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    • 专利摘要:
    The present invention relates to a positive resist material having a repeating unit represented by the following formula (2) and comprising a polymer compound having a weight average molecular weight of 1,000 to 500,000. The positive resist material of the present invention is excellent in sensitivity, resolution, and plasma etching resistance in response to high energy rays, and also excellent in heat resistance of the resist pattern. In addition, it is difficult for the pattern to easily form a projected image and is excellent in dimensional controllability.
    公开号:KR20040036695A
    申请号:KR1020040020670
    申请日:2004-03-26
    公开日:2004-04-30
    发明作者:다까노부 다께다；오사무 와따나베；준 와따나베；준 하따께야마；요이찌 오사와；도시노부 이시하라
    申请人:신에쓰 가가꾸 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Positive Resist Materials
    [1] In the copolymer of hydroxy styrene and (meth) acrylic acid ester, the alkali dissolution rate before and after exposure is compounded by blending a high molecular compound in which a part of the phenolic hydroxyl group is crosslinked by an acid labile group to the resist material as a base resin. The contrast is greatly increased, and has a high sensitivity and high resolution, and particularly relates to a forged resist material such as a chemically amplified forged resist material suitable as a fine pattern forming material for ultra-LSI production.
    [2] In recent years, with the higher integration and higher speed of LSI, finer pattern rules have been required, and far-ultraviolet lithography is promising as a next-generation fine processing technology. Ultraviolet lithography can be processed to less than 0.5 μm, and when a resist material with low light absorption is used, it is possible to form a pattern having a sidewall close to the perpendicular to the substrate.
    [3] Recently developed acid-catalyzed chemically amplified forged resist materials (described in Japanese Patent Application Publication Nos. 90-27660 and 88-27829, etc.) use KrF excimer laser of high brightness as an ultraviolet light source. It is expected to be a particularly promising resist material for far-ultraviolet lithography having high sensitivity, resolution, dry etching resistance and excellent characteristics.
    [4] As such chemically amplified forgive resist materials, a three-component system comprising a two-component system composed of a base polymer, an acid generator, a base polymer, an acid generator, and a dissolution inhibiting agent having an acid labile group is known.
    [5] For example, Japanese Patent Laid-Open Publication No. 87-115440 proposes a resist material composed of poly-p-tert-butoxystyrene and an acid generator, and similar to this proposal, is disclosed in Japanese Patent Laid-Open Publication No. 91-223858. A two-component resist material comprising a resin having a tert-butoxy group and an acid generator in a molecule, and Japanese Patent Laid-Open No. 92-2ll258 contains a methyl group, isopropyl group, tert-butyl group, tetrahydropyranyl group, and trimethylsilyl group A two-component resist material composed of polyhydroxystyrene and an acid generator has been proposed.
    [6] In addition, Japanese Patent Application Laid-Open No. 94-100488 discloses poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene], Resist materials consisting of polydihydroxystyrene derivatives such as poly [3,5-bis (2-tetrahydropyranyloxy) styrene] and an acid generator have been proposed.
    [7] However, the base resin of these resist materials has an acid labile group in the side chain, and if the acid labile group is decomposed into a strong acid such as tert-butyl group and tert-butoxycarbonyl group, the pattern shape of the resist material is T-top shaped. On the other hand, since alkoxyalkyl groups such as ethoxyethyl groups are decomposed into weak acids, they have the drawback that the pattern shape becomes considerably thinner with time from exposure to heat treatment, or because they have a large volume in the side chain. There are various problems such as falling or not satisfying sensitivity and resolution, and it is a reality that has not yet been put into practical use, and improvement of these problems is desired.
    [8] In addition, although a resist material using a copolymer of (meth) acrylate has been reported to realize higher transparency and adhesion to a substrate and to improve a hemming phenomenon to the substrate (Japanese Patent Laid-Open No. 96-101509, Patent Publication No. 96-146610) and this type of resist material have problems such as heat resistance and partial pattern collapse.
    [9] SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a positive resist material having a high sensitivity, a high resolution, an exposure margin, and a process adaptability, in particular a chemically amplified positive resist material, which is higher than a conventional positive resist material. do.
    [10] MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present invention has a repeating unit represented by the following general formula (1) or the following general formula (2), and a polymer compound having a weight average molecular weight of 1,000 to 500,000 is a positive type resist material, particularly chemically amplified. Effective as a base resin of a forged resist material, a chemically amplified forged resist material containing the polymer compound, an acid generator, and an organic solvent increases the dissolution contrast of the resist film, and in particular, the dissolution rate after exposure increases, so that a high resolution and exposure margin are allowed. Also, it has been found that the process adaptability is excellent, the practicality is high, it is advantageous for precise micromachining, and is very effective as a resist material for ultra LSI.
