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    • 专利摘要:
    The present invention provides a resist film by (a) coating a resist material containing a polymer or a copolymer and an acid generator that generates an acid upon exposure to a side chain having an acid labile group in a main chain unit of formula (5) on a substrate; 1st process, (b) a second step of prebaking the resist film, (c) a third step of performing a pattern exposure, (d) post-exposure bake fourth process, (e) a fifth step of developing the resist film to form a resist pattern, and (f) A resist pattern forming method having a sixth step of thermally flowing a resist pattern by post-baking the resist pattern. According to the present invention, the degree of integration of the semiconductor LSI can be improved, that is, the degree of processing fineness can be improved. In the formula, X 1, X 2 is -O-, -S-, -NR-, -PR- or -CR 2 -, and, R is H or an alkyl group, m is an integer from O to 3;
    公开号:KR20030032825A
    申请号:KR1020020040550
    申请日:2002-07-12
    公开日:2003-04-26
    发明作者:사또시 와따나베；도모히로 고바야시
    申请人:신에쓰 가가꾸 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Resist Patterning Process {Resist Patterning Process}
    [1] The present invention is sensitive to various radiations (ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams, X-rays, various laser lights such as ArF excimer laser), and forms a resist pattern using a positive resist material having high sensitivity and resolution. It is about how to.
    [2] In recent years, as semiconductor integrated circuits have been integrated, large scale integrated circuits (LSIs) and ultra-large scale integrated circuits (VLSIs) have been put to practical use. In addition, the minimum pattern of integrated circuits extends to the submicron region and tends to become finer in the future. . In forming the fine pattern, the target substrate on which the thin film is formed is coated with a resist, subjected to selective exposure to form a latent image of a desired pattern, and then developed to form a resist pattern, which is subjected to dry etching as a mask. The use of lithographic techniques to obtain the desired pattern by removing the resist is essential.
    [3] As the exposure light source used in this lithography technique, shorter wavelengths of ultraviolet light, vacuum ultraviolet light, electron beams (EB), X-rays, and the like have been used as light sources as the pattern becomes finer. In particular, in recent years, an excimer laser (a KrF laser having a wavelength of 248 nm and an ArF laser having a wavelength of 193 nm) or an F 2 laser having a wavelength of 157 nm has been attracting attention as an exposure light source and is expected to be effective for forming a fine pattern.
    [4] As a polymer or copolymer used for the resist material which forms a submicron pattern using the exposure light of a shorter wavelength ultraviolet-ultraviolet region, acrylic acid which has a protecting group which detaches by an adamantane skeleton and an acid in an ester part, for example is used. Polymers or copolymers of esters or α-substituted acrylic acid esters (see Japanese Patent Application Laid-open No. Hei 4-39665), polymers of acrylic esters or α-substituted acrylic esters having a protecting group which is released by the norbornane skeleton and an acid in the ester moiety Or a copolymer (see Japanese Patent Application Laid-Open No. 5-257281), a polymer or copolymer of cyclohexyl maleimide (see Japanese Patent Laid-Open Publication No. 5-257285), and a cellulose skeleton in the main chain, High molecular compounds which cause cleavage by acid (see Japanese Patent Application Laid-Open No. 6-342212), and poly Carbonyl derivatives of alcohol or polyvinyl alcohol (see Japanese Patent Application Publication Hei-7-333850 call) and a number of polymers and copolymers, etc. it has been proposed.
    [5] However, not only satisfies all the properties necessary for use as a resist material such as dry etching resistance, transparency to far ultraviolet rays, solubility in a resist solvent, wettability to a developer, adhesion to a substrate such as silicon and solubility in a release agent, Since there are no polymers and copolymers that are easy to synthesize, new developments are desired.
    [6] On the other hand, a photoresist composition (W097 / 33198, Japanese Patent Laid-Open Publication No. Hei 09-230595, Japanese Patent Laid-Open Publication) comprising a high molecular compound having a cyclic skeleton having an aliphatic cyclic hydrocarbon as a main chain and having a functional group decomposed by an acid 09-244247, Japanese Patent Application Laid-open No. Hei 10-254139), although the cyclic polymer is excellent in dry etching resistance and transparency to far ultraviolet rays, it is soluble in a resist solvent at a high concentration and developer. There have been problems such as poor wettability and poor adhesion to a silicon substrate.
    [7] In recent years, for the semiconductor microfabrication using the above-mentioned production performance, namely ultraviolet rays or far ultraviolet rays (including excimer laser, etc.), it is excellent in light transmittance and the like, has high resolution with high sensitivity, and has high affinity with alkaline developer and is good. A ring-opening metathesis polymer hydrogenated substance having a narrow molecular weight distribution as well as satisfying all the necessary performances to be used as a base polymer for a positive type photoresist composition capable of obtaining a pattern has been proposed (Japanese Patent Laid-Open No. 11-A). 130843, 11-130844, 11-130845, 11-171982, Japanese Patent Application Laid-Open No. 2000-109545, 2001-27803, and Japanese Patent Application No. 2000-113351.
    [8] On the other hand, the integration of semiconductor LSIs has generally increased at a rapid rate of four times every three years. Such improvement in density can be achieved by improving the fineness of lithographic processing. For this purpose, there have been many proposals for miniaturization techniques such as super-resolution technique at the time of exposure, development, heat flow at the time of baking after resist pattern formation, and overetching at the time of etching. The formation method of a general fine pattern is as follows.
    [9] The resist material is spin-coated over the Si wafer, and it is baked at high temperature (hereinafter referred to as PB (prebaking)), and then the resist is selectively exposed through a pattern mask. The resist on the exposed wafer is again baked at high temperature (hereinafter referred to as PEB (post exposure bake)), and then developed with a developer to form a resist pattern. Next, wet etching or dry etching is performed using the formed pattern as a mask. At this time, the resist which the exposure part solubilizes in a developing solution is called positive resist, and the resist in which the exposure part is insolubilized is called negative resist. In particular, it is known that a contact hole depth refinement, the resist pattern after the heat flow formed on the useful diameter (JSKim, JCJung, G.Lee, MHJung , KHBaik, J.Photopolym. Sci.Technol., 13, 47- (2000). ).
    [10] The resist composition comprising a polymer or a copolymer of an acrylic ester or an α-substituted acrylic ester having an ester moiety which is separated by an adamantane skeleton and an acid, and the like, even if the above heat flow process is introduced, resist problems of dry etching resistance The resist composition which cannot be solved and has insufficient performance as a resist for micromachining, and which has a cyclic skeleton having a functional group decomposed by the above-mentioned aliphatic cyclic hydrocarbon as a main chain and having a functional group decomposed by an acid has a high glass transition point and does not heat flow. There is a problem that the heat flow process cannot be introduced.
    [11] On the other hand, conventionally, the method of making a base resin by combining several types of high molecular compounds is examined variously. However, in most cases, particularly in the case where combinations of different main chain structures are combined, the resist solutions are not compatible with each other, or even if the resist solution can be used, phase separation or thinning may occur at the time of coating, and thus film formation is not preferable. Even if it could form into a film, there existed a problem of causing partial dropping of the film | membrane resulting from the nonuniform distribution of a base resin at the time of pattern formation.
    [12] This invention is made | formed in view of the said situation, and is excellent in the light transmittance with respect to ultraviolet rays and far ultraviolet rays (including an excimer laser, etc.), has high sensitivity with high sensitivity, and has high affinity with alkaline developing solution, and has a favorable pattern. By providing a heat flow process of a resist pattern after using a general fine pattern formation method using the obtained positive type resist, the pattern formation method aiming at the improvement of the integration degree of a semiconductor LSI, ie, the improvement of processing fineness, is provided. The purpose is to.
    [13] MEANS TO SOLVE THE PROBLEM The present inventors examined in order to solve the said problem, and the base resin which is a ring-opening metathesis polymer hydrogenated substance of a cyclic olefin type monomer, or a mixture of this and a poly (meth) acrylic acid derivative has the outstanding optical characteristic, an electrical characteristic, high It has been found that the present invention can be used as a base polymer for resist materials having rigidity, heat resistance, substrate adhesion, weather resistance and heat flowability.
    [14] That is, the present invention provides the following resist pattern forming method.
    [15] (A) A base resin, which is a polymer or copolymer having a structural unit represented by the following formula (5) on a substrate and partially having an acid labile group in a side chain, on the substrate, and an acid generator that generates an acid by radiation exposure. A first step of forming a resist film by applying a resist material,
    [16] (b) a second step of prebaking the resist film,
    [17] (c) a third step of subjecting the prebaked resist film to pattern exposure,
    [18] (d) a fourth step of post-exposure baking the resist film exposed to the pattern,
    [19] (e) a fifth step of developing the resist film subjected to post exposure baking to form a resist pattern, and
    [20] and (f) a sixth step of thermally flowing the resist pattern by post-baking the resist pattern.
    [21] <Formula 5>
    [22]
    [23] Wherein X 1 , X 2 is selected from -O-, -S-, -NR-, -PR-, or -CR 2- , R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and m is O or an integer of 1 to 3 is shown.
    [24] Article 2:
    [25] The base resin is a hydrogenated product of a ring-opening metathesis polymer containing a structural unit [A] represented by the following formula (1), a structural unit [B] represented by the following formula (3) and / or a structural unit [C] represented by the following formula (4): The resist pattern formation method of Claim 1.
    [26]
    [27]
    [28]
    [29] In the formula, at least one of R 1 to R 4 is a group having an acid labile group represented by the following formula (2), and others of R 1 to R 4 are hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. , A halogen atom, a linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms Alkyl group, straight, branched or cyclic alkyl carbonyl oxy group having 2 to 20 carbon atoms, aryl carbonyl oxy group having 7 to 20 carbon atoms, linear, branched or cyclic alkyl sulfonyl oxy group having 1 to 20 carbon atoms , An aryl sulfonyl oxy group having 6 to 20 carbon atoms, a straight, branched or cyclic alkoxy carbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxy carbonyl alkyl group having 3 to 20 carbon atoms R 8 to R 11 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and R 13 to R 16 represent a hydrogen atom or a straight, branched or cyclic group having 1 to 10 carbon atoms. An alkyl group of. One of Y 1 and Y 2 is-(C = O)-, the other is -CR 18 2- (R 18 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), j and n are O or an integer of 1 to 3, and X 1 , X 2 and m represent the same meaning as in claim 1.
    [30]
    [31] In the formula, the chain line represents the number of bonds, R 5 is a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 10 carbon atoms, or 1 carbon atom. A straight chain, branched or cyclic acyl group of from 10 to 10, W 1 represents a single bond or a (k + 2) valent hydrocarbon group having 1 to 10 carbon atoms, R AL represents an acid labile group, and k is O or 1 .
    [32] Article 3:
    [33] (a) A resist film is formed by applying a resist material containing a base resin, which is a mixture of a hydrogenated ring of a ring-opening metathesis polymer and a poly (meth) acrylic acid derivative, and an acid generator that generates an acid by radiation exposure on a substrate. 1st process,
    [34] (b) a second step of prebaking the resist film,
    [35] (c) a third step of subjecting the prebaked resist film to pattern exposure,
    [36] (d) a fourth step of post-exposure baking the resist film exposed to the pattern,
    [37] (e) a fifth step of developing the resist film subjected to post exposure baking to form a resist pattern, and
    [38] and (f) a sixth step of thermally flowing the resist pattern by post-baking the resist pattern.
    [39] Article 4:
    [40] The method for forming a resist pattern according to claim 3, wherein the hydrogenated product of the ring-opening metathesis polymer is a polymer compound having a weight average molecular weight of 500 to 200,000 having a repeating unit represented by the following formula (6).
    [41]
    [42] Wherein R 101 represents a hydrogen atom, a methyl group or CH 2 CO 2 R 103 , R 102 represents a hydrogen atom, a methyl group or C0 2 R 103 , and R 103 may be the same or different at R 101 and R 102 A linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, R 104 represents an acid labile group, R 105 is a halogen atom, a hydroxyl group, a straight, branched or cyclic alkoxy group having 1 to 15 carbon atoms, acyl An oxy or alkyl sulfonyl oxy group or a straight, branched or cyclic alkoxy carbonyl oxy group or alkoxy alkoxy group having 2 to 15 carbon atoms, and some or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms. and, at least one of R 106 to R 109 represents a monovalent hydrocarbon group containing a carboxyl or hydroxyl group of a carbon number of 1 to 15, the remains are each independently hydrogen atom or a carbon 1 to show the 15 straight chain, branched alkyl group or cyclic, R 106 and R 107, R 107 and R 108, or R 108 and R 109 is a ring with the carbon atoms to which they are bonded to each bonded to each other In this case, one of R 106 and R 107 , R 107 and R 108 , or R 108 and R 109 represents a divalent hydrocarbon group containing a carboxy group or hydroxyl group having 1 to 15 carbon atoms, and the other A bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms, at least one of R 110 to R 113 represents an ether, aldehyde, ketone, ester, carbonate, acid anhydride, amide, Monovalent hydrocarbon groups containing at least one substructure selected from imides, each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms; , R 110 and R 111 , R 111 and R 112 , or R 112 and R 113, may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case R 110 and R 111 , R 111 And one of R 112 or R 112 and R 113 is a divalent hydrocarbon group containing at least one substructure selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides and imides having 1 to 15 carbon atoms. And the other represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms, and X 11 to X 13 each independently represent a methylene group or an oxygen atom, but all of X 11 to X 13 Is not a methylene group at the same time, W represents a single bond or a linear, branched or cyclic (t + 2) valent hydrocarbon group having 1 to 5 carbon atoms, and in the case of a hydrocarbon group, at least one methylene group is substituted with an oxygen atom Air can form a linear or cyclic ether, is substituted with the same carbon on the two hydrogen atoms are oxygen atoms, may form a ketone, k 1 to k 3 are each independently 0 or 1, t is 0, 1 or 2, a, b, c represent the composition ratio of each repeating unit, a is greater than 0 and less than 1, b, c is 0 or more and less than 1, and satisfies a + b + c = 1, a, b , c may be present in plurality of repeating units introduced at each composition ratio.
    [43] Hereinafter, the present invention will be described in more detail, the method of forming a resist pattern of the present invention is a polymer having a structural unit represented by the following formula (5) in the main chain and partly an acid labile group in the side chain as the first bake resin of the resist material Or copolymers are used.
    [44] <Formula 5>
    [45]
    [46] Wherein, X 1, X 2 is -O-, -S-, -NR-, -PR-, or -CR 2 - is selected from, R is a hydrogen atom or a group having 1 to 20 carbon atoms, especially an alkyl group of 1 to 10 And m represents O or the integer of 1-3.
    [47] Hereinafter, the first bake resin used in the present invention will be described in more detail. The resist material of the present invention is a base resin, which is represented by the structural unit [A] represented by the following general formula (1) and the structural unit represented by the following general formula (3). It is preferable to use the hydrogenated substance of the ring-opening metathesis polymer containing [B] and / or the structural unit [C] represented by following formula (4).
    [48] <Formula 1>
    [49]
    [50] <Formula 3>
    [51]
    [52] <Formula 4>
    [53]
    [54] In the general formula (1) of the present invention, at least one of R 1 to R 4 is a group having an acid labile group represented by the following formula (2).
    [55] <Formula 2>
    [56]
    [57] In the formula, the chain line represents the number of bonds, R 5 is a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 10 carbon atoms, or 1 carbon atom. A straight chain, branched or cyclic acyl group of from 10 to 10, W 1 represents a single bond or a (k + 2) valent hydrocarbon group having 1 to 10 carbon atoms, R AL represents an acid labile group, and k is O or 1 .
    [58] In R 5 , as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, 1-ethyl cyclopentyl, 1-ethyl cyclohexyl, etc. are mentioned, As a C2-C10 linear, branched or cyclic alkoxyalkyl group, For example, methoxymethyl, 1-ethoxymethyl, 1-tert -Butoxyethyl, 1-cyclohexyl oxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetra hydropyran-2-yl and the like. As a C1-C10 linear, branched, or cyclic acyl group, formyl, acetyl, pivaloyl, cyclohexyl carbonyl, etc. are mentioned, for example. Among these R 5 , a linear or branched alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxy alkyl group having 2 to 7 carbon atoms, and a linear or branched acyl group having 2 to 7 carbon atoms are preferable. In particular, hydrogen atoms, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are preferred.
