyoxime, bis-O -(1,1,1-trifluoroethanesulfonyl) -α-diethylglyoxime, bis-O- (tert-butanesulfonyl) -α-diethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α- Diethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-diethylglyoxime, bis-O- (benzenesulfonyl) -α-diethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-diethylglyoxime Oxime, bis-O- (p-tert-butylbenzenesulfonyl) -α Diethyl glyoxime, bis -O- (xylene sulfonyl)-.alpha.-diethyl glyoxime, bis -O- (camphorsulfonyl)-.alpha.-diethyl glyoxime, and the like.

  Examples of bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoroethylsulfonylmethane, bisethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane. Can be mentioned.

  Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

  Examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Examples include benzene.

  Examples of sulfonic acid ester derivatives of N-hydroxyimide compounds include N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid. Ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-triethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N- Hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Ester, N-hydroxyglutarimide benzenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydro Siphthalimidobenzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N- Hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3 -Dicarboximide p-toluenesulfonic acid ester etc. are mentioned.

  Preferably, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylethyl (2-oxo) (Cyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) ethyl (2-oxocyclohexyl) sulfur Onium salts such as 1,2′-naphthylcarbonylethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) ) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis- Glyoxime derivatives such as O- (p-toluenesulfonyl) -α-diethylglyoxime and bis-O- (n-butanesulfonyl) -α-diethylglyoxime; Bissulfone derivatives such as butylsulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Acid ester derivatives are used.

In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types.
The addition amount of the acid generator is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight with respect to 100 parts by weight of the silicone resin. If the amount is less than 0.1 part by weight, the amount of acid generated is small and the crosslinking reaction may be insufficient. If the amount exceeds 50 parts by weight, a mixing phenomenon may occur due to the acid moving to the upper resist.

  Here, the neutralizing agent of the component (D) is a material for preventing the generated acid from diffusing into the resist layer to be applied in the next step, for example, methylol group, alkoxyethyl group, acyloxy group. An epoxy compound, a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one group selected from an ethyl group can be exemplified.

  Examples of the neutralizing agent include epoxy compounds such as tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like.

  Among the neutralizing agents, specific examples of melamine compounds include hexamethylol melamine, hexamethoxyethyl melamine, compounds in which 1 to 6 of hexamethylol melamine are methoxyethylated and mixtures thereof, hexamethoxyethyl melamine, hexaacyloxy Examples thereof include compounds in which 1 to 5 methylol groups of ethylmelamine and hexamethylolmelamine are acyloxyethylated, or a mixture thereof.

  Among the neutralizing agents, guanamine compounds include tetramethylolguanamine, tetramethoxyethylguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxyethylated, and mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine. And compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxyethylated, and mixtures thereof.

  Among the neutralizing agents, as the glycoluril compound, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxyethylglycoluril, a compound in which 1 to 4 of the methylol groups of tetramethylolglycoluril are methoxyethylated, or its Examples thereof include a mixture, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxyethylated, or a mixture thereof.

  Among the neutralizing agents, examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are converted to methoxyethyl group, or a mixture thereof. It is done.

  Next, the present invention is a method for forming a pattern on a substrate by lithography, wherein at least the antireflection film material of the present invention is applied on the substrate and baked to form an antireflection film. A photoresist film material is applied thereon, pre-baked to form a photoresist film, the pattern circuit region of the photoresist film is exposed, and then developed with a developer to form a resist pattern on the photoresist film. There is provided a pattern forming method for forming a pattern on a substrate by etching the antireflection film and the substrate using the photoresist film on which the resist pattern is formed as a mask.

Further, the reference invention is a method of forming a pattern on a substrate by lithography, and at least the antireflection film material of the present invention is applied on the substrate and baked to form an antireflection film, and the antireflection film is formed on the antireflection film. A photoresist film material is applied to the substrate, pre-baked to form a photoresist film, the pattern circuit area of the photoresist film is exposed, and then developed with a developer to form a resist pattern on the photoresist film. There is also provided a pattern forming method for etching a reflection preventing film using a patterned photoresist film as a mask, and further etching the substrate using the patterned reflection preventing film as a mask to form a pattern on the substrate. .