    [11]
    [12] <Formula 2>
    [13]
    [14] In the formula,
    [15] R 1 is a hydrogen atom or a methyl group,
    [16] R 2 is an acid labile group,
    [17] R 3 , R 4 , R 6 and R 7 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
    [18] R 5 is a linear, branched or cyclic alkylene group, alkylene ether group, cyclohexylene group or arylene group having 1 to 10 carbon atoms,
    [19] R 8 is a hydrogen atom, a methyl group, a phenyl group or a cyano group,
    [20] R 9 represents a hydrogen atom or a linear, branched or cyclic unsubstituted or vinyl group, an acetyl group, a phenyl group or a cyano group substituted alkyl group having 1 to 10 carbon atoms, and
    [21] Each unit may be composed of one kind or two kinds or more,
    [22] p, r and s are positive, q is 0 or positive,
    [23] Satisfying 0 <p / (p + q + r + s) ≤0.8, 0≤q / (p + q + r + s) ≤0.8, 0 <s / (p + q + r + s) ≤0.9 Number,
    [24] z1 is an integer of 1-3, z2 is an integer of 0-3.
    [25] Here, in the polymer compound of Formula 1 or Formula 2, a part of the phenolic hydroxyl group is crosslinked with an acid labile group. When such a high molecular compound is blended into a resist material as a base resin, in particular, since it is crosslinked by an acid labile group, it has the advantage of high dissolution inhibiting property and large dissolution contrast after exposure. That is, in the case of a polymer in which an alkoxyalkyl group is added to the side chain alone, it is difficult to form a T-top because the desorption reaction proceeds with a weak acid, but since it is sensitive to acid as described above, the time from exposure to heat treatment This has the drawback that the pattern shape is significantly thinner. Moreover, since the dissolution inhibiting effect with respect to alkali is low, in order to obtain melt | dissolution contrast, a high substitution rate body must be used, and it has a fault that heat resistance is insufficient.
    [26] On the other hand, when a compound protected with a t-BOC group in the side chain of the phenolic hydroxyl group of the polymer compound is added to the resist material, alkali dissolution inhibiting property is good, dissolution contrast can be obtained at a low substitution rate, or heat resistance. In order to be detached and alkali-soluble, a strong acid such as trifluoromethanesulfonic acid needs to be present. If such an acid is used, there is a drawback that the T-top shape is easily formed as described above.
    [27] Moreover, when the copolymer which protected (meth) acrylic acid with the acid labile group was mix | blended with a resist material, the fault of a partial pattern collapse and a hemming phenomenon will arise.
    [28] On the other hand, the chemically amplified forge type resist material using the polymer compound of Formula 1 or Formula 2 as a base resin tends to have a T-top shape, has a thin pattern shape, lacks heat resistance, and causes partial pattern collapse and hemming phenomenon. As a result, the chemically amplified formic acid resist material having extremely high sensitivity and high resolution, and capable of arbitrarily performing the dimensional control of the pattern and the shape control of the pattern by the composition, and having excellent process adaptability. It has been found that the present invention has been completed and the present invention has been completed.
    [29] Therefore, the present invention
    [30] (i) a positive resist material having a repeating unit represented by Chemical Formula 1 and comprising a polymer compound having a weight average molecular weight of l, 000 to 500,000;
    [31] (ii) acrylic acid protected by a substituent having a weight average molecular weight of 1,000 to 500,000 and which is acetal crosslinked with a butylene group represented by the above formula (2), and which is easily desorbed by an acid represented by the following formula (3) or (4). A positive resist material comprising a high molecular compound which is an ester copolymer,
    [32] (iii) a chemically amplified positive resist material comprising (A) an organic solvent, (B) a base resin, and the polymer compound of (i) or (ii) and an acid generator (C).
    [33] (iv) A chemical composition comprising (A) an organic solvent and (B) a base resin, wherein the polymer compound of (i) or (ii) is contained, (C) an acid generator, and (D) a dissolution control agent. An amplified forged resist material is provided.
    [34] Hereinafter, the present invention will be described in more detail, the polymer compound of the present invention is a copolymer having each unit represented by the following formula (1) or (2).
    [35] <Formula 1>
    [36]
    [37] <Formula 2>
    [38]
    [39] In the formula,
    [40] R 1 is a hydrogen atom or a methyl group,
    [41] R 2 is an acid labile group,
    [42] R 3 , R 4 , R 6 and R 7 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
    [43] R 5 is a linear, branched or cyclic alkylene group, alkylene ether group, cyclohexylene group or arylene group having 1 to 10 carbon atoms,
    [44] R 8 is a hydrogen atom, a methyl group, a phenyl group or a cyano group,
    [45] R 9 represents a hydrogen atom or a linear, branched or cyclic unsubstituted or vinyl group, an acetyl group, a phenyl group or a cyano group substituted alkyl group having 1 to 10 carbon atoms, and
    [46] Each unit may be composed of one kind or two kinds or more,
    [47] p, r and s are positive, q is 0 or positive,
    [48] Satisfying 0 <p / (p + q + r + s) ≤0.8, 0≤q / (p + q + r + s) ≤0.8, 0 <s / (p + q + r + s) ≤0.9 Number,
    [49] z1 is an integer of 1-3, z2 is an integer of 0-3.