    [59] In W 1, having 1 to 10 carbon atoms as the (k + 2) valent hydrocarbon group, and when k is O, C 1 -C 10 straight, branched or a divalent cyclic hydrocarbon group, e.g. methylene, Dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1, 1-dimethylethylene, 1, 2-dimethylethylene, 2 , 2-dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyl trimethylene, 2-methyl trimethylene, 3-methyl trimethylene, tetramethylene, pentamethylene, 1, 1-cyclopentylene, 1, 2-cyclopentylene, 1, 3-cyclopentylene, 1, 1-cyclohexylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, etc. are mentioned. Can be. Among these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-methyl trimethylene are preferable. In the case where k is 1, for example, one obtained by removing one hydrogen atom at any position on the hydrocarbon group exemplified in the case where k is O is used as the number of bonds.
    [60] As an acid labile group represented by said R <AL> , various selection is possible, Specifically, the group represented by the following general formula (L1)-(L4), a C4-C20, Preferably the tertiary alkyl group of 4-15, each alkyl group And a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, and the like.
    [61]
    [62] In the above formulas, R L01 and R L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl, ethyl, propyl and isopropyl groups. , n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, etc. can be illustrated, R <L03> is C1-C18, It is preferable. For example, a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom of 1 to 10, and a linear, branched or cyclic alkyl group, a part of these hydrogen atoms are hydroxyl group, alkoxy group, oxo group, amino group, alkyl amino group And substituted with these, and specifically, a substituted alkyl group
    [63] Etc. can be illustrated.
    [64] R L01 and R L02 , R L01 and R L03 , R L02 and R L03 may form a ring, and when forming a ring, R L01 , R L02 , and R L03 each have 1 to 18 carbon atoms, preferably 1 A straight or branched alkylene group of from 10 to 10;
    [65] R L04 represents a C4-C20, preferably a C3- C15 tertiary alkyl group, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above formula (L1) As the tertiary alkyl group, specifically, tert-butyl group, tert-amyl group, 1, 1-diethylpropyl group, and the following formulas [16-1] to [16-3]
    [66] Group, 2-cyclopentyl propan-2-yl group, 2-cyclohexyl propane-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (a Tantan-1-yl) propan-2-yl group, 1-ethyl cyclopentyl group, 1-butyl cyclopentyl group, 1-ethyl cyclohexyl group, 1-butyl cyclohexyl group, 1-ethyl-2-cyclopentenyl group , 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group and the like can be exemplified. Specific examples of the trialkylsilyl group include trimethylsilyl group, A triethylsilyl group, a dimethyl tert- butyl silyl group, etc. can be illustrated, Specifically, as an oxoalkyl group, 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, 5-methyl-2 -Oxo oxoran-5-yl group etc. can be illustrated and y is an integer of 0-6.
    [67] R L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or a substituted aryl group having 6 to 20 carbon atoms, and as the monovalent hydrocarbon group which may contain a hetero atom, specifically, a methyl group Linear such as ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group and cyclohexyl group Linear, branched or cyclic alkyl groups, some of these hydrogen atoms being substituted with hydroxyl groups, alkoxy groups, carboxyl groups, alkoxycarbonyl groups, oxo groups, amino groups, alkyl amino groups, cyano groups, mercapto groups, alkylthio groups, sulfo groups and the like The thing etc. can be illustrated, and as an aryl group which can be substituted, a phenyl group, a methylphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a pyrenyl group, etc. can be illustrated specifically ,. m is O or 1, n is O, 1, 2, 3, and is a number which satisfy | fills 2m + n = 2 or 3.
    [68] R L06 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or a aryl group which may be substituted with 6 to 20 carbon atoms, and specifically, the same as those for R L05 may be exemplified. R L07 to R L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, n-butyl, sec -Butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group Linear, branched or cyclic alkyl groups such as cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group and cyclohexylbutyl group, and some of these hydrogen atoms are hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, And the like substituted with an oxo group, an amino group, an alkyl amino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group and the like. R L07 to R L16 may be bonded to each other to form a ring (for example, R L07 and R L08 , R L07 and R L09 , R L08 and R L10 , R L09 and R L10 , R L11 and R L12 , R L13 , R L14, and the like), in which case, a divalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms is shown, and specifically, one hydrogen atom is removed from the example exemplified by the monovalent hydrocarbon group. It can be illustrated. In addition, R L07 to R L16 may be bonded to adjacent carbon directly to each other to form a double bond (for example, R L07 and R L09 , R L09 and R L15 , R L13 and R L15). Etc).
    [69] Specific examples of the linear or branched group among the acid labile groups represented by the general formula (L1) include the following groups.
    [70]
    [71] Specifically as a cyclic thing among the acid labile groups represented by the said general formula (L1), a tetrahydrofuran-2-yl group, 2-methyl tetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, 2-methyl tetra Hydropyran-2-yl group etc. can be illustrated.
    [72] Specific examples of the acid labile group of the general formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonyl methyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonyl methyl group, 1, 1-diethylpropyl oxy Carbonyl group, 1, 1-diethylpropyl oxycarbonylmethyl group, 1-ethylcyclopentyl oxycarbonyl group, 1-ethylcyclopentyl oxycarbonylmethyl group, 1-ethyl-2-cyclopentenyl oxycarbonyl group, 1-ethyl-2- Cyclopentenyl oxycarbonylmethyl group, 1-ethoxyethoxy carbonylmethyl group, 2-tetrahydropyranyl oxycarbonylmethyl group, 2-tetra hydrofuranyl oxycarbonylmethyl group, etc. can be illustrated.
    [73] Specific examples of the acid labile group of formula (L3) include 1-methylcyclopentyl, 1-ethyl cyclopentyl, 1-n-propyl cyclopentyl, 1-isopropyl cyclopentyl, 1-n-butyl cyclopentyl, 1 -sec-butyl cyclopentyl, 1-methyl cyclohexyl, 1-ethyl cyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1 -Cyclohexen-3-yl, 3-ethyl-1-cyclohexen-3-yl, 1-cyclohexylpentyl, 1- (2-norbornyl) cyclopentyl and the like.
    [74] As an acid labile group of the said general formula (L4), the following group can be illustrated specifically ,.
    [75]
    [76] Moreover, as a C4-C20 tertiary alkyl group, each alkyl group each C1-C6 trialkylsilyl group, a C4-C20 oxoalkyl group, the thing similar to what was mentioned in R <L04> etc. can be illustrated specifically ,. .
    [77] In addition, said acid labile group can be used individually by 1 type or in combination of 2 or more types. By using a plurality of acid labile groups, fine adjustment of the pattern profile can be performed.
    [78] The others of R 1 to R 4 are each independently a hydrogen atom, a linear or branched phase such as methyl having 1 to 20 carbon atoms, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl Or halogen atoms such as cyclic alkyl groups, chlorine atoms, bromine atoms, iodine atoms or fluorine atoms, fluoromethyl of 1 to 20 carbon atoms, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, Linear, branched or cyclic halogenated alkyl groups such as trifluoromethyl, trichloromethyl or tribromomethyl, methoxy of 1 to 20 carbon atoms, ethoxy, isopropoxy, n-butoxy, tert-butoxy Or a straight chain, branched or cyclic alkoxy group such as methoxy, methoxymethyl having 2 to 20 carbon atoms, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol, or methyl glucose Containing alkoxy saccharides such as Is a linear, branched or cyclic alkoxy alkyl group, a linear, branched or cyclic alkylcarbonyl oxy group such as acetoxy having 2 to 20 carbon atoms, or an aryl carbonyl oxy group such as naphthoyloxy having 7 to 20 carbon atoms Linear, branched or cyclic alkyl sulfonyl oxy groups such as mesyloxy having 1 to 20 carbon atoms, aryl sulfonyl oxy groups such as tosyloxy having 6 to 20 carbon atoms, methoxy carbonyl having 2 to 20 carbon atoms, and Linear, branched or cyclic alkoxy carbonyl groups such as oxycarbonyl, n-propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, tert-butoxy carbonyl, or cyclohexyl oxycarbonyl, Methoxy carbonyl methyl, 2- (methoxy carbonyl) ethyl, 1- (methoxy carbonyl) ethyl, ethoxy carbonyl methyl, 2- (ethoxy carbonyl) ethyl, n-pro Foxy Carbonyl Methyl, Isopropoxy Carbon As a specific example, linear, branched, or cyclic alkoxy carbonyl alkyl groups, such as a methyl methyl, n-butoxy carbonyl methyl, tert-butoxy carbonyl methyl, or cyclohexyl oxy carbonylmethyl, are mentioned. Among them, a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a straight, branched or cyclic group having 2 to 20 carbon atoms Alkoxy alkyl groups, straight, branched or cyclic alkoxycarbonyl groups having 2 to 20 carbon atoms, and straight, branched or cyclic alkoxy carbonyl alkyl groups having 3 to 20 carbon atoms are preferable, and more preferably hydrogen atoms and 1 carbon atoms. And a straight or branched alkyl group of 10 to 10, a straight or branched alkoxy carbonyl group of 2 to 10 carbon atoms, and a straight or branched alkoxy carbonyl alkyl group of 3 to 10 carbon atoms.
    [79] X 1 , X 2 is selected from -O-, -S-, -NR-, -PR- or -CR 2- . R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. j is 0 or an integer of 1 to 3; As X 1 , X 2 , preferably -O- or -CH 2- , more preferably all X 1 , X 2 are either -O- or -CH 2- . As m, Preferably it is O or 1.
    [80] As a specific example of Formula (1), the structural unit [A] shown by following General formula [17-1-1]-[17-4-16] is mentioned.
    [81]
    [82]
    [83]
    [84]
    [85] In the formula (3), R 8 to R 11 are each independently a hydrogen atom or methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl having 1 to 10 carbon atoms, or the like. The linear, branched, or cyclic alkyl group of may be mentioned as a specific example. X 1 and X 2 are the same as above. m is O or an integer of 1-3, Preferably it is O or 1.
    [86] As a specific example of General formula (3), the structural unit [B] shown by following General formula [18-1]-[18-16] is mentioned.
    [87]
    [88] In Formula 4, R 13 to R 16 are each independently a hydrogen atom or methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl having 1 to 10 carbon atoms. Linear, branched, or cyclic alkyl groups such as these may be cited as specific examples. X 1 and X 2 are the same as above. n is 0 or an integer of 1-3, Preferably it is 0 or 1. One of Y 1 and Y 2 is-(C = O)-and the other is -CR 18 2- (R 18 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms). Specific examples of R 18 include a hydrogen atom or a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl having 1 to 10 carbon atoms. As Y 1 and Y 2 , one side is preferably-(C = O)-and the other is -CH 2- .
    [89] As a specific example of General formula (4), the structural unit [C] represented by following General formula [19-1]-[19-16] is mentioned.
    [90]
    [91] In the present invention, the molar ratio [A] / ([B] + [C] of the structural unit [A] represented by the formula (1) and the structural unit [B] represented by the formula (3) and / or the structural unit [C] represented by the formula (4) ) Is 20/80 to 99/1, and in addition to the structural unit [A], it is essential that any certain amount of the structural unit [B] and / or [C] is present. Here, structural unit [A] contains the tertiary ester group of cyclic alkyl represented by General formula (2), ie, the group which decomposes | dissolves with the acid which generate | occur | produces with a photoacid generator at the time of exposure, and produces | generates a carboxylic acid, after exposure It is necessary in order to develop by aqueous alkali solution and to make a resist pattern. In addition, structural units [B] and / or [C] are necessary for expressing adhesiveness with a to-be-processed substrate, such as a silicon substrate. If these molar ratios [A] / ([B] + [C]) are less than 20/80, development will become inadequate, and if it exceeds 99/1, adhesiveness with a to-be-processed substrate will not be expressed. Preferably the molar ratio [A] / ([B] + [C]) is 20/80 to 95/5, more preferably 25/75 to 90/10, most preferably 30/70 to 85 / 15. These structural units are in this range, which is suitable for preparing a resist composition, and is a resist material which is dissolved in a polar solvent such as 2-heptanone and applied to a processing target substrate such as a silicon substrate together with a highly polar photosensitive agent. As extremely important. In other words, the hydrogenated substance of the ring-opening metathesis polymer increases the solubility in the polar solvent or the dissolution rate when preparing the resist material, thereby forming a uniform smooth coating film.
    [92] In the hydrogenated substance of the ring-opening metathesis polymer used in the present invention, at least one of structural unit [B] or [C] is preferable, and in addition to structural unit [A], structural units [B] and [C] Although it may be a ternary copolymer comprised from these, Preferably it is a binary copolymer comprised only one structural unit [B] or [C].
    [93] As for the hydrogenated substance of the ring-opening metathesis polymer used by this invention, the ratio (Mw / Mn) of weight average molecular weight Mw and number average molecular weight Mn is restrict | limited to the narrow molecular weight distribution of 1.0-2.O. The molecular weight distribution greatly affects the resolution when used as a resist material, and the narrower the pattern, the higher the resolution. Preferably it is 1.0-1.8, More preferably, it is the range of 1.0-1.6. As for the molecular weight of the hydrogenated substance of the ring-opening metathesis polymer of this invention, number average molecular weight Mn is 500-200,0000 normally. Preferably it is 1, OOO-100,000, More preferably, it is 3,000-50, OOO, More preferably, it is 3, OOO-20,000. In addition, the number average molecular weight and weight average molecular weight described in this specification were measured by the gel permeation chromatography (GPC) in polystyrene conversion.
    [94] In addition, the hydrogenated substance of these ring-opening metathesis polymers may consist of one structural unit each of structural unit [A], [B], and / or [C], and some or all of each structural unit may be two kinds. It may consist of the above structural unit. For example, the structural unit [A-1] and [A-2] which structural unit [A] shows with following formula (1a) and 1b, and the structural unit [B-1] which structural unit [B] shows with following formula (3a) and 3b And [B-2] and / or the structural unit [C] may be a hydrogenated product of a ring-opening metathesis polymer comprising structural units [C-1] and [C-2] represented by the following formulas 4a and 4b.
    [95]
    [96] In the formula, at least one of R 48 to R 51 is a functional group having a tertiary ester group of cyclic alkyl represented by the formula (2), and the others are each independently a hydrogen atom, a linear, branched or cyclic group having 1 to 20 carbon atoms. Alkyl group, halogen, C1-C20 linear, branched or cyclic halogenated alkyl group, C1-C20 linear, branched or cyclic alkoxy group, C2-C20 linear, branched or cyclic alkoxy Alkyl group, C2-C20 linear, branched or cyclic alkyl carbonyl oxy group, C6-C20 aryl carbonyl oxy group, C1-C20 linear, branched or cyclic alkyl sulfonyl oxy group , An aryl sulfonyl oxy group having 6 to 20 carbon atoms, a straight, branched or cyclic alkoxy carbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxy having 3 to 20 carbon atoms Selected from an alkyl group and carbonyl Viterbo, j1 is an integer of 0 or 1 to 3.
    [97]
    [98] Wherein at least one of R 52 to R 55 is a functional group having a tertiary ester group of cyclic alkyl represented by the formula (2), and the others are each independently a hydrogen atom, linear, branched or cyclic Alkyl group, halogen, linear, branched or cyclic halogenated alkyl group of 1 to 20 carbon atoms, linear, branched or cyclic alkoxy group of 1 to 20 carbon atoms, linear, branched or cyclic alkoxy of 2 to 20 carbon atoms Alkyl group, C2-C20 linear, branched or cyclic alkyl carbonyl oxy group, C6-C20 aryl carbonyl oxy group, C1-C20 linear, branched or cyclic alkyl sulfonyl oxy group , An aryl sulfonyl oxy group having 6 to 20 carbon atoms, a straight, branched or cyclic alkoxy carbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxy having 3 to 20 carbon atoms Selected from an alkyl group and carbonyl Viterbo, j2 represents an integer of 0 or 1 to 3.
    [99]
    [100] In formula, R <56> -R <59> is a hydrogen atom or a C1-C10 linear, branched or cyclic alkyl group each independently, and m1 represents the integer of 0 or 1-3.