These pattern forming methods will be described with reference to FIG.
First, the process up to the formation of the resist pattern shown in FIG.
The antireflection film 10 can be formed by applying the antireflection film material of the present invention on the substrate 12 by spin coating or the like. After application by spin coating or the like, it is desirable to evaporate the organic solvent and to bake to promote the crosslinking reaction in order to prevent mixing with the upper photoresist film 11. The baking temperature is preferably in the range of 80 to 300 ° C., and the baking time is preferably in the range of 10 to 300 seconds.

After the antireflection film 10 is formed, a photoresist film 11 is formed thereon, and spin coating is preferably used as in the formation of the antireflection film. Pre-baking is performed after applying the photoresist film material by spin coating or the like, and the pre-baking condition is preferably a temperature range of 80 to 180 ° C. and a time range of 10 to 300 seconds.
Thereafter, the pattern circuit region is exposed, post-exposure baking (PEB), and development with a developer is performed to obtain a resist pattern (FIG. 1A).

Next, the process up to the pattern formation shown in FIG.
In order to etch the antireflection film 10 using the photoresist film 11 as a mask, etching is performed using a chlorofluorocarbon gas, nitrogen gas, carbon dioxide gas, or the like. The antireflection film 10 formed of the antireflection film material of the present invention is characterized in that the etching rate with respect to the gas is high and the film loss of the upper photoresist film 11 is small.

Etching of the next substrate 12 includes etching mainly using a chlorofluorocarbon gas when the layer 12a to be processed on the base layer 12b is SiO ₂ or SiN, chlorine based on p-Si (p-type Si), Al, or W, Etching mainly using bromine-based gas. The antireflection film 10 formed of the antireflection film material of the present invention is excellent in etching resistance to chlorine and bromine, and can be applied as a hard mask particularly when the layer to be processed is p-Si, Al, W, or the like. Even when the layer 12a to be processed is an SiO ₂ or SiN film, the antireflection film 10 formed of the antireflection film material of the present invention has an etching rate higher than that of the photoresist film 11, but is higher than that of the substrate 12. Is slow and can function as a hard mask.
Therefore, when a pattern is created by etching away the layer 12a to be processed of the substrate 12, the photoresist film 11 may be used as a mask, or the antireflection film 10 on which the pattern is formed may be processed as a mask. .

Further, the reference invention is a method of forming a pattern on a substrate by lithography, and at least an organic film is formed on the substrate, and the antireflection film material of the present invention is applied on the organic film and baked. An antireflection film is formed, a photoresist film material is applied on the antireflection film, prebaked to form a photoresist film, the pattern circuit area of the photoresist film is exposed, and then developed with a developer. Forming a resist pattern on the photoresist film, etching the antireflection film using the photoresist film on which the resist pattern is formed as a mask, etching the organic film using the antireflection film on which the pattern is formed as a mask, and There is provided a pattern forming method for forming a pattern on a substrate by etching the substrate.

  Thus, the antireflection film formed from the antireflection film material of the present invention can be applied as an intermediate layer in a multilayer resist process such as a three-layer resist process. This pattern forming method will be described with reference to FIG.

First, the process up to the formation of the resist pattern shown in FIG.
An organic film 23 is formed on the substrate 22 by spin coating or the like. Since this organic film 23 acts as a mask when etching the substrate 22, it is desirable that the etching resistance is high, and it is required not to mix with the upper silicon-containing antireflection film 20, so that the organic film 23 is applied by spin coating or the like. It is desirable to crosslink later with heat or acid. An antireflection film 20 and a photoresist film 21 formed from the antireflection film material of the present invention are formed on the organic film 23 by the same method as described above. Thereafter, a resist pattern is obtained by exposing the pattern circuit area and developing with a developer (FIG. 2A).
Here, examples of the organic film include resins such as cresol novolak, naphthol novolak, catol dicyclopentadiene novolak, amorphous carbon, polyhydroxystyrene, acrylate, methacrylate, polyimide, and polysulfone.