    [50] In Formula 1 or Formula 2, R 1 is a hydrogen atom or a methyl group. Moreover, although various things are selected as an acid instability group of R <2> , it is especially preferable that they are a trialkylsilyl group of 1-4 carbon atoms of a tetrahydropyranyl group, a tetrahydrofuranyl group, or an alkyl group.
    [51] As an alkyl group of R <3> , R <4> , R <6> and R <7> , a methyl group, an ethyl group, a propyl group, n-butyl group, isobutyl group, tert- butyl group, hexyl group, cyclohexyl group, etc. are mentioned.
    [52] Examples of R 5 include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, an alkylene ether group having an oxygen atom interposed in these alkylene groups, a cyclohexylene group, a phenylene group, a xylene group, and the like. Although it is mentioned, it is preferable that it is C2-C6, and the butylene group which is a C4 linear alkylene group is especially preferable.
    [53] Examples of the unsubstituted alkyl group for R 9 include the same alkyl groups as those exemplified above, but R 9 is preferably a tertiary alkyl group as the acid labile group, particularly preferably an alkyl group represented by the following general formula (3).
    [54]
    [55] In the formula,
    [56] R 10 is methyl group, ethyl group, isopropyl group, vinyl group, acetyl group, phenyl group or cyano group,
    [57] n is an integer of 0-3.
    [58] As a cyclic alkyl group of General formula (3), a 5-membered ring is more preferable. Specific examples include 1-methylcyclopentyl, 1-ethylcyclopentyl, l-isopropylcyclopentyl, 1-vinylcyclopentyl, 1-acetylcyclopentyl, 1-phenylcyclopentyl, 1-cyanocyclopentyl and 1-methyl Cyclohexyl, 1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-vinylcyclohexyl, 1-acetylcyclohexyl, 1-phenylcyclohexyl, 1-cyanocyclohexyl and the like.
    [59] Moreover, as R <9> , the substituted alkyl group represented by following formula (4) is also suitable.
    [60]
    [61] Wherein R l1 may be one of a vinyl group, an acetyl group, a phenyl group and a cyano group
    [62] As a specific example, 1-vinyl dimethyl, 1-acetyl dimethyl, 1-phenyl dimethyl, 1-cyano dimethyl, etc. are mentioned.
    [63] Further, in consideration of the properties of the resist material in which the polymer compound of the present invention is blended as the base resin, p, r and s are each positive numbers, q is O or positive numbers, and preferably the following formula is satisfied.
    [64] 0 <p / (p + q + r + s) ≦ 0.8, preferably 0.02 ≦ p / (p + q + r + s), more preferably p / (p + q + r + s) ≦ 0.4.
    [65] 0 ≦ q / (p + q + r + s) ≦ 0.8, preferably 0 ≦ q / (p + q + r + s) ≦ 0.5.
    [66] 0 <s / (p + q + r + s) ≦ 0.9, preferably 0 <s / (p + q + r + s) ≦ 0.5, more preferably 0 <s / (p + q + r + s) ≤ 0.3.
    [67] 0 <r / (p + q + r + s) ≦ 0.8, preferably 0 <r / (p + q + r + s) ≦ 0.7.
    [68] 0 <(p + q) / (p + q + r + s) ≦ 0.8, preferably 0.07 ≦ (p + q) / (p + q + r + s) ≦ 0.5.
    [69] If any one of p, r and s is O, and the polymer compound of Formula 1 forms a structure that does not include any unit, the contrast of alkali dissolution rate decreases and the resolution deteriorates. If the ratio of p to the whole (p + q + r + s, hereinafter equal) is less than 0.02, there is a possibility that the advantages of the acid labile crosslinking group may not be derived. , if the total ratio of the total of p and q exceeds 0.8, the crosslinking becomes excessive and becomes a gel, and the solubility in alkali disappears, causing a change in film thickness, stress or bubbles in the film during alkali development, or less hydrophilic groups. Therefore, adhesiveness with a board | substrate may be inferior. If the ratio of r exceeds 0.8, the contrast of dissolution rate will worsen. Moreover, when the ratio of s is too big | large, the alkali dissolution rate of an unexposed part becomes very slow and dry etching resistance will also fall. In addition, by appropriately selecting the values of p, q, r and s within the above ranges, the dimensional control of the pattern and the shape of the pattern can be arbitrarily performed.
    [70] In addition, z1 of Chemical Formula 1 is an integer of 1 to 3. In addition, z2 is an integer of 0-3.
    [71] In the polymer compound of the present invention, the content of the acid labile group affects the dissolution rate contrast of the resist film and relates to resist material properties such as pattern dimension control and pattern shape.
    [72] Each of the polymer compounds of the present invention needs to have a weight average molecular weight (the measuring method is described later) of 1,000 to 500,000, preferably 3,000 to 30,000. If the weight average molecular weight is too small, the heat resistance of the resist material is inferior. If the weight average molecular weight is too large, alkali solubility is lowered and a hemming phenomenon is likely to occur after pattern formation.