    [101]
    [102] In formula, R <60> -R <63> is respectively independently a hydrogen atom or a C1-C10 linear, branched or cyclic alkyl group, m <2> represents O or the integer of 1-3.
    [103]
    [104] In formula, R <64> -R <67> is respectively independently a hydrogen atom or a C1-C10 linear, branched or cyclic alkyl group, Y <3> and Y <4> are-(C = O)-, and the other is Is -CH 2- , n- represents 0 or an integer of 1 to 3;
    [105]
    [106] In the formula, each of R 68 to R 71 is independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, Y 5 and Y 6 are each-(C = O)-and the other Is -CH 2- , and n2 represents O or an integer of 1 to 3;
    [107] As a hydrogenated substance of the ring-opening metathesis copolymer used by this invention, in addition to a structural unit [A] and [B] and / or [C], it has a structural unit [D] represented by following Chemical formula 5a as a structural unit further. It is preferable because it improves a board | substrate adhesiveness and affinity to a developing solution further.
    [108]
    [109] In the formula, at least one of R 19 to R 22 is a functional group having a carboxylic acid group represented by the following formula (6a), and the others are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , A halogen atom, a linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms Alkyl group, C2-C20 linear, branched or cyclic alkyl carbonyl oxy group, C6-C20 aryl carbonyl oxy group, C1-C20 linear, branched or cyclic alkyl sulfonyl oxy group , An aryl sulfonyl oxy group having 6 to 20 carbon atoms, a straight, branched or cyclic alkoxy carbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxy having 3 to 20 carbon atoms Selected from Viterbo carbonyl group and, X 1, X 2 are as defined above, and, p represents an integer of 0 or 1 to 3.
    [110]
    [111] In the formula, the chain line represents the number of bonds, and R 23 represents a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 10 carbon atoms, or 1 carbon atom. A straight chain, branched or cyclic acyl group of from 10 to 10 is represented, W 2 represents a single bond or a (q + 2) valent hydrocarbon group having 1 to 10 carbon atoms, and q is 0 or 1.
    [112] In R 23 , as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, 1-ethyl cyclopentyl, 1-ethyl cyclohexyl, etc. are mentioned, As a C2-C10 linear, branched or cyclic alkoxy alkyl group, For example, methoxymethyl, 1-ethoxyethyl, 1- tert-butoxyethyl, 1-cyclohexyl oxyethyl, 1-ethoxy propyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetra hydropyran-2-yl and the like. As a C1-C10 linear, branched, or cyclic acyl group, formyl, acetyl, pivaloyl, cyclohexyl carbonyl, etc. are mentioned, for example. Among these R 23 , a linear or branched alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxy alkyl group having 2 to 7 carbon atoms, and a linear or branched acyl group having 2 to 7 carbon atoms are preferable. In particular, hydrogen atoms, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are preferred.
    [113] In the W 2, The group q + 2-valent hydrocarbon group of a carbon number of 1 to 10, when q is O, and C 1 -C 10 straight, branched or a divalent cyclic hydrocarbon group, e.g., methylene, dimethylmethylene , Ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1, 1-dimethylethylene, 1, 2-dimethylethylene, 2, 2 -Dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyl trimethylene, 2-methyl trimethylene, 3-methyl trimethylene, tetramethylene, pentamethylene, 1, 1-cyclopentylene, 1, 2-cyclopentylene, 1, 3-cyclopentylene, 1, 1-cyclohexylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, etc. are mentioned. have. Among these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-methyl trimethylene are preferable. When q is 1, the thing which removed one hydrogen atom in arbitrary positions on the hydrocarbon group illustrated by the case where q was 0, for example is mentioned as bond water. Most preferred W 2 is a single bond.
    [114] The others of R 19 to R 22 are each independently a hydrogen atom, linear, branched or straight chain such as methyl having 1 to 20 carbon atoms, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl; Halogen such as cyclic alkyl group, chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl of 1 to 20 carbon atoms, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoro Linear, branched or cyclic halogenated alkyl groups such as rommethyl, trichloromethyl or tribromomethyl, methoxy having 1 to 12 carbon atoms, ethoxy, isopropoxy, n-butoxy, tert-butoxy or men Linear, branched or cyclic alkoxy groups such as oxy, methoxymethyl having 2 to 20 carbon atoms, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol, or methyl glucose Containing alkoxy sugars Arylcarbonyl oxy groups such as linear, branched or cyclic alkoxy alkyl groups, linear, branched or cyclic alkyl carbonyl oxy groups such as acetoxy having 2 to 20 carbon atoms, naphthoyl oxy having 6 to 20 carbon atoms, Linear, branched or cyclic alkyl sulfonyl oxy groups such as mesyloxy having 1 to 20 carbon atoms, aryl sulfonyl oxy groups such as tosyloxy having 6 to 20 carbon atoms, methoxy carbonyl and ethoxy having 2 to 20 carbon atoms Linear, branched or cyclic alkoxycarbonyl groups, such as carbonyl, n-propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, tert-butoxy carbonyl, or cyclohexyl oxycarbonyl, carbon atoms 3-20 methoxy carbonyl methyl, 2- (methoxy carbonyl) ethyl, 1- (methoxy carbonyl) ethyl, ethoxy carbonyl methyl, 2- (ethoxy carbonyl) ethyl, n-propoxy Carbonyl Methyl, Isopropoxy Carbonyl Specific examples include linear, branched or cyclic alkoxy carbonyl alkyl groups such as methyl, n-butoxy carbonyl methyl, tert-butoxy carbonyl methyl, or cyclohexyl oxy carbonyl methyl. Among them, a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a straight, branched or cyclic group having 2 to 20 carbon atoms Alkoxy alkyl groups, straight, branched or cyclic alkoxycarbonyl groups having 2 to 20 carbon atoms, and straight, branched or cyclic alkoxy carbonyl alkyl groups having 3 to 20 carbon atoms are preferred, and more preferably hydrogen atoms and 1 carbon atoms. A straight or branched alkyl group of 10 to 10, a straight or branched alkoxy carbonyl group of 2 to 10 carbon atoms, and a straight or branched alkoxy carbonyl alkyl group of 3 to 10 carbon atoms.
    [115] As R <23> , a hydrogen atom or a linear or branched alkyl group, such as a C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, is mentioned as a specific example. As p, Preferably it is 0 or 1.
    [116] As a specific example of general formula (5a), the structural unit [D] represented by the following general formula [20-1-1]-[20-4-16] is mentioned.
    [117]
    [118]
    [119]
    [120]
    [121] In a preferred embodiment of the present invention, the structural unit [D] represented by the formula (5a) to the structural unit [A] represented by the formula (1), the structural unit [B] represented by the formula (3) and the structural unit [C] represented by the formula (4) ] Molar ratio ([A] + [B] + [C]) / [D] is from 100 / O to 20/80, and in addition to structural units [A], [B] and [C] ] Is preferably present in a certain amount. Here, the structural unit [D] extremely improves the adhesion to the substrate to be treated such as a silicon substrate and further improves the affinity with the developer. Preferably the molar ratio ([A] + [B] + [C]) / [D] is 98/2 to 50/50, more preferably 97/3 to 60/40, most preferably 95/5 To 70/30. The hydrogenated substance of the ring-opening metathesis copolymer used in the present invention is a structure represented by the following general formula [7] in addition to the structural units [A] and [B] and / or [C], preferably [D]. Unit [E] may be further included as a structural unit.
    [122]
    [123] In the formula, at least one of R 25 to R 28 is a functional group having a carboxylic acid ester group represented by the following formula (8), and the others are each independently a hydrogen atom, a linear, branched or cyclic group having 1 to 20 carbon atoms. An alkyl group, a halogen atom, a straight, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a straight, branched or cyclic group having 2 to 20 carbon atoms Alkoxy alkyl group, straight, branched or cyclic alkyl carbonyl oxy group having 2 to 20 carbon atoms, aryl carbonyl oxy group having 6 to 20 carbon atoms, linear, branched or cyclic alkyl sulfonyl oxy having 1 to 20 carbon atoms Period, C6-C20 aryl sulfonyl oxy group, C2-C20 linear, branched or cyclic alkoxy carbonyl group, C3-C20 linear, branched or cyclic egg It is selected from a cooxy carbonyl alkyl group, X <1> , X <2> is the same as the above, may be same or different, and r represents the integer of 0 or 1-3.
    [124]
    [125] In the formula, the chain line represents the number of bonds, R 29 represents a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 10 carbon atoms, or 1 carbon atom. A straight, branched or cyclic acyl group having from 10 to 10, R 30 is a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 10 carbon atoms, or A linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, W 3 represents a single bond or a (s + 2) valent hydrocarbon group having 1 to 10 carbon atoms, and s is 0 or 1;
    [126] In R 28 , as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, 1-ethyl cyclopentyl, 1-ethyl cyclohexyl, etc. are mentioned, As a C2-C10 linear, branched or cyclic alkoxy alkyl group, For example, methoxymethyl, 1-ethoxyethyl, 1- tert-butoxyethyl, 1-cyclohexyl oxyethyl, 1-ethoxy propyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetra hydropyran-2-yl and the like. As a C1-C10 linear, branched, or cyclic acyl group, formyl, acetyl, pivaloyl, cyclohexyl carbonyl, etc. are mentioned, for example. Among these R 28 , a linear or branched alkyl group having 1 to 6 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 7 carbon atoms, and a linear or branched acyl group having 2 to 7 carbon atoms are preferable. In particular, hydrogen atoms, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are preferred.
    [127] In R 29 , examples of the linear or branched alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. As a 2-10 linear, branched or cyclic alkoxy alkyl group, For example, methoxymethyl, 1-ethoxyethyl, 1-tert-butoxyethyl, 1-cyclohexyl oxyethyl, 1-ethoxy propyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, etc. are mentioned, As a C1-C20 linear, branched or cyclic halogenated alkyl group, it is an example. Examples thereof include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl and the like. Among these R 29 , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl are particularly preferable.
    [128] In W 3 , the s + divalent hydrocarbon group having 1 to 10 carbon atoms is a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms when s is O. For example, methylene and dimethylmethylene , Ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1, 1-dimethylethylene, 1, 2-dimethylethylene, 2, 2 -Dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyl trimethylene, 2-methyl trimethylene, 3-methyl trimethylene, tetramethylene, pentamethylene, 1, 1-cyclopentylene, 1, 2-cyclopentylene, 1, 3-cyclopentylene, 1, 1-cyclohexylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, etc. are mentioned. have. Among these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-methyl trimethylene are preferable. In the case where s is 1, for example, one obtained by removing one hydrogen atom at any position on the hydrocarbon group exemplified in the case where s is O is used as the number of bonds. Most preferred W 3 is a single bond.
    [129] The others of R 24 to R 27 are each independently a hydrogen atom, a linear, branched or straight chain such as methyl having 1 to 20 carbon atoms, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl Halogen such as cyclic alkyl group, chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl of 1 to 20 carbon atoms, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoro Linear, branched or cyclic halogenated alkyl groups such as chloromethyl, trichloromethyl or tribromomethyl, methoxy having 1 to 20 carbon atoms, ethoxy, isopropoxy, n-butoxy, tert-butoxy or men Linear, branched or cyclic alkoxy groups such as oxy, methoxymethyl having 2 to 20 carbon atoms, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymentool, or methyl glucose Containing alkoxy sugars Aryl carbonyl oxy groups such as linear, branched or cyclic alkoxy alkyl groups, linear, branched or cyclic alkyl carbonyl oxy groups such as acetoxy having 2 to 20 carbon atoms, naphthoyl oxy having 6 to 20 carbon atoms, Linear, branched or cyclic alkyl sulfonyl oxy groups such as methyloxy having 1 to 20 carbon atoms, aryl sulfonyl oxy groups such as tosyloxy having 6 to 20 carbon atoms, methoxy carbonyl having 2 to 20 carbon atoms, and ethoxy Linear, branched or cyclic alkoxycarbonyl groups, such as carbonyl, n-propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, tert-butoxy carbonyl, or cyclohexyl oxycarbonyl, carbon atoms 3-20 methoxy carbonyl methyl, 2- (methoxy carbonyl) ethyl, 1- (methoxy carbonyl) ethyl, ethoxy carbonyl methyl, 2- (ethoxy carbonyl) ethyl, n-propoxy Carbonyl Methyl, Isopropoxy Carbo It may be mentioned methyl, n- butoxycarbonyl, methyl, tert- butoxycarbonyl methyl, or cyclohexyloxy-carbonyl straight, branched or cyclic alkoxycarbonylalkyl group of such as methyl as a specific example. Among them, a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a straight, branched or cyclic group having 2 to 20 carbon atoms Alkoxy alkyl groups, straight, branched or cyclic alkoxycarbonyl groups having 2 to 20 carbon atoms, and straight, branched or cyclic alkoxy carbonyl alkyl groups having 3 to 20 carbon atoms are preferable, and more preferably hydrogen atoms and 1 to 1 carbon atoms. A linear or branched alkyl group of 1O, a straight or branched alkoxy carbonyl group of 2 to 10 carbon atoms, and a straight or branched alkoxy carbonyl alkyl group of 3 to 10 carbon atoms.
    [130] X 1 and X 2 are the same as above, and when r is 1 to 3, they may be the same or different. As R <30> , a hydrogen atom or a linear or branched alkyl group, such as C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, is mentioned as a specific example. As r, Preferably, it is O or 1.
    [131] As a specific example of General formula (7), the structural unit [E] shown by following General formula [21-1-1]-[21-4-16] is mentioned.
    [132]
    [133]
    [134]
    [135]
    [136] The hydrogenated substance of the ring-opening metathesis copolymer used in the present invention is in addition to structural units [A] and [B] and / or [C], preferably [D], and optionally [E]. , Structural unit [F] shown by following formula (13) can be further included as a structural unit. The introduction ratio of the structural unit [F] can be 0 to 50 mol%, particularly 0 to 30 mol%, based on the total of the structural units [A] to [E].
    [137]
    [138] In formula, R <72> -R <75> is respectively independently a hydrogen atom, a C1-C20 linear, branched or cyclic alkyl group, a halogen, a C1-C20 linear, branched or cyclic halogenated alkyl group, carbon number A straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 20 carbon atoms, a hydroxyl group, a straight, branched or cyclic hydroxy alkyl group having 1 to 20 carbon atoms, Cyano group, straight, branched or cyclic cyano alkyl group having 2 to 20 carbon atoms, straight, branched or cyclic alkyl carbonyl oxy group having 2 to 20 carbon atoms, straight, branched or having 3 to 20 carbon atoms Cyclic alkyl carbonyl oxyalkyl groups, aryl carbonyl oxy groups having 6 to 20 carbon atoms, linear, branched or cyclic alkyl sulfonyl oxy groups having 1 to 20 carbon atoms, linear, branched or cyclic groups having 2 to 20 carbon atoms of An alkyl sulfonyl oxyalkyl group, aryl sulfonyl oxy group having 6 to 20 carbon atoms, X 6 is -O- or -CR 76 2- (R 76 is a hydrogen atom or linear or branched C1-C10 Alkyl group), and may be the same or different, and v represents 0 or an integer of 1 to 3.
    [139] In the hydrogenated substance of the ring-opening metathesis copolymer used in the present invention, the structural unit [A] represented by the formula (1) and the structural unit [B] represented by the formula (3) and / or the structural unit [C] represented by the formula (4) The molar ratio of [A] / ([B] and [C]) is 20/80 to 99/1. Here, the structural unit [A] contains a tertiary ester group of cyclic alkyl which is decomposed by the acid generated in the photoacid generator at the time of exposure, and is required to develop a resist pattern by developing with an aqueous alkali solution after exposure. , Structural units [B] and [C] are necessary for expressing adhesion with a substrate to be treated such as a silicon substrate. If these molar ratios [A] / ([B] and [C]) are less than 20/80, development will become inadequate, and if it exceeds 99/1, adhesiveness with a to-be-processed substrate will not be expressed. Moreover, the structural unit [D] represented by General formula (6) contains a carboxylic acid group, can improve adhesiveness with the to-be-processed substrate like a silicon substrate, and can improve the solubility to a solvent. In addition, the molar ratio ([A] + [B] + [C]) / [D] of the structural unit [A], [B] and [C] and the structural unit [D] is 100/0 to 20 / When it exists in the range of 80, since the wet tension improves at the time of image development by the aqueous alkali solution after exposure, it is preferable because it solves image development unevenness. These structural units are within this range, which is suitable for preparing a resist composition, and is a resist which is dissolved in a polar solvent such as 2-heptanone, for example, with a high polarity photosensitive agent, and applied to a target substrate such as a silicon substrate. It is extremely important as an ash. In other words, when the hydrogenated substance of the ring-opening metathesis polymer prepares the resist composition, it is possible to form a uniform smooth coating film by increasing the solubility or dissolution rate in the polar solvent. In addition, when the structural unit [E] is contained in addition to the structural units [A] and [B] and / or [C], it contains an ester group which is different in reactivity from the ester group contained in the structural unit [A]. It is useful because the decomposability during exposure can be freely controlled. The molar ratio ([A] + [B] + [C]) / [E] of the preferred structural unit in this case is in the range of 100 / O to 40/60. In the case where the structural unit [E] has an acid labile group, [E] can be contained in place of the structural unit [A], and the molar ratio of the preferred structural unit in this case is ([E] + [B] + [C]. ]) / [D] is between 100 / O and 20/80.