  Next, as shown in FIG. 2B, the antireflection film 20 is etched using the photoresist film 21 on which the pattern is formed as a mask, and the resist pattern is transferred to the antireflection film 20. Next, as shown in FIG. 2C, the pattern formed on the antireflection film 20 is transferred to the organic film 23 by oxygen plasma etching or the like. At this time, the photoresist film 21 is also etched away. Next, as shown in FIG. 2D, the layer to be processed 22a is etched on the base layer 22b to form a pattern on the substrate 22.

  The thickness of each film and each layer is, for example, 50 to 2000 nm for the organic film, 50 to 2000 nm for the antireflection film, and 0.1 to 1 μm (preferably 100 to 500 nm) for the resist film, but is not limited thereto. It is not a thing.

  The substrate used at this time is not particularly limited, and a silicon wafer or the like is used.

A known resist composition can be used for forming the resist layer, and for example, a combination of a base resin, an organic solvent, and an acid generator can be used.
Base resins include polyhydroxystyrene and its derivatives, polyacrylic acid and its derivatives, polymethacrylic acid and its derivatives, copolymers formed from hydroxystyrene, acrylic acid, methacrylic acid and their derivatives, cycloolefin And three or more copolymers selected from maleic anhydride and acrylic acid and derivatives thereof, cycloolefin and derivatives thereof, and three or more copolymers selected from maleimide, acrylic acid and derivatives thereof, polynorbornene, and Examples thereof include one or more polymer polymers selected from the group consisting of metathesis ring-opening polymers. In addition, the main skeleton remains after the induction, such as acrylic acid derivatives such as acrylic acid esters, methacrylic acid derivatives such as methacrylic acid derivatives, and alkoxystyrenes such as hydroxystyrene derivatives. Means what

As a resist for KrF excimer laser, polyhydroxystyrene (PHS), a copolymer selected from hydroxystyrene, styrene, acrylic acid ester, methacrylic acid ester and maleimide N carboxylic acid ester, for ArF excimer laser The resist includes polyacrylate ester, polymethacrylate ester, alternating copolymerization system of norbornene and maleic anhydride, alternating copolymerization system of tetracyclododecene and maleic anhydride, polynorbornene system, and ring-opening polymerization. However, the present invention is not limited to these polymerization polymers.

  In the case of a positive resist, the dissolution rate of the unexposed area is generally lowered by substituting the hydroxyl group of the phenol or carboxyl group with an acid labile group. That is, a hydrogen atom of a carboxyl group or a hydrogen atom of a phenolic hydroxyl group is substituted with an acid labile group having an alkali dissolution control ability, and the acid labile group is dissociated by the action of an acid generated by exposure to dissolve in an aqueous alkali solution. It can be used as a positive resist material in combination with a base resin that increases.

Examples of the organic solvent and acid generator used in the resist composition include the same organic solvent as the component (B) and acid generator as the component (C) of the antireflection film material.
The addition amount of each component of the resist composition is, for example, the addition amount of the base resin is the same as the addition amount of the silicone resin as the component (A) in the antireflection film material, and the organic solvent used in the resist composition The amount of the acid generator added is also the same as that of the organic solvent as the component (B) and the acid generator as the component (C) of the antireflection film material.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples, reference synthesis examples, polymerization examples , reference examples, and examples, but the present invention is not limited to these descriptions.
Reference synthesis example 1
A 3000 ml glass flask was charged with 1400 g of methanol, 700 g of pure water and 50 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 217 g of 3-glycidoxypropyltrimethoxysilane and 43 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and methanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. The polymer 1 (Polymer 1) was obtained under reduced pressure.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the ratio of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 10.2%. Si-OH / Si-OR was calculated by ¹³ C-NMR, and Si-OH / Si-OR = 100/0.