    [73] In the polymer compound of the present invention, when the molecular weight distribution (Mw / Mn) of the polyhydroxystyrene and the (meth) acrylic acid ester copolymer to be used is large, low molecular weight and high molecular weight polymers are present, It is difficult to design, and it may become difficult to manufacture the resist material which has the same performance. Therefore, as the pattern rule becomes finer, the influence of these molecular weights and molecular weight distribution tends to be large. Therefore, in order to obtain a resist material suitable for fine pattern dimensions, the copolymer molecular weight of hydroxystyrene and (meth) acrylic acid ester used for crosslinking is obtained. The distribution is preferably 1.0 to 2.0, in particular monodispersed to 1.0 to 1.5.
    [74] The polymer compound of the present invention can be produced by introducing an acid labile crosslinking group into a copolymer of hydroxystyrene and (meth) acrylic acid ester by chemical reaction.
    [75] This crosslinking reaction is performed by adding a hydrogen atom of a part of hydroxyl groups of a polyhydroxystyrene unit to a vinyl group of the following divinyl ether compound using an acid as a catalyst, so that a part of hydroxyl groups of the polyhydroxystyrene (total hydroxyl group 1) To p mole relative to mole).
    [76]
    [77] In formula, R <1> , R <3> -R <9> , p, q, r, and s are the same as the above.
    [78] Here, as said divinyl ether compound, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1, 4- butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl Ether, tetraethylene ethylene glycol divinyl ether, 1,4-di (vinyl ethermethyl) cyclohexane, 1,4-di (vinyl ether methoxy) benzene, 1,4-di (vinyl ether ethoxy) benzene And divinyl ether derivatives. Moreover, it is especially preferable that carbon number of a crosslinked alkyl chain is 2-6, and it is more preferable to use 1, 4- butanediol divinyl ether of 4 carbon number.
    [79] The reaction is preferably performed in the presence of a solvent such as dimethylformamide, tetrahydrofuran, dimethylacetamide, and the like, and examples of the acid include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid pyridinium salt. The amount of the polyhydroxystyrene used is preferably 0.1 to 10 mol% based on 1 mol of the total hydroxyl groups of the reacted polyhydroxystyrene. The reaction temperature is preferably from room temperature to 60 ° C, and the reaction time is usually 1 to 20 hours.
    [80] As a method for crosslinking and protecting a portion of the hydroxyl groups of the polyhydroxystyrene with an alkoxyalkyl group, a hydrogenated alkali such as NaH or a base such as triethylamine or pyridine in the presence of a solvent such as dimethyl sulfoxide or tetrahydrofuran The method of making haloethyl ether, such as a 4-4-butanediol dichloroethyl ether, react with polyhydroxy styrene can also be used. In this case, as for the usage-amount of bases, such as alkali hydrogen, triethylamine, and pyridine, the quantity in which a predetermined | prescribed crosslinking group is introduce | transduced with respect to 1 mol of all hydroxyl groups of polyhydroxy styrene to react is preferable. As for reaction temperature, 0-50 degreeC is preferable, and reaction time is 1 to 20 hours normally.
    [81] The chemically amplified forged resist material of the present invention comprises (A) an organic solvent, (B) a base resin, and the polymer compound, (C) an acid generator, (D) a dissolution controller, and (E) a basic compound. It is preferable.
    [82] As the organic solvent (A) used in the present invention, any solvent may be used as long as it is an organic solvent in which an acid generator, a base resin, a dissolution controller, and the like are soluble. As such an organic solvent, for example, cyclohexanone, Ketones such as methyl-2-n-amyl ketone, alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol, Ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl Esters such as ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl-3-methoxypropionate and ethyl-3-ethoxypropionate Although these can be used individually by 1 type or in mixture of 2 or more types, It is not limited to these. In this invention, diethylene glycol dimethyl ether and l-ethoxy-2-propanol which are the most excellent in the solubility of the acid generator in a resist component among these organic solvents are used preferably.
    [83] As for the usage-amount of the organic solvent, 200-1,000 parts, especially 400-800 parts are suitable with respect to 100 parts (weight part, below same) of base resin.
    [84] Examples of the acid generator of component (C) include an onium salt of formula (6), a diazomethane derivative of formula (7), a glyoxime derivative of formula (8), a β-ketosulphone derivative, a disulfone derivative, a nitrobenzylsulfonate derivative, Sulfonic acid ester derivatives, imide-ylsulfonate derivatives, and the like.
    [85] (R 30) b M + K -
    [86] In the formula,
    [87] R 30 represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms,
    [88] M + represents iodonium or sulfonium,
    [89] K − represents a non-nucleophilic counter ion,
    [90] b is 2 or 3.