    [140] The hydrogenated substance of the ring-opening metathesis copolymer used in the present invention is a structural unit [A] represented by formula (1), a structural unit [B] represented by formula (3) and / or a structural unit [C] represented by formula (4), and as necessary A cyclic olefin monomer corresponding to each of the structural unit [E] represented by the general formula (7) and the structural unit [F] represented by the general formula (13) can be polymerized with a ring-opening metathesis catalyst and hydrogenated under a hydrogenation catalyst. have.
    [141] The cyclic olefin monomer corresponding to the structural unit [A] represented by the formula (1) is a cyclic olefin monomer having the structure of the following formula [9], and the cyclic olefin monomer corresponding to the structural unit [B] represented by the formula (3) is the following formula The cyclic olefin monomer which has a structure of [10], The cyclic olefin monomer corresponding to the structural unit [C] represented by General formula (4) is a cyclic olefin monomer which has a structure of following General formula (11), The structural unit represented by General formula (E) The cyclic olefin monomer corresponding to the above is a cyclic olefin monomer having a structure of the following formula (12), and the cyclic olefin monomer corresponding to the structural unit [F] represented by the formula (13) is a cyclic olefin monomer having the structure of the following formula (14).
    [142]
    [143]
    [144]
    [145]
    [146]
    [147] In the formula, R 1 to R 75 , X 1 , X 2 , X 6 , Y 1 , Y 2 , j, m, n, r and v are the same as the above definitions.
    [148] The hydrogenated substance of the ring-opening metathesis copolymer used in the present invention is a cyclic olefin monomer using a living ring-opening metathesis catalyst, preferably in the presence of a chain transfer agent such as olefin or diene, in a solvent or without solvent. After superposition | polymerization, it can obtain by hydrogenating in a solvent using a hydrogenation catalyst under hydrogen pressure.
    [149] Moreover, in the hydrogenated substance of the ring-opening metathesis copolymer obtained by superposition | polymerization and hydrogenation, at least one part of the tertiary ester group of cyclic alkyl in Formula (2) and / or the ester group in Formula (8) is decomposed, and carboxyl is decomposed. By converting into an acid, the structural unit [A] represented by the formula (1) and the structural unit [B] represented by the formula (3) and / or the structural unit [C] represented by the formula (4), the structural unit [D] represented by the formula (5), and It consists of structural unit [E] represented by General formula (7) as needed, and structural unit [F] represented by General formula (13) as needed, and the structural molar ratio [A] / ([B] and [C]) is 20/80. The hydrogenated substance of the ring-opening metathesis polymer having a ratio of from 99 to 99/1 and a weight average molecular weight Mw and a number average molecular weight Mn (Mw / Mn) of 1.0 to 2.O can be produced.
    [150] As a method of decomposing and converting at least a part of the tertiary ester group of the cyclic alkyl in the general formula (2) and / or the ester group in the general formula (8) to a carboxylic acid, a conventional method can be applied, and specifically, basic conditions Hydrolysis under, hydrolysis under acidic conditions, hydrolysis under neutral conditions, and acid decomposition can be exemplified, but is not limited thereto.
    [151] Moreover, the structural unit [A] shown by General formula (1) and the structural unit [B shown by general formula (3) are converted by converting the carboxylic acid functional group of the hydrogenated substance of the ring-opening metathesis polymer which has a carboxylic acid functional group obtained by the said method into ester. And / or the structural unit [C] represented by the general formula (4), the structural unit [D] represented by the general formula (5) if necessary, the structural unit [E] represented by the general formula (7) if necessary, and further represented by the general formula (13) as necessary. It consists of a structural unit [F], the structural molar ratios [A] / ([B] and [C]) are 20/80-99/1, and the ratio (Mw / of weight average molecular weight Mw and number average molecular weight Mn) Hydrogenated additions of the ring-opening metathesis polymers having Mn) of 1.0 to 2.O can be prepared.
    [152] As a method of converting a carboxylic acid functional group into an ester, a conventional method can be applied, and specifically, esterification by dehydration condensation reaction with alcohols, esterification by an ortho-alkylating agent, and addition of olefins in the presence of an acid. Esterification by, condensation reaction with halides using organic basic compounds, alkoxy alkyl esterification by addition of alkyl vinyl ethers, carboxylic acid to acid halides by thionyl chloride, etc. Although the method of esterifying by contacting with alcohols after conversion, the method of esterifying by contacting the metal salt of carboxylic acid with a halide, etc. can be illustrated, but it is not limited to these.
    [153] Next, the base resin in the resist material used for the resist pattern formation method of this invention is a hydrogenated substance and poly (meth) acrylic acid derivative of a ring-opening metathesis polymer.
    [154] In this case, as a hydrogenated substance of the ring-opening metathesis polymer used by this invention, it is especially preferable that it is the weight average molecular weights 500-200, OOO which has a repeating unit represented by following formula (6).
    [155] <Formula 6>
    [156]
    [157] Wherein R 101 represents a hydrogen atom, a methyl group or CH 2 CO 2 R 103 , R 102 represents a hydrogen atom, a methyl group or CO 2 R 103 , and R 103 may be the same or different at R 101 and R 102 A linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, R 104 represents an acid labile group, R 105 is a halogen atom, a hydroxyl group, a straight, branched or cyclic alkoxy group having 1 to 15 carbon atoms, acyl An oxy or alkyl sulfonyl oxy group or a straight, branched or cyclic alkoxy carbonyl oxy group or alkoxy alkoxy group having 2 to 15 carbon atoms, and some or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms. and, at least one of R 106 to R 109 represents a monovalent hydrocarbon group containing a carboxyl or hydroxyl group of a carbon number of 1 to 15, the remains are each independently hydrogen atom or a carbon 1 to show the 15 straight chain, branched alkyl group or cyclic, R 106 and R 107, R 107 and R 108, or R 108 and R 109 is a ring with the carbon atoms to which they are bonded to each bonded to each other In this case, one of R 106 and R 107 , R 107 and R 108 , or R 108 and R 109 represents a divalent hydrocarbon group containing a carboxy group or hydroxyl group having 1 to 15 carbon atoms, and the other A bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms, at least one of R 110 to R 113 represents an ether, aldehyde, ketone, ester, carbonate, acid anhydride, amide, Monovalent hydrocarbon groups containing at least one substructure selected from imides, each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms; . R 110 and R 111 , R 111 and R 112 , or R 112 and R 113, may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case R 110 and R 111 , R 111 and One of R 112 or R 112 and R 113 is a divalent hydrocarbon group containing at least one substructure selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides and imides having 1 to 15 carbon atoms. And the other represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms, and X 11 to X 13 each independently represent a methylene group or an oxygen atom, but all of X 11 to X 13 Does not form a methylene group at the same time, W represents a single bond or a linear, branched or cyclic (t + 2) valent hydrocarbon group having 1 to 5 carbon atoms, and in the case of a hydrocarbon group, at least one methylene group is an oxygen atom. The ring to which they are attached may form a chain or cyclic ether, is substituted with the same carbon on the two hydrogen atoms are oxygen atoms, may form a ketone, and k 1 to k 3 is O or 1, each independently, t is O, 1 Or 2, a, b, and c represent a composition ratio of each repeating unit, a is greater than 0 and less than 1, b, c is 0 or more and less than 1 and satisfies a + b + c = 1, In addition, a plurality of repeating units introduced at each composition ratio of a, b, and c may be present.
    [158] Here, R 101 represents a hydrogen atom, a methyl group or CH 2 CO 2 R 103 . R 102 represents a hydrogen atom, a methyl group or CO 2 R 103 . R 103 represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert -Amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethyl cyclopentyl group, butyl cyclopentyl group, ethyl cyclohexyl group, butyl cyclohexyl group, adamantyl group, ethyl adamantyl group And a butyl adamantyl group can be exemplified. R 104 represents an acid labile group, and specific examples thereof will be described later. R 105 is a halogen atom, a hydroxyl group, a straight, branched or cyclic alkoxy group having 1 to 15 carbon atoms, an acyl oxy or alkyl sulfonyl oxy group, or a straight, branched or cyclic alkoxy carbon having 2 to 15 carbon atoms A carbonyl oxy group or an alkoxy alkoxy group, and part or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms, specifically fluorine, chlorine, bromine, hydroxyl group, methoxy group, ethoxy group, propoxy group, isopro Fox group, n-butoxy group, sec-butoxy group, tert-butoxy group, tert-amyloxy group, n-pentoxy group, n-hexyl oxy group, cyclopentyl oxy group, cyclohexyl oxy group, ethyl cyclopentyl oxy group , Butyl cyclopentyl oxy, ethyl cyclohexyl oxy, butyl cyclohexyl oxy, adamantyl oxy, ethyl adamantyl oxy, butyl adamantyl oxy, formyloxy group, acetoxy group, ethyl carbonyl Oxy , Pivaloyl oxy, methane sulfonyl oxy, ethane sulfonyl oxy, n-butane sulfonyl oxy, trifluoro acetoxy group, trichloro acetoxy group, 2, 2, 2-trifluoro ethyl Carbonyl oxy group, methoxy methoxy group, 1-ethoxy ethoxy group, 1-ethoxy propoxy group, 1-tert-butoxy ethoxy group, 1-cyclohexyl oxyethoxy group, 2-tetra hydrofuranyl jade Examples of the group include 2-tetra hydropyranyl oxy, methoxy carbonyl oxy, ethoxy carbonyl oxy, tert-butoxy carbonyl oxy and the like.
    [159] At least one of R 106 to R 109 represents a monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Indicates. As a monovalent hydrocarbon group containing a C1-C15 carboxyl group or a hydroxyl group, specifically, carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, 2-carboxyethoxy carbonyl , 4-carboxy butoxy carbonyl, 2-hydroxyethoxy carbonyl, 4-hydroxybutoxy carbonyl, carboxy cyclopentyl oxy carbonyl, carboxy cyclohexyl oxy carbonyl, carboxy norbornyl oxy carbonyl, carboxy Adamantyl oxy carbonyl, hydroxy cyclopentyl oxy carbonyl, hydroxy cyclohexyl oxy carbonyl, hydroxy norbornyl oxy carbonyl, hydroxy adamantyl oxy carbonyl and the like. As a C1-C15 linear, branched, cyclic alkyl group, the thing similar to what was illustrated by R <103> can be illustrated specifically ,. R 106 and R 107 , R1 07 and R 108 , or R 108 and R 109 , respectively, may combine with each other to form a ring with the carbon atoms to which they are bonded, in which case R 106 and R 107 , R 107 and One of R 108 or R 108 and R 109 represents a divalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the other is a single bond or a linear, branched or cyclic alkylene having 1 to 15 carbon atoms. Group. As a bivalent hydrocarbon group containing a C1-C15 carboxy group or a hydroxyl group, what specifically removed one hydrogen atom from what was illustrated by the said monovalent hydrocarbon group containing a said carboxyl group or a hydroxyl group etc. can be illustrated. As a C1-C15 linear, branched, cyclic alkylene group, what specifically removed one hydrogen atom from what was illustrated by R <103> can be illustrated.
    [160] At least one of R 110 to R 113 represents a monovalent hydrocarbon group containing at least one substructure selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides, imides having 2 to 15 carbon atoms, The remainders each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Specific examples of the monovalent hydrocarbon group containing at least one substructure selected from ethers, ketones, esters, carbonates, acid anhydrides, amides, and imides having 2 to 15 carbon atoms include methoxymethyl and methoxy methoxymethyl. , Formyl, methylcarbonyl, formyl oxy, acetoxy, pivaloyl oxy, formyl oxymethyl, acetoxy methyl, fivaloyl oxymethyl, methoxy carbonyl, 2-oxo oxolan-3-yl oxy Carbonyl, 4, 4-Dimethyl-2-oxooxoran-3-yl oxycarbonyl, 4-methyl-2-oxooxan-4-yl oxycarbonyl, 2-oxo-1, 3-dioxolane- 4-yl methyl oxy carbonyl, 5-methyl-2-oxooxoran-5-yl oxy carbonyl and the like can be exemplified. As a C1-C15 linear, branched, cyclic alkyl group, the thing similar to what was illustrated by R <103> can be illustrated specifically ,. R 110 and R 111 , R 111 and R 112 , or R 112 and R 113, may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case R 110 and R 111 , R 111 and One of R 112 or R 112 and R 113 represents a divalent hydrocarbon group containing at least one substructure selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides and imides having 1 to 15 carbon atoms The other represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. As a divalent hydrocarbon group containing at least 1 sort (s) of substructure chosen from C1-C15 ether, aldehyde, ketone, ester, carbonate, acid anhydride, amide, and imide, Specifically, 2-oxa propane-1, 3-diyl, 1, 1-dimethyl-2-oxapropane-1, 3-diyl, 1-oxo-2-oxapropane-1, 3-diyl, 1, 3-dioxo-2-oxapropane-1, Ethers, aldehydes, ketones having 1 to 15 carbon atoms above, in addition to 3-diyl, 1-oxo-2-oxabutane-1, 4-diyl, 1, 3-dioxo-2-oxabutane-1, 4-diyl and the like Examples of the monovalent hydrocarbon group containing at least one partial structure selected from esters, carbonates, acid anhydrides, amides, and imides include one hydrogen atom removed. As a C1-C15 linear, branched, cyclic alkylene group, what specifically removed one hydrogen atom from what was illustrated by R <3> can be illustrated.
    [161] X 11 to X 13 each independently represent a methylene group or an oxygen atom, but not all of X 11 to X 13 can be methylene groups at the same time. W represents a single bond or a linear, branched or cyclic (t + 2) valent hydrocarbon group having 1 to 5 carbon atoms, and in the case of a hydrocarbon group, one or more methylene groups are substituted with an oxygen atom to form a chain or cyclic ether. And two hydrogen atoms on the same carbon may be substituted with an oxygen atom to form a ketone. For example, when t = O, specifically methylene, ethylene, trimethylene, tetramethylene, pentamethylene, 1, 2 -Propanediyl, 1, 3-butane diyl, 1-oxo-2-oxapropane-1, 3-diyl, 3-methyl-1-oxo-2-oxabutane-1, 4-diyl and the like can be exemplified; In the case of other than t = 0, the (t + 2) valence group which removed t hydrogen atoms in the said specific example can be illustrated. k 1 to k 3 are each independently 0 or 1. t is 0, 1 or 2. a, b, c represent the composition ratio of each repeating unit, a is more than 0 and less than 1, b, c is 0 or more and less than 1, and satisfy | fills a + b + c = 1. The range of a, b, and c is preferably 0.1 ≦ a ≦ O.9, O ≦ b ≦ O.8, O ≦ c ≦ O.8, and more preferably 0.2 ≦ a ≦ O.8, 0 ≤ b ≤ 0.7, O ≤ c ≤ 0.7, more preferably 0.3 ≤ a ≤ 7.7, 0 ≤ b ≤ 0.6, O ≤ c ≤ 0.6. In addition, a plurality of repeating units introduced at each composition ratio of a, b, and c may be present. When the composition ratio of each repeating unit is changed, various characteristics such as developer affinity, substrate adhesion, and etching resistance are changed, so that the performance of the resist material can be finely adjusted by appropriately adjusting the values of a, b, and c.