Reference synthesis example 2
A 3000 ml glass flask was charged with 1400 g of ethanol, 700 g of pure water and 50 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 139 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 32 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and ethanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. The polymer 2 (Polymer 2) was obtained under reduced pressure.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by C ¹³ -NMR as follows.
Subsequently, the ratio of terminal groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 3.2%. Si-OH / Si-OR was calculated by ¹³ C-NMR, and Si-OH / Si-OR = 90/10.

Reference synthesis example 3
A 3000 ml glass flask was charged with 1500 g of ethanol, 750 g of pure water, and 150 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 450 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 162 g of 3-glycidoxypropyltrimethoxysilane and 138 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C. The mixture was stirred at 0 ° C. for 4 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and ethanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. The polymer 3 (Polymer 3) was obtained under reduced pressure.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the proportion of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 19%, and Si—OH / Si—OR was calculated by ¹³ C-NMR to find Si—OH / Si—. OR = 97/3.

Synthesis example 4
A 3000 ml glass flask was charged with 1400 g of ethanol, 700 g of pure water and 50 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 139 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 32 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and ethanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 1000 g of acetic acid was added, and the ethyl acetate was removed under reduced pressure while heating the liquid temperature to 40 ° C. Distilled off. The acetic acid solution of the obtained polymer was stirred at 40 ° C. for 12 hours. Subsequently, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added to the obtained solution, and polymer 4 (Polymer 4) was obtained under reduced pressure while heating the liquid temperature to 40 ° C.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the ratio of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 20.5%. Si-OH / Si-OR was calculated by ¹³ C-NMR, and Si-OH / Si-OR = 40/60.

Synthesis example 5
A 3000 ml glass flask was charged with 1400 g of methanol, 700 g of pure water and 50 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 217 g of 3-glycidoxypropyltrimethoxysilane and 43 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and methanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 1000 g of acetic acid was added, and the ethyl acetate was removed under reduced pressure while heating the liquid temperature to 40 ° C. Distilled off. To the obtained acetic acid solution of the polymer, 1.6 g of a 60% aqueous perchloric acid solution was added at room temperature, followed by stirring at 70 ° C. for 45 hours. To the obtained polymer solution, 3000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, and then 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added to the obtained solution. Polymer 5 (Polymer 5) was obtained under reduced pressure while heating the liquid temperature to 40 ° C.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the ratio of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 15.6%, and Si—OH / Si—OR was calculated by ¹³ C-NMR to find Si—OH / Si-OR = 70/30.

Reference synthesis example 6
A 3000 ml glass flask was charged with 1400 g of methanol, 700 g of pure water and 50 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 217 g of 3-glycidoxypropyltrimethoxysilane and 43 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and methanol was distilled off under reduced pressure. To the resulting liquid was added 2000 ml of ethyl acetate, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, and ethyl acetate was distilled off under reduced pressure while heating the liquid temperature to 40 ° C. The obtained polymer was dissolved in 1000 ml of methanol, 5 g of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was added at room temperature, and the mixture was stirred at 65 ° C. for 40 hours. After 25 g of acetic acid was added to the obtained polymer solution to stop the reaction, methanol was distilled off at 40 ° C. under reduced pressure. To the obtained polymer, 3000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, and then 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. Under reduced pressure, Polymer 6 was obtained.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the ratio of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 41.6%. Si-OH / Si-OR was calculated by ¹³ C-NMR, and Si-OH / Si-OR = 80/20.

Synthesis example 7
A 3000 ml glass flask was charged with 1400 g of ethanol, 700 g of pure water and 50 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 139 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 32 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and ethanol was distilled off under reduced pressure. To the resulting liquid was added 2000 ml of ethyl acetate, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, and ethyl acetate was distilled off under reduced pressure while heating the liquid temperature to 40 ° C. The obtained polymer was dissolved in a mixed solution of 1000 ml of methanol and 1000 ml of tetrahydrofuran, 5 g of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was added at room temperature, and the mixture was stirred at 65 ° C. for 30 hours. . After 25 g of acetic acid was added to the obtained polymer solution to stop the reaction, ethanol and tetrahydrofuran were distilled off at 40 ° C. under reduced pressure. To the obtained polymer, 3000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, and then 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. Under reduced pressure, Polymer 7 (Polymer 7) was obtained.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the proportion of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 5.7%, and Si—OH / Si—OR was calculated by ¹³ C-NMR to find Si—OH / Si-OR = 85/15.