    [91] Examples of the alkyl group for R 30 include a methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, 2-oxocyclohexyl group, norbornyl group, adamantyl group and the like. As an aryl group, alkoxyphenyl groups, such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, 2-methylphenyl Alkylphenyl groups, such as group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and a dimethylphenyl group, are mentioned. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned. Examples of non-nucleophilic counter ions of K − include halide ions such as chloride ions and bromide ions, triflate, fluoroalkylsulfonates such as 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate, and tosyl Alkyl sulfonates, such as aryl sulfonates, a mesylate, butane sulfonate, such as a late, a benzene sulfonate, 4-fluorobenzene sulfonate, a 1,2,3,4,5-pentafluorobenzene sulfonate, are mentioned. have.
    [92]
    [93] In the formula, R 31 and R 32 represent a linear, branched or cyclic alkyl group or a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.
    [94] As an alkyl group of R <31> and R <32> , a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc. are mentioned. Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, and nonafluorobutyl group. As an aryl group, alkoxyphenyl groups, such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, 2-methylphenyl Alkylphenyl groups, such as group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and a dimethylphenyl group, are mentioned. Examples of the halogenated aryl group include fluorobenzene groups, chlorobenzene groups, 1,2,3,4,5-pentafluorobenzene groups, and the like. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.
    [95]
    [96] Wherein R 33 , R 34 and R 35 are linear, branched or cyclic alkyl or halogenated alkyl groups having 1 to 12 carbon atoms, aryl or halogenated aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms; In addition, R 34 and R 35 may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R 34 and R 35 each represent a linear or branched alkylene group having 1 to 6 carbon atoms.
    [97] Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group for R 33 , R 34 and R 35 include the same groups as described for R 31 and R 32 . Further, as the R 34 and the alkylene group of R 35 it may be mentioned methylene group, ethylene group, propylene group, butylene group, hexylene group and the like.
    [98] Specifically, for example, trifluoromethanesulfonic acid diphenyl iodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyl iodonium, p-toluenesulfonic acid diphenyl iodonium, p-toluene Sulfonic acid (p-tert-butoxyphenyl) phenyl iodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-part Methoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid triphenyl Sulfonium, butanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-toluenesulfonic acid trimethyl Sulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, p-toluenesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid dimethylphenylsulfonium, p- Onium salts such as toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonate) Ponyyl) 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) di Azomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclo Diazomethane derivatives such as hexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane, bis-o- (p -Toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime , Bis-o- (p-toluenesulfonyl) -2,3-pentanedioneglyoxime, bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, bis-o -(n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclo Hexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedioneglyoxime, bis-o- (n-butanesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, Bis-o- (methanesulfonyl) -α-dimethylgly Shim, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, Bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) glyoxime derivatives, such as -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, and bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl Β-ketosulfone derivatives such as 2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane, diphenyl disulfone and dicyclohexyl disulfone Sulfone derivatives, p-toluenesulfonic acid 2,6-dinitrobenzyl, p-toluenesulfonic acid 2,4-dinitrobenzyl, etc. Nitrobenzyl sulfonate derivatives, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluene Sulfonic acid ester derivatives such as sulfonyloxy) benzene, phthalimide-yl-triplate, phthalimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-triplate, 5- Imide-yl-sulfonate derivatives such as norbornene-2,3-dicarboxyimide-yl-tosylate and 5-norbornene-2,3-dicarboxyimide-yl-n-butylsulfonate; Trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, and 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 Onium salt, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (Isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butyl Diazomethane derivatives such as sulfonyl) diazomethane, bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime Glyoxime derivatives are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. The onium salt is excellent in the effect of improving the formation, and the diazomethane derivative and the glyoxime derivative are excellent in the effect of reducing standing waves, but by combining the two, fine adjustment of the profile can be performed.
    [99] It is preferable that the compounding quantity of an acid generator shall be 0.2-20 parts, especially 0.5-15 parts with respect to 100 parts of all base resins, and when it is too small, the amount of acid generation at the time of exposure may be small, and a sensitivity and resolution may fall, and when too much The transmittance | permeability of a resist may fall and resolution may fall.
    [100] (D) Dissolution control agent can further be added to the resist material of this invention. As a dissolution control agent, the hydrogen atom of the said phenolic hydroxyl group of the compound which has a weight average molecular weight of 100-1,000, and has 2 or more phenolic hydroxyl groups in a molecule | numerator is substituted by the ratio of an average l0-100% as a whole by an acid labile group. One compound is preferred. In addition, the weight average molecular weight of the compound is 100 to 1,000, preferably 150 to 800. The compounding quantity of a dissolution control agent is 0-50 parts with respect to 100 parts of base resin, Preferably it is 5-50 parts, More preferably, it is 10-30 parts, It can use individually or in mixture of 2 or more types. When there is little compounding quantity, the improvement of resolution may not be seen, and when too much, there exists a tendency for the film | membrane decrease of a pattern to occur and the resolution falls.
    [101] In addition, a basic compound can be mix | blended with the resist material of this invention as (E) additive.