    [162] As the acid labile group of R 104, the same group as the acid labile group of R AL can be used.
    [163] Although the specific example of the repeating unit introduce | transduced in composition ratio a is shown below among the hydrogenated substance of the ring-opening metathesis polymer represented by the said Formula (6), this invention is not limited to this.
    [164]
    [165] Although the specific example of the repeating unit introduced in composition ratio b is shown below among the hydrogenated products of the ring-opening metathesis polymer represented by the said Formula (6), this invention is not limited to this.
    [166]
    [167] Although the specific example of the repeating unit introduce | transduced in composition ratio c is shown below among the hydrogenated products of the ring-opening metathesis polymer represented by the said Formula (6), this invention is not limited to this.
    [168]
    [169] In addition, when the weight average molecular weight of the hydrogenated substance of the 2nd ring-opening metathesis polymer used preferably for the resist material of this invention is measured using gel permeation chromatography (GPC) in polystyrene conversion, it is 500-200. , OOO, More preferably, it is 3, OOO-20, OOO. If it is out of this range, etching resistance may fall extremely, or the dissolution rate difference before and after exposure may not be secured, and resolution may deteriorate.
    [170] In addition, the hydrogenated substance of the second ring-opening metathesis polymer which is preferably used as the resist material of the present invention has a ratio (Mw / Mn, degree of dispersion) of the weight average molecular weight and the number average molecular weight of 1.O to 2.O. It is desirable to be within a relatively narrow range of. When the degree of dispersion is widened, the uniformity of the polymer compound may be lowered, the resolution may be lowered, or in some cases, the etching resistance may be lowered.
    [171] The hydrogenated product of the second ring-opening metathesis polymer which is preferably used as the resist material of the present invention can be obtained by polymerizing a monomer providing the repeating unit with a ring-opening metathesis catalyst and hydrogenating it under a hydrogenation catalyst. Although it can carry out by the method mentioned above, it is not limited to this.
    [172] Although the high molecular compound which has a repeating unit represented by following General formula (15) as a poly (meth) acrylic acid derivative preferably used as the resist material of this invention is mentioned, for example, It is not limited to this.
    [173]
    [174] In formula, R <114> , R <116> , R <118> and R <120> represent a hydrogen atom or a methyl group each independently, R < 115 > represents an acid labile group, R < 17 > contains a hydrogen atom or a C1-C15 carboxyl group or a hydroxyl group Represents a monovalent hydrocarbon group, R 119 represents a monovalent hydrocarbon group containing at least one substructure selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides, imides having 2 to 15 carbon atoms, and Y 11 is an atomic group for forming a 5- or 6-membered ring together with the two carbon atoms to be bonded, and contains at least one substructure selected from esters, carbonates, acid anhydrides, amides, and imides in the ring structure formed; Y 12 is an atomic group that forms a 5- or 6-membered ring together with one carbon atom to be bonded, and includes esters, carbonates, acid anhydrides, At least one substructure selected from amides and imides, d, e, f, g, h, i represent the composition ratio of each repeating unit, d is greater than 0 and less than 1, e, f, g, h, i is a number equal to or greater than 0 and less than 1, which satisfies d + e + f + g + h + i = 1 and is introduced at each composition ratio of d, e, f, g, h, i There may be a plurality of units each.
    [175] Here, R 114 , R 116 , R 118 and R 120 each independently represent a hydrogen atom or a methyl group. R 115 represents an acid labile group, and specifically, the same as those exemplified for R 104 (R AL ) can be exemplified. R 117 represents a hydrogen atom or a monovalent hydrocarbon group containing a carboxy group or hydroxyl group having 1 to 15 carbon atoms, specifically, a hydrogen atom, carboxyethyl, carboxybutyl, carboxy cyclopentyl, carboxy cyclohexyl, carboxynorbornyl, carboxya Danmantil, hydroxyethyl, hydroxybutyl, hydroxy cyclopentyl, hydroxy cyclohexyl, hydroxy norbornyl, hydroxy adamantyl and the like. R 119 represents a monovalent hydrocarbon group containing at least one substructure selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides and imides having 2 to 15 carbon atoms, specifically methoxymethyl, 2-oxooxoran-3-yl, 4,4-dimethyl-2-oxooxoran-3-yl, 4-methyl-2-oxooxan-4-yl, 2-oxo-1, 3-dioxolane 4-yl methyl, 5-methyl-2-oxooxoran-5-yl, etc. can be illustrated. Y 11 is an atomic group that forms a five-membered or six-membered ring together with the two carbon atoms to which it is bonded, and contains at least one substructure selected from esters, carbonates, acid anhydrides, amides, and imides in the ring structure; Specifically, 1-oxo-2-oxapropane-1, 3-diyl, 1-oxo-2-oxabutane-1, 4-diyl, 2-oxo-1, 3-dioxapropane-1, 3- Diyl, 1, 3-dioxo-2-oxapropane-1, 3-diyl, 1-oxo-2-azapropane-1, 3-diyl, 1-oxo-2-methyl-2-azapropane-1, 3-diyl, 1-oxo-2-azabutane-1, 4-diyl, 1, 3-dioxo-2-azapropane-1, 3-diyl, 1, 3-dioxo-2-methyl-2- Azapropane-1, 3-diyl and the like can be exemplified. Y 12 is an atomic group that forms a five-membered or six-membered ring together with one carbon atom to be bonded, and contains at least one substructure selected from esters, carbonates, acid anhydrides, amides, and imides in the ring structure formed; . 1-oxo-2-oxabutane-1, 4-diyl, 1-oxo 2-oxapentin-1, 5-diyl, 1-oxo-2-azabutane-1, 4-diyl, 1-oxo-2- Methyl-2-azabutane-1, 4-diyl, 1-oxo-2-azapentane-1, 5-diyl, 1-oxo-2-methyl-2-azapentane-1, 5-diyl and the like Can be. d, e, f, g, h represent the composition ratio of each repeating unit, d is more than 0 and less than 1, e, f, g, h, i is the number of 0 or more and less than 1, d + e + f + g satisfies + h + i = 1 The ranges of d, e, f, g, and h are preferably O, 1 ≦ d ≦ O.9, O ≦ e ≦ 0.8, O ≦ f ≦ O.8, 0 ≦ g ≦ O.8, O ≦ h≤O8, O≤i≤O8, more preferably 0.2≤d≤O8, O≤e≤O7, O≤f≤O7, O≤g≤O7 , O ≦ h ≦ 0.7, O ≦ i ≦ 0.7, more preferably 0.3 ≦ d ≦ O.7, 0 ≦ e ≦ O.6, O ≦ f ≦ 0.6, O ≦ g ≦ O.6, O ≦ h≤0.6, 0≤i≤0.6. In addition, a plurality of repeating units introduced at each composition ratio of d, e, f, g, h, and i may exist. By changing the composition ratio of each repeating unit, various characteristics such as developer affinity, substrate adhesion, and etching resistance are changed. Thus, by adjusting the values of d, e, f, g, h, and i appropriately, the performance of the resist material is finely adjusted. Can be.
    [176] In addition, when the weight average molecular weight of the poly (meth) acrylic acid derivative used preferably for the resist material of this invention is measured using the gel permeation chromatography (GPC) in polystyrene conversion, it is 1, OOO-500, OOO, More preferably, they are 3, OOO-100, OOO. If it is out of this range, etching resistance may fall extremely or resolution difference may not be ensured before and after exposure, and resolution may fall.
    [177] In addition, the poly (meth) acrylic acid derivative preferably used as the resist material of the present invention has a ratio (Mw / Mn, degree of dispersion) of the weight average molecular weight and the number average molecular weight within a relatively narrow range of 1.0 to 3.O. It is desirable to have. When the degree of dispersion is widened, the uniformity of the polymer compound may be lowered, the resolution may be lowered, or, in some cases, the etching resistance may be lowered.
    [178] The production of the poly (meth) acrylic acid derivative which is preferably used as the resist material of the present invention can be carried out by the method described in, for example, Patent Publication No. 2000-159758 and the like, but is not limited thereto.
    [179] The blending ratio of the hydrogenated product of the ring-opening metathesis polymer and the poly (meth) acrylic acid derivative preferably used as the resist material of the present invention is preferably 90:10 to 10:90, more preferably 80:20 as a weight ratio. To 20:80. When the compounding ratio of the hydrogenated substance of the ring-opening metathesis polymer is too small, the etching resistance may be lowered, and when the compounding ratio of the poly (meth) acrylic acid derivative is too small, the resolution improvement effect may be insufficient.
    [180] The resist material which contains as a base resin the hydrogenated substance of the ring-opening metathesis polymer which has a specific structure of this invention is suitable as a positive resist material, especially a chemically amplified positive resist material, The said ring-opening metathesis polymer as a base resin In addition to the hydrogenated substance, a compound (hereinafter referred to as an acid generator) and an organic solvent which generate an acid in response to a high energy ray or an electron beam are contained.
    [181] As the acid generator used in the present invention,
    [182] i.Onium salt of formula (16aa), (16ab) or (16ac)
    [183] ii. diazomethane derivatives of the formula (16b),
    [184] iii.glyoxime derivatives of formula (16c),
    [185] iv. a bissulfone derivative of formula (16d)
    [186] v. sulfonic acid esters of N-hydroxy imide compounds of formula (16e),
    [187] vi.β-ketosulfonic acid derivatives,
    [188] vii. disulfone derivatives,
    [189] viii. nitrobenzylsulfonate derivatives, and
    [190] ix. sulfonic acid ester derivatives;
    [191]
    [192]
    [193] In formula, R <151a> , R <151b> , R <151c> is a C1-C12 linear, branched or cyclic alkyl group, an alkenyl group, an oxoalkyl group, or an oxo alkenyl group, a C6-C20 aryl group, or C7-C20 each An aralkyl group of 12 or an aryloxoalkyl group, a part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like, and R 151b and R 151c may be bonded to form a ring to form a ring In the case, R 151b and R 151c each represent an alkylene group having 1 to 6 carbon atoms, and K − represents a non-nucleophilic counter ion.
    [194] R 151a , R 151b , and R 151c may be the same as or different from each other, and specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropyl methyl, 4-methylcyclohexyl, cyclohexyl methyl, norbornyl, adamantyl have. Examples of the alkenyl group include vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like. 2-oxo cyclopentyl group, 2-oxo cyclohexyl group, etc. are mentioned as an oxoalkyl group, 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2 -(4-methylcyclohexyl) -2-oxoethyl group etc. are mentioned. As an aryl group, such as a phenyl group, a naphthyl group, and a p-methoxy phenyl group, m-methoxy phenyl group, o-methoxy phenyl group, an ethoxy phenyl group, p-tert- butoxyphenyl group, m-tert- butoxyphenyl group, etc. Alkylphenyl groups, such as an alkoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethyl phenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and dimethyl phenyl group, alkyl, such as methyl naphthyl group and ethyl naphthyl group Alkoxy naphthyl groups such as naphthyl group, methoxy naphthyl group and ethoxy naphthyl group, dialkoxy naphthyl groups such as dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Can be mentioned. Examples of the aralkyl group include benzyl group, phenylethyl group and phenethyl group. As an aryl oxo alkyl group, 2-aryl-2-oxo, such as a 2-phenyl- 2-oxo ethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group, etc. Ethyl group etc. are mentioned. Examples of non-nucleophilic counter ions of K − include halide ions such as chloride ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1, 1, 1-trifluoro ethanesulfonate and nonafluoro butanesulfonate, and tosyl Alkyl sulfonates, such as an aryl sulfonate, a xylate, butane sulfonate, such as a late, a benzene sulfonate, 4-fluoro benzene sulfonate, 1, 2, 3, 4, 5-pentafluorobenzene sulfonate, is mentioned. have.
    [195]
    [196] In the formula, R 152a and R 152b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R 153 represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and R 154a And R 154b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K − represents a non-nucleophilic counter ion.
    [197] Specific examples of R 152a and R 152b 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 and cyclo A pentyl group, a cyclohexyl group, a cyclopropyl methyl group, 4-methyl cyclohexyl group, a cyclohexyl methyl group, etc. are mentioned. Examples of R 153 include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1, 4-cyclohexylene group, 1 and 2-cyclohexylene group, 1, 3-cyclopentylene group, 1, 4-cyclooctylene group, 1, 4-cyclohexane dimethylene group, etc. are mentioned. Examples of R 154a and R 154b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 2-oxocycloheptyl group, and the like. K - may be the same as described in the formulas 16aa and 16ab.
    [198]
    [199] In formula, R <155> , R <156> represents a C1-C12 linear, branched or cyclic alkyl group or a halogenated alkyl group, a C6-C20 aryl group or a halogenated aryl group, or a C7-C12 aralkyl group.
    [200] Examples of the alkyl group of R 155 and R 156 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, amyl group and cyclo A pentyl group, a cyclohexyl group, a cycloheptyl 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-methoxy phenyl group, m-methoxy phenyl group, o-methoxy phenyl group, ethoxy phenyl group, p-tert- butoxyphenyl group, and m-tert- butoxyphenyl group, 2-methylphenyl Alkylphenyl groups, such as group, 3-methylphenyl group, 4-methylphenyl group, ethyl phenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and a dimethyl phenyl group, are mentioned. As a halogenated aryl group, a fluoro phenyl group, a chlorophenyl group, 1, 2, 3, 4, 5-pentafluoro phenyl group, etc. are mentioned. A benzyl group, a phenethyl group, etc. are mentioned as an aralkyl group.
    [201]
    [202] In formula, R <157> , R <158> and R <159> are a C1-C12 linear, branched or cyclic alkyl group or a halogenated alkyl group, a C6-C20 aryl group or a halogenated aryl group, or a C7-C12 aralkyl group R 158 and R 159 may combine with each other to form a cyclic structure. When forming a cyclic structure, R 1 58 and R 159 each represent a linear or branched alkylene group having 1 to 6 carbon atoms.
    [203] Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group for R 157 , R 158 and R 159 include the same groups as described for R 155 and R 156 . Moreover, as an alkylene group of R <158> , R <159> , a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, etc. are mentioned.
    [204]
    [205] In formula, R <151a> , R <151b> is as above.
    [206]
    [207] In the formula, R 160 represents an allylene 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, wherein some or all of the hydrogen atoms of these groups are again linearly having 1 to 4 carbon atoms. Or a branched alkyl group or alkoxy group, nitro group, acetyl group, or phenyl group, R 161 is a linear, branched or substituted alkyl group having 1 to 8 carbon atoms, alkenyl group or alkoxy alkyl group, phenyl group, or A naphthyl group, wherein some or all of the hydrogen atoms of these groups are again an alkyl or alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl, alkoxy, nitro or acetyl group having 1 to 4 carbon atoms; Hetero aromatic groups having 3 to 5 carbon atoms; Or a chlorine atom or a fluorine atom.
    [208] Here, as an allylene group of R 160 , 1, 2-phenylene group, 1, 8-naphthylene group, etc. are mentioned, As an alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbor Examples of the egg-2 and 3-diyl groups include alkenylene groups such as 1, 2-vinylene groups, 1-phenyl-1, 2-vinylene groups, 5-norbornene-2 and 3-diyl groups. . Examples of the alkyl group of R 161 are the same as those of R 151a to R 151c, and the alkenyl group includes a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, and 3-pente A nilyl group, 4-pentenyl group, dimethyl allyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group, etc. Examples of the alkoxy alkyl group include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group and pentyl Oxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxy A pentyl group, a methoxyhexyl group, a methoxy heptyl group, etc. are mentioned.
    [209] In addition, examples of the alkyl group having 1 to 4 carbon atoms which may be further substituted include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. A phenyl group which may be substituted with an alkyl group, an alkoxy group, a nitro group, or an acetyl group having 1 to 4 carbon atoms, such as a period, an ethoxy group, a propoxy group, an isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group Examples of the phenyl group, tolyl group, p-tert-butoxyphenyl group, p-acetylphenyl group, p-nitrophenyl group, and the like include a pyridyl group, a prill group, and the like as a hetero aromatic group having 3 to 5 carbon atoms.