Reference synthesis example 8
A 3000 ml glass flask was charged with 1400 g of methanol, 700 g of pure water and 50 g of a 25 wt% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 300 g of tetramethoxysilane, 217 g of 3-glycidoxypropyltrimethoxysilane and 43 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and methanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. The polymer 8 (Polymer 8) was obtained under reduced pressure.
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the proportion of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 38.7%. Si-OH / Si-OR was calculated by ¹³ C-NMR, and Si-OH / Si-OR = 60/40.

Comparative Synthesis Example 1
Dissolve 23.6 g of 3-glycidoxypropyltrimethoxysilane and 19.8 g of phenyltrimethoxysilane in 200 g of tetrahydrofuran (THF) and 100 g of pure water, bring the liquid temperature to 35 ° C., and dropwise add 37% hydrochloric acid over 21 g for 1 hour. Then, the temperature was raised to 64 ° C., and a silanol condensation reaction, an epoxy group ring-opening reaction, and a hydrochloric acid addition reaction were carried out. 200 g of diethyl ether was added to the reaction liquid, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 200 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the pressure was reduced while heating the liquid temperature to 60 ° C. Underneath, THF and diethyl ether water were removed to obtain Comparative Polymer 1 (Reference Polymer 1).
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the proportion of end groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 55.6%, and Si—OH / Si—OR was calculated by ¹³ C-NMR to calculate Si—OH / Si-OR = 50/50.

Comparative Synthesis Example 2
In 200 g of tetrahydrofuran and 100 g of pure water, 42.6 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 19.8 g of phenyltrimethoxysilane are dissolved to bring the liquid temperature to 35 ° C. 7 g was added, and then the temperature was raised to 60 ° C. to conduct a silanol condensation reaction.
200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, 1% of 60% by weight nitric acid was added to the weight of the organic liquid layer, washed twice with 300 g of ultrapure water, and propylene glycol monoethyl ether acetate. 200 g of (PGMEA) was added, and THF and diethyl ether water were removed under reduced pressure while heating the liquid temperature to 60 ° C. to obtain Comparative Example Polymer 2 (Reference Polymer 2).
The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the ratio of terminal groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 30.2%. Si-OH / Si-OR was calculated by ¹³ C-NMR, and Si-OH / Si-OR = 15/85.

Examples, Reference Examples, and Comparative Examples [Adjustment of Antireflection Film Material]
FC-430 (manufactured by Sumitomo 3M Co.) 0.1 weight using the polymer compounds obtained in Synthesis Examples 4 to 5 , 7 and Reference Synthesis Examples 1 to 3, 6, 8 and Comparative Synthesis Examples 1 to 2 % In an organic solvent containing 1% and filtered through a 0.1 μm fluororesin filter (Examples 5 to 7 and Reference Examples 1 to 4 and 8) Examples 1-2) were prepared respectively.

Each composition in Table 1 is as follows.
Polymers 1 to 8: Synthetic Examples 4 to 5, 7 and those obtained from Reference Synthetic Examples 1 to 3, 6, and 8 Comparative Polymer 1: Obtained from Comparative Synthetic Example 1 Comparative Polymer 2: Obtained from Comparative Synthetic Example 2 Acid generator: AG1, AG2 (see the following structural formula)
Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

The antireflection film material thus prepared was applied on a silicon substrate and baked at 200 ° C. for 120 seconds to form an antireflection film having a thickness of 193 nm.
After forming the antireflection film, A. The refractive index (n, k) of the antireflection film at a wavelength of 193 nm was determined with a Woollam Inc. variable incidence ellipsometer (VASE), and the results are shown in Table 1.