    [102] As the basic compound to be blended as the additive (E), a compound capable of suppressing the diffusion rate when the acid generated in the acid generator diffuses into the resist film is suitable. The diffusion speed can be suppressed to improve the resolution, suppress the change in sensitivity after exposure, or reduce the dependence on the substrate and the environment, thereby improving the improvement in exposure margin, the improvement in pattern profile, and the like. As such a basic compound, primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, and nitrogen having a hydroxyl group Included compound, nitrogen-containing compound having hydroxyphenyl group, alcoholic nitrogen-containing compound, amide derivative and the like.
    [103] Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified, and secondary As aliphatic amines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N , N-dimethyltetraethylenepentamine and the like are exemplified, tertiary aliphatic amines West trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexyl Amines, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N , N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like are exemplified.
    [104] In addition, examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline , 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., Pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and the like), oxazole derivatives (e.g. oxazole, isoxazole, etc.), thia Sol derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc. ), Pyrazole derivatives, furazane derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrroli) Dine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- ( 1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine , Dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyri Chopped derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine oil Sieve, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indolin derivatives, quinoline derivatives (e.g. quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnaline derivatives, quinazoline Derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenadine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.
    [105] In addition, examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylosin, and leucine). , Methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like, and nitrogen-containing compounds having a sulfonyl group include 3-pyridine sulfonic acid, p-toluene sulfonic acid pyridinium, and the like. Illustrative examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolmethanol hydrate and monoethanolamine , Diethanolamine, triethanolamine, N-ethyl diethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-imino Ethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2 -Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxy Hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolysine, 3-quinuclidinol, 3 -Tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. are illustrated. . Examples of the amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Phthalimide, succinimide, maleimide, etc. are illustrated as an imide derivative.
    [106] Moreover, the compound which substituted one part or all part of the hydroxyl group of the nitrogen-containing compound which has this hydroxyl group by methyl group, ethyl group, methoxymethyl group, methoxyethoxymethyl group, acetyl group, ethoxyethyl group, etc. is mentioned, Ethanolamine , Methyl ethanol, acetyl, methoxymethyl, and methoxyethoxymethyl substituents of diethanolamine and triethanolamine are preferably used. Specifically, tris (2-methoxyethyl) amine, tris (2-ethoxyethyl) amine, tris (2-acetoxyethyl) amine, tris {2- (methoxymethoxy) ethyl} amine, tris {2 -(Methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2 -(1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- { (2-hydroxyethoxy) ethoxy} ethyl] amine can be mentioned.
    [107] Moreover, a basic compound can be used individually by 1 type or in combination of 2 or more types, The compounding quantity is suitable to mix 0-2 parts, especially 0.01-1 part with respect to 100 parts of solid content in a resist material. If there is too much compounding quantity, a sensitivity may fall.
    [108] To the resist material of the present invention, a surfactant for improving the coatability as an optional component other than the above components, a light absorbing material for reducing the influence of diffuse reflection on the substrate, and the like can be added. In addition, the addition amount of an arbitrary component can be made into the normal amount in the range which does not impair the effect of this invention.
    [109] In this case, as a surfactant, a perfluoroalkyl polyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkyl EO addition product, etc. are mentioned, As a light absorbing material, a diaryl sulfoxide, Diaryl sulfone, 9, 10- dimethyl anthracene, 9-fluorenone, etc. are mentioned.
    [110] In order to form a pattern using the positive resist material of the present invention, known lithography can be employed, for example, spin coating on a silicon wafer to apply 0.5 to 2.0 μm and prebaking at 80 to 120 ° C. Thereafter, high-energy rays such as far ultraviolet rays, electron beams and X-rays are irradiated and exposed, followed by post-exposure baking (PEB) at 70 to 120 ° C. for 30 to 200 seconds, followed by development with an aqueous alkali solution. In addition, the material of the present invention is particularly suitable for fine patterning by far ultraviolet rays and electron beams of 254 to 193 nm, even among high energy rays.
    [111] <Example>
    [112] Hereinafter, the present invention will be described in detail with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.
    [113] Synthesis Example 1
    [114] Into a 2 L flask, 93.8 g of α-methylhydroxystyrene, 54.7 g of methacrylic acid 1-ethylcyclopentyl ester, and 1.5 L of THF were added as a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 13.lg of AIBN was added as a polymerization initiator, and it heated up to 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, and the white solid obtained by precipitation in 10 L of water was filtered, and it dried under reduced pressure at 60 degreeC, and obtained 120 g of white polymers. By measuring the resulting polymer (Poly 1) as C l3, l H-NMR and GPC, to obtain the results shown below.
    [115] Copolymer composition ratio (molar ratio)
    [116] α-methylhydroxystyrene: methacrylic acid 1-ethylcyclopentyl ester = 69: 31
    [117] Weight average molecular weight (Mw) = 12,000
    [118] Dispersion (Mw / Mn) = 1.48
    [119] Synthesis Example 2
    [120] The copolymer (Poly 2) which shows the following analysis result was obtained from (alpha) -methylhydroxy styrene and methacrylic acid 1-phenyldimethyl ester by the method similar to the synthesis example 1.