    [210] Specifically, for example, trifluoromethane sulfonic acid diphenyl iodonium, trifluoromethane sulfonic acid (p-tert-butoxyphenyl) phenyl iodonium, p-toluene sulfonic acid diphenyl iodonium, p-toluene sulfonic acid (p -tert-butoxyphenyl) phenyliodonium, trifluoromethane sulfonic acid triphenylsulfonium, trifluoromethane sulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethane sulfonic acid bis (p-tert -Butoxyphenyl) phenylsulfonium, trifluoromethane sulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) di Phenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutane sulfonic acid triphenylsulfonium, butane Sulfonic acid triphenylsulfonium, trifluoromethane sulfonic acid trimethyl sulfonium, p-toluenesulfonic acid tri Methyl sulfonium, trifluoromethane sulfonic acid cyclohexyl methyl (2-oxocyclohexyl) sulfonium, p-toluenesulfonic acid cyclohexyl methyl (2-oxocyclohexyl) sulfonium, trifluoromethane sulfonic acid dimethyl phenylsulfonium, p -Toluenesulfonic acid dimethyl phenylsulfonium, trifluoromethane sulfonic acid dicyclohexyl phenylsulfonium, p-toluenesulfonic acid dicyclohexyl phenylsulfonium, trifluoromethane sulfonic acid trinaphthylsulfonium, trifluoromethane sulfonic acid cyclohexyl methyl ( 2-oxocyclohexyl) sulfonium, trifluoromethane sulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethane sulfonate ], Onium salts such as 1,2'-naphthylcarbonyl methyl tetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonate) Ponyl) Diazome , Bis (cyclohexyl sulfonyl) diazomethane, bis (cyclopentyl sulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec- Butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropyl sulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl ) Diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexyl sulfonyl- (tert- Butylsulfonyl) diazomethane, 1-cyclohexyl sulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Diazomethane derivatives, bis-O- (p-toluenesulfonyl) -α-dimethyl glyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluene Sulfonyl) -α-dicyclohexyl glyoxime, bis-O- (p-toluenesulfonyl ) -2,3-pentanedioneglyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3, 4-pentanedioneglyoxime, bis-O- (n-butanesulfonyl) -α- Dimethyl glyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexyl glyoxime, bis-O- (n- Butanesulfonyl) -2, 3-pentanedioneglyoxime, bis-O- (n-butanesulfonyl) -2-methyl-3, 4-pentanedioneglyoxime, bis-O- (methanesulfonyl) -α -Dimethyl glyoxime, bis-O- (trifluoromethane sulfonyl) -α-dimethyl glyoxime, bis-O- (1, 1, 1-trifluoroethane sulfonyl) -α-dimethyl glyoxime, bis -O- (tert-butanesulfonyl) -α-dimethyl glyoxime, bis-O- (perfluorooctane sulfonyl) -α-dimethyl glyoxime, bis-O- (cyclohexane sulfonyl) -α-dimethyl Glyoxime, bis-O- (benzenesulfonyl) -α-dimethyl glyoxime, bis-O- (p-fluorobenzene sulfonyl) -α-dimethyl glyoxime, bis-O- (p-tert-butylbenzene Sulfonyl) -α-dimethyl glyoxime, Glyoxime derivatives such as bis-O- (xylenesulfonyl) -α-dimethyl glyoxime, bis-O- (camphorsulfonyl) -α-dimethyl glyoxime, bisnaphthyl sulfonylmethane, bistrifluoromethyl Bissulphone derivatives such as sulfonylmethane, bismethyl sulfonylmethane, bisethyl sulfonylmethane, bispropyl sulfonylmethane, bisisopropyl sulfonylmethane, bis-p-toluenesulfonylmethane, bisbenzene sulfonylmethane, Β-ketosulfone derivatives such as -cyclohexyl carbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane, diphenyldisulfone, dicyclohexyl Disulfone derivatives such as disulfone, nitrobenzyl sulfonate derivatives such as p-toluenesulfonic acid 2,6-dinitrobenzyl and p-toluenesulfonic acid 2,4-dinitrobenzyl, and 1, 2 and 3-tris (methanesulfonyl Oxy) benzene, 1, 2, 3-tris (trifluoromethane sulfonyloxy) benzene, 1, 2, 3-tris (p-toluenesulfonyl oxy) benzene Sulfonic acid ester derivatives, N-hydroxy succinimide methanesulfonic acid ester, N-hydroxy succinimide trifluoromethane sulfonic acid ester, N-hydroxy succinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1- Propanesulfonic acid ester, N-hydroxysuccinic imide 2-propanesulfonic acid ester, N-hydroxy succinimide 1-pentanesulfonic acid ester, N-hydroxy succinimide 1-octane sulfonic acid ester, N-hydroxy succinimide p-toluenesulfonic acid ester, N-hydroxy succinimide p-methoxybenzenesulfonic acid ester, N-hydroxy succinimide 2-chloroethane sulfonic acid ester, N-hydroxy succinimidebenzene sulfonic acid ester, N-hydroxy Succinimide-2, 4, 6-trimethyl benzenesulfonic acid ester, N-hydroxy succinimide 1-naphthalenesulfonic acid ester, N-hydroxy succinimide 2-naphthalenesulfonic acid ester, N-hydride Hydroxy-2-phenylsuccinimidemethane sulfonic acid ester, N-hydroxy maleimide methane sulfonic acid ester, N-hydroxy maleimide ethane sulfonic acid ester, N-hydroxy-2-phenyl maleimide methane sulfonic acid ester, N-hydroxy Glutalimide methane sulfonic acid ester, N-hydroxyglutal imide benzene sulfonic acid ester, N-hydroxy phthalimide methane sulfonic acid ester, N-hydroxy phthalimide benzene sulfonic acid ester, N-hydroxy phthalimide tri Fluoromethane sulfonic acid ester, N-hydroxy phthalimide p-toluenesulfonic acid ester, N-hydroxy naphthalimide methane sulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N-hydroxy-5- Norbornene-2,3-dicarboxyimidemethane sulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimide trifluoromethane sulfonic acid ester, N-hydroxy-5 Sulfonic acid ester derivatives of N-hydroxyimide compounds such as -norbornene-2 and 3-dicarboxyimide p-toluenesulfonic acid ester; and the like, but trifluoromethane sulfonic acid triphenylsulfonium and trifluoromethane sulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethane sulfonic 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, trifluoromethane sulfonic acid trinaphthylsulfonium, trifluoromethane sulfonic acid cyclohexyl methyl (2-oxocyclohexyl Onium salts such as sulfonium, trifluoromethane sulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, 1, 2'-naphthylcarbonyl methyl tetrahydro thiophenium triflate, bis ( Benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazo Carbon, bis (cyclohexyl sulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis ( diazomethane derivatives such as n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane and bis (tert-butylsulfonyl) diazomethane, bis-O- (p-toluenesulfonyl) glyoxime derivatives such as -α-dimethyl glyoxime, bis-O- (n-butanesulfonyl) -α-dimethyl glyoxime, bissulphone derivatives such as bisnaphthyl sulfonylmethane, N-hydroxy succinimide methane Sulfonic acid ester, N-hydroxy succinimide trifluoromethane sulfonic acid ester, N-hydroxy succinimide 1-propanesulfonic acid ester, N-hydroxy succinimide 2-propanesulfonic acid ester, N-hydroxy succinimide 1-pentanesulfonic acid ester, N-hydroxy succinimide p-toluenesulfonic acid ester, N-hydroxy naphthalimide The methanesulfonate, N- hydroxy-naphthalimide is N- hydroxy acid ester derivative of roksiyi imide compounds such as benzene sulfonic acid imide ester is preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more type. The onium salt is excellent in the rectangularity improvement effect, and the diazo methane derivative and the glyoxime derivative are excellent in the standing wave reduction effect. Therefore, fine adjustment of the profile can be performed by combining both.
    [211] The amount of the acid generator added is preferably 0.1 parts to 15 parts, and more preferably 0.5 to 8 parts with respect to 100 parts (based on the weight of the base resin). If there is less than 0, 1 part, a sensitivity may be bad, and when more than 15 parts, transparency may become low and resolution may fall.
    [212] The organic solvent used in the present invention may be any organic solvent which can dissolve a base resin, an acid generator, and other additives. As such an organic solvent, for example, ketones such as cyclohexanone and methyl-2-amyl ketone, 3-methoxy butanol, 3-methyl-3-methoxy butanol, 1-methoxy-2-propanol and 1- Alcohols such as oxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert Esters such as -butyl ether acetate, and the like can be used alone or in combination of two or more thereof. It can be, but is not limited to these. In the present invention, among these organic solvents, propylene glycol monomethyl ether acetate, which is a safety solvent, and a mixed solvent thereof, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which are excellent in solubility of an acid generator in a resist component, are preferable. Is used.
    [213] The usage-amount of the organic solvent is suitable for 200-1, OOO parts, especially 400-800 parts with respect to 100 parts of base resins.
    [214] To the resist material of the present invention, a high molecular compound different from the hydrogenated substance of the ring-opening metathesis polymer and poly (meth) acrylic acid derivative preferably used in the present invention can be added.
    [215] Specific examples of the polymer compound include, but are not limited to, those having a weight average molecular weight of 1, OOO to 500, OOO, preferably 5,000 to 100,000 represented by the following general formula (R1) and / or the following general formula (R2). .
    [216]
    [217] In the formula, R 001 represents a hydrogen atom, a methyl group or CH 2 CO 2 R 003 , R 002 represents a hydrogen atom, a methyl group or C0 2 R 003 , R 003 is a straight, branched or cyclic having 1 to 15 carbon atoms Represents an alkyl group, R 004 represents a hydrogen atom or a monovalent hydrocarbon group containing a carboxyl group or hydroxyl group having 1 to 15 carbon atoms, and at least one of R 005 to R 008 contains 1 carboxyl group or hydroxyl group containing 1 to 15 carbon atoms A hydrocarbon group, and the rest each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and R 005 to R 008 may combine with each other to form a ring, in which case R at least one of 005 to R 008 represents a divalent hydrocarbon group containing a carboxyl or hydroxyl group of a carbon number of 1 to 15, the remains are each independently a single bond or Denotes having 1 to 15 straight-chain, branched or cyclic alkylene group of, R 009 is at least one kind of 2 to 15 carbon atoms in the ether, aldehyde, ketone, ester, carbonate, acid anhydride, amide, already selected in the de A monovalent hydrocarbon group containing a partial structure, and at least one of R 010 to R 013 is at least one selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides, and imides having 2 to 15 carbon atoms A monovalent hydrocarbon group containing a partial structure, the remainder each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and R 010 to R 013 may be bonded to each other to form a ring; and, in that case R 010 to R 013, at least one of the pieces is 1 to 15 carbon atoms in the ether, aldehyde, ketone, ester, carbonate, acid anhydride, amide, Represents an at least divalent hydrocarbon group containing a partial structure of one selected from polyimide, and the remains are each independently a single bond or represents C 1 -C 15 straight, branched or cyclic alkylene group of, R 014 has a carbon number of 7 Or an alkyl group containing a polycyclic hydrocarbon group or a polycyclic hydrocarbon group of 15 to 15, R 015 represents an acid labile group, R 016 represents a hydrogen atom or a methyl group, R 017 is a linear, branched or A cyclic alkyl group, X represents CH 2 or an oxygen atom, k 'is 0 or 1, and a1', a2 ', a3', b1 ', b2', b3 ', c1', c2 ', c3' , d1 ', d2', d3 ', and e' are numbers of 0 or more and less than 1, and a1 '+ a2' + a3 '+ b1' + b2 '+ b3' + c1 '+ c2' + c3 '+ d1' + d2 '+ d3' + e '= 1 is satisfied, and f', g ', h', i ', j' are more than 0 and less than 1, and f '+ g' + h '+ i' + j '= 1 is satisfied, x', y 'and z' are integers of 0 to 3, and 1≤x '+ y' + z'≤5, and 1≤y '+ z'≤3. The Group.
    [218] In addition, the specific example of each group is the same as the above description.
    [219] The polymer compound is added for fine adjustment of the resist performance, and in order not to impair the characteristics of the present invention, the addition amount is suitably small. Specifically, the compounding ratio of the sum total of the hydrogenated substance of the ring-opening metathesis polymer and the poly (meth) acrylic acid derivative and the high molecular compound of the present invention is preferably 100: O to 70:30, particularly 100: O to It is preferable to exist in the range of the weight ratio of 80:20. In the case where the polymer compound is blended in excess of this range, it is possible to obtain a desirable performance as a resist material, such as partial dropping of the film during the phase separation pattern formation during film formation.
    [220] In addition, the high molecular compound is not limited to 1 type, but can add 2 or more types. By using a plurality of high molecular compounds, the performance of the resist material can be adjusted.
    [221] The dissolution control agent can be further added to the resist material of the present invention. As the dissolution control agent, the average molecular weight is 100 to 1, OOO, preferably 150 to 800, and the hydrogen atom of the phenolic hydroxyl group of the compound having two or more phenolic hydroxyl groups in the molecule The compound which substituted the hydrogen atom of the carboxyl group of the compound which substituted by the ratio of 0-100 mol% or the compound which has a carboxyl group in the molecule | numerator in the ratio of 50-100 mol% of the average by the acid labile group is mix | blended.
    [222] The substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is, on average, at least O mol%, preferably at least 30 mol%, of the entire phenolic hydroxyl group, and its upper limit is 100 mol%, more preferably 80 Molar%. The substitution rate by the acid labile group of the hydrogen atom of the carboxyl group is 50 mol% or more, preferably 70 mol% or more of the whole carboxyl group on average, The upper limit is 100 mol%.
    [223] In this case, as a compound which has two or more such phenolic hydroxyl groups, or a compound which has a carboxyl group, what is represented by following General formula (D1)-(D14) is preferable.
    [224]
    [225] (Wherein R 201 and R 202 each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, and R 203 represents a hydrogen atom or a linear or branched phase having 1 to 8 carbon atoms) Or an alkyl group or an alkenyl group or-(R 207 ) h C00H, R 204 represents-(CH 2 ) i- (i = 2 to 10), an allylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group and an oxygen atom Or a sulfur atom, R 205 represents an alkylene group having 1 to 10 carbon atoms, an allylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom, and R 206 represents a hydrogen atom or a C 1-8 member A chain or branched alkyl group, an alkenyl group, or a phenyl group or a naphthyl group substituted with a hydroxyl group, respectively, R 207 represents a linear or branched alkylene group having 1 to 10 carbon atoms, and R 208 represents a hydrogen atom or a hydroxyl group J is 0 to 5 Integer, u, h is O or 1, s, t, s ', t', s '', t '' are s + t = 8, s '+ t' = 5, s '' + t '' = 4 is satisfied and at least one hydroxyl group is present in each phenyl skeleton, and α is a number having a molecular weight of 100 to 1,000 of the compounds of the formulas (D8) and (D9).)
    [226] In the above formulas, R 201 and R 202 are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R 203 are , for example, R 201 , R 202 , or -COOH , -CH 2 COOH, R 204, for example, ethylene group, phenylene group, carbonyl group, sulfonyl group, oxygen atom, sulfur atom, etc., R 205, for example, methylene group, or R 204 , such as R 206 , Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group substituted with a hydroxyl group, and a naphthyl group.
    [227] As an acid labile group of a dissolution control agent, although it can use various, Specifically, the tree represented by the following general formula (L1)-(L4), a C4-C20 tertiary alkyl group, and a C1-C6 tree of each alkyl group, respectively Alkyl silyl group, a C4-C20 oxo alkyl group, etc. are mentioned.
    [228]
    [229] (Wherein R LO1 and R L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R L03 is a monovalent compound which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms) A hydrocarbon group, R L01 and R L02 , R LO1 and R L03 , R L02 and R L03 may combine to form a ring, and in the case of forming a ring, R L01 , R L02 , and R L03 each may have 1 to 4 carbon atoms. A straight or branched alkylene group of 18, R L04 is a C4-20 tertiary alkyl group, each alkyl group is a C1-6 trialkylsilyl group, a C4-20 oxoalkyl group or the above formula ( Represents a group represented by L1), R 105 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or a substituted aryl group having 6 to 20 carbon atoms, and R 106 represents a hetero atom having 1 to 8 carbon atoms May contain A monovalent hydrocarbon group or a C6-C20 substitutable aryl group, R L07 to R L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and R L07 To R L16 may be bonded to each other to form a ring, in which case, a divalent hydrocarbon group may contain a hetero atom having 1 to 15 carbon atoms, and R L07 to R L16 are bonded to adjacent carbons; Directly bond and form a double bond, y is an integer from 0 to 6, m is 0 or 1, n is any one of O, 1, 2, 3, and 2m + n = 2 or 3 Is a satisfying number.)