As shown in Table 1, the antireflection films of Examples 5 to 7, Reference Examples 1 to 4 and Comparative Examples 1 to 2 have a refractive index n value of 1.5 to 1.9 and a k value of 0. It can be seen that it has an optimum n value and k value that are sufficient to exhibit a sufficient antireflection effect. Furthermore, it was found that there was almost no change in film thickness even after standing at room temperature for 3 months.

[Preparation of photoresist film material]
The following polymer (Polymer A) is used as the base resin for the photoresist film material.
-Polymer C) was prepared.

The polymer A is a polymer composed of the repeating units s and t shown above. The copolymerization ratio and weight average molecular weight (Mw) of this polymer are shown below.
Copolymerization molar ratio s: t = 0.40: 0.60
Weight average molecular weight (Mw) = 8800

The polymer B is a polymer composed of the repeating units u and v shown above. The copolymerization ratio and weight average molecular weight (Mw) of this polymer are shown below.
Copolymerization molar ratio u: v = 0.50: 0.50
Weight average molecular weight (Mw) = 8300

The polymer C is a polymer composed of the repeating units w and x shown above. The copolymerization ratio and weight average molecular weight (Mw) of this polymer are shown below.
Copolymerization molar ratio w: x = 0.40: 0.60
Weight average molecular weight (Mw) = 18300

Using the prepared polymers (polymer A to polymer C), photoresist film materials 1 to 3 for ArF lithography were prepared with the compositions shown in Table 2 below. Each composition in Table 2 is as follows.
Polymer: Polymer A to Polymer C
Acid generator: PAG1 (see structural formula below)
Base additive: Triethanolamine Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

[Observation of pattern shape and etching resistance test]
(1) Observation of pattern shape The above prepared antireflection film materials (Examples 5 to 7, Reference Examples 1 to 4, 8, and Comparative Examples 1 to 2) were applied on a silicon substrate and baked at 200 ° C. for 120 seconds. Thus, an antireflection film having a thickness of 193 nm was formed.

  Next, on the antireflection film, the above-prepared photoresist film materials 1 to 3 are applied in the combinations shown in Table 3, and baked at 120 ° C. for 60 seconds to prepare a 250 nm-thick photoresist film. did.

  Next, the film was exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 ring illumination, Cr mask), baked at 110 ° C. for 90 seconds (PEB), and 2.38 wt%. Development was performed with an aqueous tetramethylammonium hydroxide (TMAH) solution to obtain a positive resist pattern of 0.13 μm line and space. The resulting resist pattern shape (cross-sectional shape of the photoresist film) was observed for occurrence of tailing, undercutting, and intermixing, and the results are shown in Table 3.

As a result, when the antireflection film materials of Examples 5 to 7 and Reference Examples 1 to 4 and 8 are used, the photoresist film causes skirting, undercut, and intermixing phenomenon near the boundary with the antireflection film. It was confirmed that a rectangular pattern was obtained. However, when the antireflection film material of Comparative Example 1 was used, slightly reverse taper and skirting were observed.

(2) Etching resistance test Antireflection film formed from the antireflection film material (Examples 5 to 7, Reference Examples 1 to 4, 8, Comparative Examples 1 to 2), and the photoresist film material (photoresist film material) The etching resistance of the photoresist film formed from 1 to 3) was evaluated under the following two conditions.

(I) Etching Test with CHF ₃ / CF ₄ Gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the thickness difference between the antireflection film, the photoresist film, and the SiO ₂ film before and after etching was measured.
Etching conditions are as shown below.
Chamber pressure 40Pa
RF power 1,300W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
Time 10sec
The results are shown in Table 4.

As shown in Table 4, the antireflection film formed from the antireflection film material of the present invention (Examples 5 to 7, Reference Examples 1 to 4 and 8) has a rate of dry etching with CHF ₃ / CF ₄ gas. However, it is sufficiently faster than the photoresist film and sufficiently slower than the SiO ₂ film. Therefore, when the layer to be processed of the substrate is a SiO ₂ film, it has a sufficient function as a hard mask in substrate etching.