    [121] Copolymer composition ratio (molar ratio)
    [122] α-methylhydroxystyrene: methacrylic acid 1-phenyldimethyl ester = 72:28
    [123] Weight average molecular weight (Mw) = l4,000
    [124] Dispersion (Mw / Mn) = l.62
    [125] Synthesis Example 3
    [126] To a 2 L flask, 113.4 g of hydroxystyrene, 54.7 g of methacrylic acid 1-ethylcyclopentyl ester, and 1.5 L of THF were added as a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 13.lg of AIBN was added as a polymerization initiator, and it heated up to 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, and the white solid obtained by precipitation in 10 L of water was filtered, and it dried under reduced pressure at 60 degreeC, and obtained 132 g of white polymers. The polymer was dissolved again in 1.0 L of ethanol, 50 g of sodium hydroxide was added to deprotection reaction, and neutralized with hydrochloric acid (28 wt%) while cooling. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 109 g of a white polymer. The obtained polymer (Poly 3) was measured by 13 C, 1 H-NMR and GPC to obtain the following analysis results.
    [127] Copolymer composition ratio (molar ratio)
    [128] Hydroxystyrene: methacrylic acid 1-ethylcyclopentyl ester = 72: 28
    [129] Weight average molecular weight (Mw) = 12,000
    [130] Dispersion (Mw / Mn) = 1.49
    [131] Synthesis Example 4
    [132] The copolymer (Poly 4) of the following analysis results was obtained from hydroxystyrene and methacrylic acid 1-phenyldimethyl ester by the same method as in Synthesis Example 3.
    [133] Copolymer composition ratio (molar ratio)
    [134] Hydroxystyrene: Methacrylic acid 1-phenyldimethyl ester = 75: 25
    [135] Weight average molecular weight (Mw) = 13,000
    [136] Dispersion (Mw / Mn) = 1.41
    [137] Synthesis Example 5
    [138] 50 g of α-methylhydroxystyrene: methacrylic acid 1-ethylcyclopentyl ester copolymer (Poly 1) was dissolved in 0.5 L of THF in a 2 L flask, and 2.0 g of triethylamine was added thereto. 1,4-butanedioldichloroethyl ether was added dropwise while stirring at 0 ° C. After the reaction for 1 hour, the precipitated solid was precipitated in 5 L of water (20 ml of acetic acid) and filtered, and then the obtained solid was dissolved in an acetone solution again, precipitated with 5 L of water, filtered, and dried in vacuo. As for the obtained polymer, it was confirmed that hydroxyl group hydrogen atom of polyhydroxy styrene was bridge | crosslinked by 4.5% by 1 H-NMR (Poly 5).
    [139] Synthesis Example 6
    [140] The crosslinking reaction of Poly2, Poly3, and Poly4 was performed by the method similar to the synthesis example 5, and the polymer of the crosslinking rate shown below was obtained.
    [141] (Poly 6): Reaction of Poly 2, crosslinking rate 4.1%
    [142] (Poly 7): Reaction of Poly 3, crosslinking rate 6.6%
    [143] (Poly 8): React Poly 4, crosslinking rate 5.2%
    [144] <Example, Comparative Example>
    [145] (Poly 5) to (Poly 8) obtained in the above Synthesis Example were used as base resin (part by weight = 80), and p-toluenesulfonic acid triphenylsulfonium derivative (part by weight = 3) as the acid generator, and a basic compound Triethanolamine (part by weight = 0.1) as a solvent, and 2,2-bis (4-tbutylcarboxyphenyl) propane (part by weight = 0.2) as a dissolution control agent, and propylene glycol monoethyl acetate / ethyl lactate (part by weight = 530, 7/3), the resist material was combined, and each resist was filtered through a 0.2 micrometer Teflon filter, and the resist liquid was produced, respectively.
    [146] In addition, the resist liquid was prepared similarly to the above using the polymer represented by (Poly 1)-(Poly 4) as a base resin for comparison.
    [147] The obtained resist liquid was spin coated onto a silicon wafer and applied to a thickness of 0.8 탆. This silicon wafer was then baked at 100 ° C. for 120 seconds using a hot plate. This was exposed using an excimer laser stepper (Nikon, NSR2005EX8A, NA = 0.5), baked at 90 ° C. for 60 seconds, and developed with an aqueous solution of 2.38% tetramethylammonium hydroxide to give a positive pattern. there was. The obtained resist pattern was evaluated as follows. The results are shown in Table 1.
    [148] Assessment Methods:
    [149] First, sensitivity (Eth) was calculated | required. Subsequently, the exposure amount which resolves 0.35 micrometer line and space 1: 1 is made into the optimal exposure amount Eop, and the minimum line width of the line and space separated by this exposure amount was made into the resolution of an evaluation resist. The shape of the resolved resist pattern was observed using a scanning electron microscope. In addition, unevenness (partial pattern collapse, hemming phenomenon) of 0.22 μm line and space was measured by a scanning electron microscope.