    [230] In addition, about the specific example of each group, it is the same as the above description.
    [231] The compounding quantity of the said dissolution control agent is 0-50 parts with respect to 100 parts of base resin, Preferably it is O-40 parts, More preferably, it is O-30 parts, It can use individually or in mixture of 2 or more types. When the compounding quantity exceeds 50 parts, a film streak of a pattern may arise and the resolution may fall.
    [232] In addition, the above dissolution control agent is synthesized by introducing an acid labile group to the compound having a phenolic hydroxyl group or carboxyl group using an organic chemical formulation.
    [233] Moreover, a basic compound can be mix | blended with the resist material of this invention.
    [234] As a basic compound, the compound which can suppress the diffusion rate at the time when the acid which arises from an acid generator diffuses in a resist film is suitable. By compounding the basic compound, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure can be suppressed, or the substrate and the environmental dependence can be reduced, and the exposure margin, the pattern profile, and the like can be improved. .
    [235] Examples of the basic compound include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen compounds having a carboxyl group, nitrogen compounds having a sulfonyl group, and nitrogen containing hydroxyl groups. The compound, the nitrogen-containing compound which has a hydroxy phenyl group, an alcoholic nitrogen compound, an amide derivative, an imide derivative, etc. are mentioned.
    [236] Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine and pentylamine , tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylene pentamine and the like are exemplified As secondary aliphatic amines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine , Dicyclopentyl amine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylene diamine, N, N -Dimethylethylene diamine, N, N-dimethyl tetraethylene pentamine and the like are exemplified, As tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, Tricyclopentyl amine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetra Methylene methylene diamine, N, N, N ', N'- tetramethylethylenediamine, N, N, N', N'- tetramethyl tetraethylene pentamine, etc. are illustrated.
    [237] In addition, examples of the mixed amines include dimethyl ethylamine, methylethyl propylamine, benzylamine, phenethylamine, benzyldimethyl amine, and the like. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methyl aniline, N-ethyl aniline, N-propyl aniline, N, N-dimethyl aniline, 2-methyl aniline, 3-methyl aniline, 4-methyl aniline, ethyl aniline, propyl aniline, trimethyl aniline, 2-nitro aniline, 3-nitro aniline, 4-nitro aniline, 2, 4-dinitro aniline, 2, 6-dinitro aniline, 3, 5-di Nitroaniline, N, N-dimethyl toluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g. pyrrole, 2H-pyrrole, 1-methyl pyrrole, 2, 4-dimethyl pyrrole, 2, 5-dimethyl pyrrole, N-methyl pyrrole and the like), oxazole derivatives (e.g. oxazole, isoxazole, etc.), thiazole derivatives ( For example thiazole, isothiazole, etc., imidazole derivatives (for example imidazole, 4-methyl imidazole, 4-meth) 2-phenylimidazole, etc.), pyrazole derivatives, prazan derivatives, pyrroline derivatives (e.g. pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g. pyrrolidine , N-methyl pyrrolidine, pyrrolidinone, N-methyl pyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butyl) Pyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxy Pyridine, Butoxypyridine, Dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidino pyridine, 1-methyl-4-phenylpyridine, 2- (1-ethyl propyl) pyridine, aminopyridine, dimethyl amino Pyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indolin derivatives, quinoline derivatives (e.g. quinoline, 3-quinoline carbonitrile, etc.), isoquinoline derivatives, cinnaline derivatives , Quinazoline derivatives, quinoxaline derivatives, pphthalazine derivatives, prine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1, 10-phenanthroline derivatives, adenine derivatives , Adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.
    [238] As the nitrogen-containing compound having a carboxyl group, for example, amino benzoic acid, indole carboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylosin, leucine, Methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxy alanine), and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridine sulfonic acid and p-toluene sulfonic acid pyridinium. As a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxy phenyl group, an alcoholic nitrogen compound, 2-hydroxy pyridine, amino cresol, 2, 4-quinoline diol, 3-indolemethanol hydrate, monoethanolamine, Diethanolamine, triethanolamine, N-ethyl diethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2, 2'-imino die Tanol, 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, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxy Hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1, 2-propanediol, 3-pyrrolidino-1, 2-propanediol, 8-hydroxy eurolidine, 3-quinuclidinol, Examples include 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, and the like. do. Examples of the amide derivatives include formamide, N-methyl formamide, N, N-dimethyl formamide, acetamide, N-methyl acetamide, N, N-dimethyl acetamide, propionamide, benzamide and the like. Phthalimide, succinimide, maleimide, etc. are illustrated as an imide derivative.
    [239] Moreover, 1 type, or 2 or more types chosen from the basic compound represented by following formula (17) can also be mix | blended.
    [240] N (X) n (Y) 3-n
    [241] Wherein n is 1, 2 or 3, and Y each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a hydroxyl group or an ether structure, and each of X is Independently the formulas (X1) to (X3)
    [242]
    [243] (Wherein R 300 , R 302 and R 305 represent a linear or branched alkylene group having 1 to 4 carbon atoms, and R 301 , R 304 , R 306 represent a hydrogen atom or a linear, minute having 1 to 20 carbon atoms). Terrestrial or cyclic alkyl groups, and may contain one or more hydroxy groups, ether structures, ester structures, or lactone rings, and R 303 represents a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms.) The group represented by is represented, and two or three X can combine and form a ring.
    [244] Specific examples of the basic compound represented by the above formula (17) include tris (2-methoxy methoxyethyl) amine, tris {2- (2-methoxy ethoxy) ethyl} amine, and tris {2- (2-methoxy eth. Methoxy methoxy) ethyl} amine, tris {2- (1-methoxy ethoxy) ethyl} amine, tris {2- (1-ethoxy ethoxy) ethyl} amine, tris {2- (1-ethoxy pro Foxy) ethyl} amine, tris [2- {2- (2-hydroxy ethoxy) ethoxy} ethyl] amine, 4, 7, 13, 16, 21, 24-hexaoxa-1, 10-diazabicyclo [8. 8. 8] hexacoic acid, 4, 7, 13, 18-tetraoxa-1, 10-diazabicyclo [8.5.5] eichoic acid, 1, 4, 10, 13-tetraoxa-7, 16-diazabi Cyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-form Wheat oxyethyl) amine, tris (2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, Tris (2-valeryloxyethyl) amine, tris (2-pivaloyl oxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxy acetoxy) ethyl amine, tris (2- Methoxy carbonyl oxyethyl) amine, tris (2-tert-butoxy carbonyl oxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxy carbonyl methyl) Oxyethyl] amine, tris [2- (tert-butoxy carbonyl methyl oxy) ethyl] amine, tris [2- (cyclohexyl Cycarbonyl methyl oxy) ethyl] amine, tris (2-methoxy carbonyl ethyl) amine, tris (2-ethoxy carbonyl ethyl) amine, N, N-bis (2-hydroxyethyl) 2- (meth Oxycarbonyl) ethyl amine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethyl amine, N, N-bis (2-hydroxyethyl) 2- (ethoxy carbonyl) Ethyl amine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethyl amine, N, N-bis (2-hydroxyethyl) 2- (2-methoxy ethoxy carbonyl) Ethyl amine, N, N-bis (2-acetoxyethyl) 2- (2-methoxy ethoxy carbonyl) ethyl amine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxy ether Oxycarbonyl) ethyl amine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxy ethoxy carbonyl) ethyl amine, N, N-bis (2-hydroxyethyl) 2-[( Methoxy carbonyl) methoxy carbonyl] ethyl amine, N, N-bis (2-acetoxyethyl) 2-[(methoxy carbonyl) methoxy carbonyl] ethyl amine, N, N-ratio (2-hydroxyethyl) 2- (2-oxopropoxy carbonyl) ethyl amine, N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxy carbonyl) ethyl amine, N, N -Bis (2-hydroxyethyl) 2- (tetra hydrofurfuryloxy carbonyl) ethyl amine, N, N-bis (2-acetoxyethyl) 2- (tetra hydrofurfuryloxy carbonyl) ethyl amine, N , N-bis (2-hydroxyethyl) 2-[(2-oxo tetrahydrofuran-3-yl) oxy carbonyl] ethyl amine, N, N-bis (2-acetoxyethyl) 2-[(2 -Oxo tetrahydrofuran-3-yl) oxy carbonyl] ethyl amine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxybutoxy carbonyl) ethyl amine, N, N-bis ( 2-formyl oxyethyl) 2- (4-formyl oxy butoxycarbonyl) ethyl amine, N, N-bis (2-formyl oxyethyl) 2- (2-formyl oxy ethoxy carbonyl) ethyl Amine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethyl amine, N- (2-hydroxyethyl) bis [2- (methoxy carbonyl ) Ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxy carbonyl) ethyl] amine , N- (2-acetoxyethyl) bis [2- (ethoxy carbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxy carbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxy carbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxy carbonyl) ethyl] amine, N -Butyl bis [2- (methoxy carbonyl) ethyl] amine, N-butyl bis [2- (2-methoxy ethoxy carbonyl) ethyl] amine, N-methyl bis (2-acetoxyethyl) amine, N-ethyl bis (2-acetoxyethyl) amine, N-methyl bis (2-pivaloyloxyethyl) amine, N-ethyl bis [2- (methoxy carbonyl oxy) ethyl] amine, N-ethyl bis [2- (tert-butoxy carbonyl oxy) ethyl] amine, tris (methoxy carbonyl methyl) amine, tris (ethoxy carbonyl methyl) amine, N-butylbis (methoxy carbonyl methyl) a Min, N-hexyl bis (methoxy carbonyl methyl) amine, (beta)-(diethyl amino) -delta-valerolactone, etc. can be illustrated.
    [245] Moreover, 1 type, or 2 or more types chosen from the basic compound which has a cyclic structure represented by following formula (18) can also be mix | blended.
    [246]
    [247] In formula, X is the same as the above, R <307> is a C2-C20 linear, branched alkylene group, and may contain one or more carbonyl group, ether structure, ester structure, or sulfide structure.
    [248] Specific examples of the basic compound having a cyclic structure represented by the formula (18) include 1- [2- (methoxy methoxy) ethyl] pyrrolidine, 1- [2- (methoxy methoxy) ethyl] piperidine, 4- [2- (methoxy methoxy) ethyl] morpholine, 1- [2-[(2-methoxy ethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxy Ethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxy ethoxy) methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl, 2-piacetic acid Ferridino ethyl, 2-morpholino ethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidino ethyl propionic acid, 2-morpholino ethyl, methoxyacetic acid 2- (1- Pyrrolidinyl) ethyl, 4- [2- (methoxy carbonyl oxy) ethyl] morpholine, 1- [2- (t-butoxy carbonyl oxy) ethyl] piperidine, 4- [2- (2 -Methoxy ethoxy carbonyl oxy) ethyl] morpholine, 3- (1-pyrrolidinyl) methyl propionate, 3-piperidino propionic acid Methyl 3-morpholino propionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholino propionate, 3-piperidino propionic acid Methoxycarbonyl methyl, 3- (1-pyrrolidinyl) propionic acid 2-hydroxyethyl, 3-morpholino propionic acid 2-acetoxyethyl, 3- (1-pyrrolidinyl) propionic acid 2-oxo tetrahydrofuran 3-yl, 3-morpholino propionic acid tetrahydrofurfuryl, 3-piperidino propionic acid glycidyl, 3-morpholino propionic acid 2-methoxyethyl, 3- (1-pyrrolidinyl) propionic acid 2- (2-methoxy ethoxy) ethyl, 3-morpholino propionate butyl, 3-piperidino propionate cyclohexyl, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino- γ-butylolactone, β-morpholino-δ-barellolactone, 1-pyrrolidinyl methyl acetate, piperidino methyl acetate, morpholino Acid can be exemplified such as methyl, ethyl thio-morpholino-methyl, 1-pyrrolidinyl ethyl, morpholino ethyl 2-methoxyethyl.
    [249] Moreover, 1 type, or 2 or more types chosen from the basic compound which has a cyano group represented by following formula (19-22) can also be mix | blended.
    [250]
    [251]
    [252]
    [253]
    [254] In the formula, X, R 307 and n are the same as above, and R 308 and R 309 are each independently a linear or branched alkylene group having 1 to 4 carbon atoms.
    [255] Specific examples of the basic compound having a cyano group represented by Formulas 19 to 22 include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-amino propiononitrile, and N , N-bis (2-acetoxyethyl) -3-amino propiononitrile, N, N-bis (2-formyl oxyethyl) -3-amino propiononitrile, N, N-bis (2-methoxy Ethyl) -3-amino propiononitrile, N, N-bis [2- (methoxy methoxy) ethyl] -3-amino propiononitrile, N- (2-cyanoethyl) -N- (2-meth Methyl oxyethyl) -3-amino propionate, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-amino methyl propionate, N- (2-acetoxyethyl) -N- (2 -Cyanoethyl) -3-amino propionate methyl, N- (2-cyanoethyl) -N-ethyl-3-amino propiononitrile, N- (2-cyanoethyl) -N- (2-hydroxy Ethyl) -3-amino propiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminoprop Piononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-amino propiononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl ) -3-amino propiononitrile, N- (2-cyanoethyl) -N- [2- (methoxy methoxy) ethyl] -3-amino propiononitrile, N- (2-cyanoethyl)- N- (3-hydroxy-1-propyl) -3-amino propiononitrile, N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-amino propiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-amino propiononitrile, N- (2-cyanoethyl) -N-tetra hydrofurfuryl-3- Amino propiononitrile, N, N-bis (2-cyanoethyl) -3-amino propiononitrile, diethylamino acetonitrile, N, N-bis (2-hydroxyethyl) amino acetonitrile, N, N -Bis (2-acetoxyethyl) amino acetonitrile, N, N-bis (2-formyl oxyethyl) amino acetonitrile, N, N-bis (2-methoxyethyl) amino Cetonitrile, N, N-bis [2- (methoxy methoxy) ethyl] amino acetonitrile, N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate methyl, N-cyanomethyl -N- (2-hydroxyethyl) -3-aminopropionate methyl, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, N-cyanomethyl-N- (2- Hydroxyethyl) amino acetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) amino acetonitrile, N-cyanomethyl-N- (2-formyl oxyethyl) amino acetonitrile, N -Cyanomethyl-N- (2-methoxyethyl) amino acetonitrile, N-cyanomethyl-N- [2- (methoxy methoxy) ethyl] amino acetonitrile, N- (cyanomethyl) -N -(3-hydroxy-1-propyl) amino acetonitrile, N- (3-acetoxy-1-propyl) -N- (cyanomethyl) amino acetonitrile, N-cyanomethyl-N- (3- Formyl oxy-1-propyl) amino acetonitrile, N, N-bis (cyanomethyl) amino acetonitrile, 1-pi Lidine Propiononitrile, 1-piperidine propiononitrile, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile, 3-diethyl amino Cyanomethyl propionate, N, N-bis (2-hydroxyethyl) -3-aminocyanomethyl propionate, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N -Bis (2-formyl oxyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis (2-methoxyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (meth Methoxy methoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethyl aminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-sia Noethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyl oxyethyl) -3-aminopropionic acid (2- Cyanoethyl), N, N-bis (methok Ethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxy methoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), 1-pyrrolidine propionic acid Cyanomethyl, 1-piperidine propionate cyanomethyl, 4-morpholine propionic acid cyanomethyl, 1-pyrrolidine propionic acid (2-cyanoethyl), 1-piperidine propionic acid (2-cyanoethyl) And 4-morpholine propionic acid (2-cyanoethyl).
    [256] The compounding quantity of the said basic compound is 0.001-10 parts with respect to 1 part of acid generators, Preferably it is 0.01-1 part. When the compounding quantity is less than 0.001 part, the effect as an additive may not fully be acquired, and when it exceeds 10 parts, resolution and a sensitivity may fall.