(Ii) Etching test with Cl ₂ / BCl ₃ -based gas Using a dry etching apparatus L-507D-L made by Nidec Anelva, the thickness difference between the antireflection film and p-Si before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30ml / min
BCl ₃ gas flow rate 30ml / min
CHF ₃ gas flow rate 100ml / min
O ₂ gas flow rate 2ml / min
60 sec
The results are shown in Table 5.

As shown in Table 5, the antireflection film formed from the antireflection film material of the present invention (Examples 5 to 7, Reference Examples 1 to 4 and 8) has a rate of dry etching with a Cl ₂ / BCl ₃ gas. However, it is sufficiently slower than p-Si. Therefore, when the processed layer of the substrate is p-Si, the performance as a hard mask is satisfied.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

It is explanatory drawing regarding the pattern formation method of this invention, (a) The resist pattern after image development, (b) The pattern after board | substrate dry etching is shown. It is explanatory drawing regarding another pattern formation method, (a) The resist pattern after image development, (b) The pattern transcribe | transferred to the antireflection film, (c) The pattern transcribe | transferred to the organic film, (d) After board | substrate dry etching Shows the pattern. It is a graph which shows the relationship between the film thickness of an anti-reflective film, and a reflectance, and shows the board | substrate reflectance with respect to various k value.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Antireflection film 11 Photoresist film 12 Substrate 12a Processed layer 12b Underlayer 20 Antireflection film 21 Photoresist film 22 Substrate 22a Processed layer 22b Underlayer 23 Organic film

Claims (5)

The following general formula (1)

(In the above formula, R ^1a is an organic group having a carbon-oxygen single bond and / or a carbon-oxygen double bond, R ² is a monovalent organic group having a light absorbing group and includes a benzene ring, X is the same or different halogen atom, hydrogen atom, hydroxy group, alkoxy group having 1 to 6 carbon atoms, or alkylcarbonyloxy group having 1 to 6 carbon atoms, and m and n are each an integer of 0 to 3. And 0 <(4-mn) ≦ 4 is satisfied.)
It can be obtained by hydrolyzing and condensing a mixture of two or more silicon-containing compounds represented by the formula (1), having a weight average molecular weight based on GPC of 500 to 1,000,000, and the terminal being Si—OH and / or Si—OR. An organic group having different carbon-oxygen bonds by modifying an epoxy ring of a silicone resin containing a silicon atom and having a molar ratio of Si—OH to Si—OR of 100/0 to 20/80 A modified silicone resin for antireflection obtained by conversion ,
The repeating unit of the modified silicone resin for antireflection is
The following general formula (2) corresponding to n = 0

(In the above formula (2), Y and Z are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. .)
Or the following general formula (3)

(In the above formula (3), Y is an alkylcarbonyl group having 1 to 8 carbon atoms , and Z is a hydrogen atom .)
A modified silicone resin for antireflection comprising a repeating unit represented by formula (I) and a repeating unit corresponding to m = 0.   An antireflection film material comprising the modified silicone resin for antireflection according to claim 1, an organic solvent, and an acid generator.   Further, it contains a neutralizing agent for preventing the acid generated in the antireflective film from diffusing into the resist layer coated on the antireflective film, and the neutralizing agent contains a methylol group, an alkoxyl The antireflection film material according to claim 2, which is an epoxy compound, a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one group selected from an ethyl group and an acyloxyethyl group.   A method of forming a pattern on a substrate by lithography, wherein at least the antireflection film material according to claim 2 is applied on the substrate and baked to form an antireflection film, the antireflection film A photoresist film material is applied thereon, pre-baked to form a photoresist film, the pattern circuit region of the photoresist film is exposed, and then developed with a developer to form a resist pattern on the photoresist film, A pattern forming method comprising: forming a pattern on the substrate by etching the antireflection film and the substrate using the photoresist film on which the resist pattern is formed as a mask.   An antireflection film obtained by applying the antireflection film material according to claim 2 or 3 onto a substrate and baking it.

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