    [150] Resist Used PolymerResolution (μm)Partial pattern collapseHeming phenomenon Example 1Poly 50.18In a little○ Example 2Poly 60.18none○ Example 3Poly 70.18none○ Example 4Poly 80.18In a little◎ Comparative Example 1Poly 10.2has existX Comparative Example 2Poly 20.2In a little△ Comparative Example 3Poly 30.18has existX Comparative Example 4Poly 40.18has exist△
    [151] From the results in Table 1, it was confirmed that in the case of the chemically amplified forged resist material of the present invention, a pattern with improved resolution and partial pattern collapse and hemming phenomenon was obtained.
    [152] The forged resist material of the present invention is excellent in sensitivity, resolution, and plasma etching resistance in response to high energy rays, and also excellent in heat resistance of the resist pattern. In addition, the pattern does not easily form a protruding shape and is excellent in dimensional controllability. In addition, partial pattern collapse and hemming phenomenon peculiar to the (meth) acrylic acid copolymer are also improved. Therefore, the positive resist material of the present invention can be a resist material having a low absorption at the exposure wavelength of the KrF excimer laser, especially from these characteristics, and can easily form a fine pattern perpendicular to the substrate, It is suitable as a fine pattern forming material for ultra LSI production.
    权利要求:
    Claims (7)
    [1" claim-type="Currently amended] A positive resist material having a repeating unit represented by the following formula and comprising a high molecular weight compound having a weight average molecular weight of 1,000 to 500,000.

    In the formula,
    R 1 is a hydrogen atom or a methyl group,
    R 3 , R 4 , R 6 and R 7 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
    R 5 is a linear, branched or cyclic alkylene group, alkylene ether group, or arylene group having 1 to 10 carbon atoms,
    R 8 is a hydrogen atom, a methyl group, a phenyl group or a cyano group,
    R 9 represents a hydrogen atom or a linear, branched or cyclic unsubstituted or vinyl group, an acetyl group, a phenyl group or a cyano group substituted alkyl group having 1 to 10 carbon atoms, and
    Each unit may be composed of one kind or two kinds or more,
    p, r and s are positive,
    0 <p / (p + r + s) ≦ 0.8, 0 <s / (p + r + s) ≦ 0.9,
    z2 is an integer of 0-3.
    [2" claim-type="Currently amended] A positive resist material having a repeating unit represented by the following formula (2) and comprising a polymer compound having a weight average molecular weight of 1,000 to 500,000.
    <Formula 2>

    In the formula,
    R 1 is a hydrogen atom or a methyl group,
    R 8 represents a hydrogen atom, a methyl group, a phenyl group or a cyano group,
    R 9 represents a hydrogen atom or a linear, branched or cyclic unsubstituted or vinyl group, an acetyl group, a phenyl group or a cyano group substituted alkyl group having 1 to 10 carbon atoms, and
    Each unit may be composed of one kind or two kinds or more,
    p, r and s are positive, q is O or positive,
    Satisfying O <p / (p + q + r + s) ≤0.8, 0≤q / (p + q + r + s) ≤0.8, 0 <s / (p + q + r + s) ≤0.9 Number,
    z2 is an integer of 0-3.
    [3" claim-type="Currently amended] The forged resist material according to claim 1, wherein R 9 is a tertiary alkyl group represented by the following general formula (3).
    <Formula 3>

    In the formula,
    R 10 is a methyl group, ethyl group, isopropyl group, vinyl group, acetyl group, phenyl group or cyano group,
    n is an integer of 0-3.
    [4" claim-type="Currently amended] The forged resist material according to claim 1 or 2, wherein R 9 is a tertiary alkyl group represented by the following general formula (4).
    <Formula 4>

    In formula, R <11> is a vinyl group, an acetyl group, a phenyl group, or a cyano group.
    [5" claim-type="Currently amended] (A) an organic solvent,
    (B) the polymer compound according to any one of claims 1 to 4 as a base resin, and
    (C) acid generator
    A chemically amplified forgive resist material comprising a.
    [6" claim-type="Currently amended] (A) an organic solvent,
    (B) the polymer compound according to any one of claims 1 to 4 as the base resin,
    (C) an acid generator, and
    (D) dissolution control agent
    A chemically amplified forgive resist material comprising a.
    [7" claim-type="Currently amended] The chemically amplified positive resist material according to claim 5 or 6, further comprising a basic compound as an additive (E).
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    同族专利:
    公开号 | 公开日
    TW487828B|2002-05-21|
    US6156481A|2000-12-05|
    KR20000029366A|2000-05-25|
    KR100504644B1|2005-08-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-10-29|Priority to JP30772798
    1998-10-29|Priority to JPJP-P-1998-00307727
    2004-03-26|Application filed by 신에쓰 가가꾸 고교 가부시끼가이샤
    2004-04-30|Publication of KR20040036695A
    优先权:
    申请号 | 申请日 | 专利标题
    JP30772798|1998-10-29|
    JPJP-P-1998-00307727|1998-10-29|
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