    [257] Moreover, the compound which has group represented by -C-COOH in a molecule | numerator can be mix | blended with the resist material of this invention.
    [258] As a compound which has group represented by -C-COOH in a molecule | numerator, 1 type (s) or 2 or more types of compounds chosen from the following group I and II can be used, for example, It is not limited to these. By combining this component, the PED stability of the resist is improved and the edge roughness on the nitride film substrate is improved.
    [259] [Group I]
    [260] Some or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by the formulas (A1) to (A10) are substituted by -R 401 -COOH (R 401 is a linear or branched alkylene group having 1 to 10 carbon atoms). And a molar ratio of the phenolic hydroxyl group (C) in the molecule and the group (D) represented by ≡C-COOH is C / (C + D) = 0.1 to 1.0.
    [261] [Group II]
    [262] The compounds represented by the following formulas (A11) to (A15).
    [263]
    [264] (Wherein, R 408 represents a hydrogen atom or a methyl group, R 402 , R 403 represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, respectively, and R 404 represents a hydrogen atom or 1 carbon atom) Straight or branched alkyl group or alkenyl group of 8 to 8 or-(R 409 ) h -COOR 'group (R' represents a hydrogen atom or -R 409 -COOH), R 405 represents-(CH 2 ) i -(i = 2 to 10), an allylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R 406 represents an alkylene group having 1 to 10 carbon atoms, an allylene group having 6 to 10 carbon atoms and a carbonyl group , A sulfonyl group, an oxygen atom or a sulfur atom, R 407 represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group substituted with a hydroxyl group, respectively, and R 409 represents carbon number 1-10 linear or branched alkyl Represents a group, R 410 represents a hydrogen atom or a C 1 -C 8 linear or branched alkyl group or an alkenyl group, or a -R 411 -COOH of a terrestrial, R 411 is C 1 -C 10 straight or branched alkylene group of J is an integer from 0 to 5, u, h is 0 or 1, and s1, t1, s2, t2, s3, t3, s4, t4 are s1 + t1 = 8, s2 + t2 = 5, s3, respectively. satisfies + t3 = 4 and s4 + t4 = 6, and has at least one hydroxyl group in each phenyl skeleton, κ is a number having a weight average molecular weight of 1, OOO to 5, OOO of a compound of Formula (A6) is the number of the compound of general formula (A7) having a weight average molecular weight of 1, OOO to 10, OOO.)
    [265]
    [266] (Wherein, R 402 , R 403 , R 411 represent the same meaning as described above, R 412 represents a hydrogen atom or a hydroxyl group, s5, t5 is s5 ≧ O, t5 ≧ O, and s5 + t5 = 5) Is a satisfying number, and h 'is O or 1).
    [267] Although the compound specifically, shown by following formula (AI-1-14) and AII-1-10 is mentioned as this component, It is not limited to these.
    [268]
    [269] (Wherein R ″ represents a hydrogen atom or a CH 2 COOH group, and in each compound, 10 to 100 mol% of R ″ is a CH 2 COOH group, and α and κ represent the same meanings as above).
    [270]
    [271] In addition, the compound which has group represented by -C-COOH in the said molecule can be used individually by 1 type or in combination of 2 or more types.
    [272] The amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 3 parts, further preferably 100 parts of the base resin. Preferably from 0.1 to 2 parts. When more than 5 parts, the resolution of a resist material may fall.
    [273] Moreover, an acetylene alcohol derivative can be mix | blended with the resist material of this invention as an additive, and, thereby, storage stability can be improved.
    [274] As an acetylene alcohol derivative, what is represented by following General formula (S1), (S2) can be used suitably.
    [275]
    [276] (Wherein, R 501 , R 502 , R 503 , R 504 and R 505 each represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, X, Y represents 0 or an integer, The following values O≤X≤30, O≤Y≤30, and O≤X + Y≤40 are satisfied.)
    [277] As the acetylene alcohol derivative, preferably, quinolin 61, surfinol 82, surfinol 104, surfinol 104E, surfinol 104H, surfinol 104A, surfinol TG, surfinol PC, surfinol 440, surfinol 465, surfinol And 485 (manufactured by Air Products and Chemicals Inc.) and Sufinol E1004 (manufactured by Nisshin Chemical Co., Ltd.).
    [278] The amount of the acetylene alcohol derivative added is 0.01 to 2% by weight, more preferably 0.02 to 1% by weight in 100% by weight of the resist composition. When the amount is less than 0.01% by weight, the effect of improving the coatability and the storage stability may not be sufficiently obtained. When the amount is more than 2% by weight, the resolution of the resist material may decrease.
    [279] The resist material of this invention can add the surfactant normally used in order to improve applicability | paintability as an arbitrary component other than the said component. In addition, the addition amount of an arbitrary component can be made into the normal amount in the range which does not prevent the effect of this invention.
    [280] Here, it is preferable that it is nonionic as surfactant, and a perfluoroalkyl polyoxyethylene ethanol, a fluorinated alkylester, a perfluoroalkyl amine oxide, a perfluoroalkyl EO addition product, a fluorine-containing organosiloxane compound, etc. are mentioned. Can be mentioned. For example, Flora "FC-430", "FC-431" (all of which are manufactured by Sumitomo 3M Co., Ltd.), Spron "S-141", "S-145", "KH-10", "KH-" 20 '', `` KH-30 '', `` KH-40 '' (all manufactured by Asahi Glass Co., Ltd.), Udonin `` DS-401 '', `` DS-403 '', `` DS-451 '' (all Daikin Industries Co., Ltd. Co., Ltd.), mega pack `` F-8151 '' (made by Dainippon Ink Industries Co., Ltd.), `` X-70-092 '', `` X-70-093 '' (all made by Shin-Etsu Chemical Co., Ltd.) Can be mentioned. Preferably, flora also "FC-430" (made by Sumitomo 3M), "KH-20", "KH-30" (all are manufactured by Asahi Glass Co., Ltd.), "X-70-093" (Shin-Etsu Chemical Co., Ltd. product) is mentioned.
    [281] In the present invention, the following process using the above-mentioned resist material:
    [282] (a) A resist is applied by applying a resist material containing a base resin comprising a hydrogenated substance of a ring-opening metathesis polymer or a mixture of a poly (meth) acrylic acid derivative and a acid generator that generates an acid by radiation exposure on a substrate. A first process of forming a film,
    [283] (b) a second step of prebaking the resist film,
    [284] (c) a third step of subjecting the prebaked resist film to pattern exposure,
    [285] (d) a fourth step of post-exposure baking the resist film exposed to the pattern,
    [286] (e) a fifth step of forming the resist pattern by developing the post-exposure baked resist film; and
    [287] (f) A resist pattern is formed by the 6th process of heat-flowing a resist pattern by post-baking the said resist pattern.
    [288] In this case, the first to fifth steps can be carried out by employing a known lithography technique, and for example, coating is carried out on a substrate such as a silicon wafer so as to have a film thickness of 0.2 to 2.0 탆 by a method such as spin coating. Then, this is prebaked on a hot plate at 60 to 150 캜 for 1 to 10 minutes, preferably at 80 to 130 캜 for 1 to 5 minutes. Then, a mask for forming a desired pattern is covered on the resist film, and high energy rays or electron beams such as far ultraviolet rays, excimer lasers, X-rays or the like are exposed at an exposure dose of about 1 to 200 mJ / cm 2 , preferably 5 to After irradiation to about 100 mJ / cm 2 , post exposure bake (PEB) on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 130 ° C. for 1 to 3 minutes. Again, 0.1 to 3 minutes, preferably 0.5 to 2 minutes, using a developing solution of an aqueous alkali solution such as 0.1% to 5%, preferably 2-3% tetramethylammonium hydroxide (TMAH), The desired pattern is formed on a board | substrate by developing by normal methods, such as the dipping method, the puddle method, and the spray method. In addition, the material of the present invention is particularly suitable for fine patterning by far ultraviolet rays or excimer lasers, X-rays and electron beams of 248 to 193 nm, among high energy rays. Moreover, when the said range is out of an upper limit and a lower limit, a desired pattern may not be obtained.
    [289] After resist pattern formation, it can heat-flow by the following processes. The apparatus is not limited as long as it can be heated such as a hot plate or an oven, and may be either a contact type or a non-contact type. In view of temperature uniformity, it is preferable to use a non-contact hot plate. The heating temperature is preferably in the range of 100 to 220 캜 where the resist heat flows, and particularly preferably in the range of 130 to 180 캜 where the temperature uniformity of the hot plate is easily controlled. If the temperature is lower than 100 ° C, heat flow may not occur. If the temperature is higher than 220 ° C, excessive heat flow may result in remarkable thermal decomposition of the photoacid generator and the polymer. The heating time is preferably in the range of 30 seconds to 10 minutes, and particularly preferably in the range of 45 seconds to 120 seconds from the viewpoint of throughput. As a heating method, the method of single stage heating or two stage heating or more (multistage heating) can be used. One-stage heating is a method of finishing in one heat flow process so as to have a target gksms hole size, and multistage heating is a method of gradually making a desired hole size by repeating the heat flow process.
    [290] <Example>
    [291] Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to a following example.
    [292] [Examples 1 and 2, Comparative Examples 1 and 2]
    [293] After the resist material was combined with the composition shown in Table 1, it filtered with the filter made from Teflon (trademark) of 0.2 micrometer of pore diameters, and it was made into the resist liquid. However, what used the solvent containing 0.15 weight% of KH-20 (made by Asahi Glass Co., Ltd.) which is surfactant. The resist liquid was spin-coated on a silicon wafer coated with ARC19 (manufactured by Sipplay) 82 nm, which is an organic antireflection film, and applied to a thickness of 0.4 탆. Then, the silicon wafer was baked (PB) for 60 seconds at a temperature for obtaining an optimal pattern using a hot plate. This was exposed using an ArF excimer laser stepper (NA = O.55), and baked (PEB) for 60 seconds at a temperature for obtaining an optimum pattern, followed by an aqueous solution of 2.38% of tetramethyl ammonium hydroxide. The development was carried out to obtain a positive pattern.
    [294] Evaluation of the resist material was made about the following items. First, the exposure amount resolving the contact hole diameter of 200 nm of 500 nm pitch was calculated | required, and it was set as the sensitivity (mJ / cm <2> ). Next, it baked for 90 second at 150 degreeC, and measured the dimension of a contact hole diameter using the scanning electron microscope (SEM). The dimension (nm) of the contact hole diameter after baking 150 degreeC is excellent in the one closer to the target dimension (160 nm).
    [295] In addition, the etching process was performed using the oxide film etching conditions (see below) using CHF 3 / CF 4 gas, and the film streaks of the unexposed portions were measured to determine the etching rate. The etching rate of the KrF resist SEPR-430S (manufactured by Shin-Etsu Chemical Co., Ltd.) was set to one. The smaller the etching rate, the better. Moreover, the surface roughness of the resist film after etching was calculated | required using atomic force microscope (AFM), and it was set as Rms (nm). Rms is better at the smaller number.
    [296] The composition and evaluation results of each resist material are shown in Tables 1 and 2. In addition, the structure of used resin is described with the weight average molecular weight (Mw).
    [297] (a)
    [298] (b)
    [299] (c)
    [300] Suzyx / y / zMwMw / MnAcid generatorBasic compoundsolvent Example 1Formula (a) -1 (80)35/19/46140001.5PAG1 (1)TMMEA (0.12)PG / BL (550) Example 2Formula (a) -2 (80)35/15/50140001.5PAG1 (1)TMMEA (0.12)PG / BL (550) Comparative Example 1Formula (b) (80)-70001.8PAG1 (1)TMMEA (0.12)PG / BL (550) Comparative Example 2Formula (c) (80)-120001.5PAG1 (1)TMMEA (0.12)PG / BL (550) PG / BL: A mixed solvent of propylene glycol methyl ether acetate (90 wt%) and γ-butyrolactone (10 wt%) PAG1: triphenylsulfonium nonafluoro butylsulfonateTMMEA: tris (2-methoxymethoxyethyl) In an amine * table | surface, the numerical value in parentheses shows a compounding quantity and is a weight part.
    [301] PB (℃)PEB (℃)Sensitivity (mJ / cm 2 )Dimensions of contact hole diameter after 150 ° C bakingEtching rateRms Example 1100110561620.981.1 Example 2100110581580.981.1 Comparative Example 1130110551991.051.6 Comparative Example 2130130621731.3316.0
    [302] [Examples 3 to 10 and Comparative Examples 3 to 5]
    [303] After the resist material was combined with the composition shown in Table 3, it filtered with the filter made from Teflon (trademark) of 0.2 micrometer of pore diameters, and it was made into the resist liquid. However, what used the solvent containing 0.15 weight% of KH-20 (made by Asahi Glass Co., Ltd.) which is surfactant. The resist liquid was spin-coated on a silicon wafer coated with ARC19 (manufactured by Sipplay) 82 nm, which is an organic antireflection film, and applied to a thickness of 0.4 탆. Then, the silicon wafer was baked (PB) for 60 seconds at a temperature for obtaining an optimal pattern using a hot plate. This was exposed using an ArF excimer laser stepper (NA = O.55), and baked (PEB) for 60 seconds at a temperature for obtaining an optimum pattern, followed by an aqueous solution of 2.38% tetramethyl ammonium hydroxide. The development was carried out to obtain a positive pattern.
    [304] Evaluation of the resist material was made about the following items. First, the exposure amount resolving the contact hole diameter of 200 nm of 500 nm pitch and 1200 nm pitch was calculated | required, and it was set as the sensitivity (mJ / cm <2> ). Next, baking was performed at 145 degreeC for 90 second, the dimension of the contact hole diameter of 500 nm pitch and 1200 nm pitch was measured using the scanning electron microscope (SEM), and the dimension difference was made into the index dependence index. It can be said that the pitch dependence by flow temperature is smaller and the one where the dimension of both pitches after a flow approaches 190 nm, and a smaller dimension difference is favorable.
    [305] Furthermore, the etching process was performed using oxide film etching conditions (see below) using CHF 3 / CF 4 gas, and the film streaks of the unexposed portions were measured to determine the etching rate. The etching rate of the KrF resist SEPR-430S (manufactured by Shin-Etsu Chemical Co., Ltd.) was set to 1. The smaller the etching rate, the better. In addition, the surface roughness of the resist film after etching was calculated | required using atomic force microscope (AFM), and it was set as Rms (nm). Rms is better at the smaller number.
    [306] The composition and evaluation result of each resist material are shown in Tables 3-6. In addition, the structure of used resin is described with the weight average molecular weight (Mw).
    [307] (a)
    [308] (b)
    [309] Resin 1Resin 2Acid generatorBasic compoundsolvent Example 3Formula (a) (64)Formula (b) (16)PAG1 (1)TMMEA (0.12)PG / CyHo (550) Example 4Formula (a) (40)Formula (b) (40)PAG1 (1)TMMEA (0.12)PG / CyHo (550) Comparative Example 3Formula (a) (80)-PAG1 (1)TMMEA (0.12)PG / CyHo (550) Comparative Example 4Formula (b) (80)-PAG1 (1)TMMEA (0.12)PG / CyHo (550) PG / CyHo: Mixture of propylene glycol methyl ether acetate (70 wt%) and cyclohexanone (30 wt%) PAG1: Triphenylsulfonium nonafluorobutyl sulfonateTMMEA: Tris (2-methoxymethoxyethyl) amine * In the table | surfaces, the numerical value in parentheses shows a compounding quantity, and is a weight part.
    [310] PB (℃)PEB (℃)500nm and 1200nm pitch sensitivity (mJ / cm 2 ) (500nm / 1200nm)Dimension / 1200nm pitch / dimension (nm) of 500nm pitch contact hole diameter after 145 degrees Celsius bakingEtching rateRms (nm) Example 310011056/67193/189/41.021.9 Example 410011056/63192/189/31.075.9 Comparative Example 310011056/72190/169/310.981.1 Comparative Example 413013040/45200/200/0 (no flow)1.3316.0
    [311]
    [312]
    [313] Resin 1Resin 2Acid generatorBasic compoundsolvent Example 5Formula (a) (40)Formula (b-2) (40)PAG1 (1)TMMEA (0.12)PG / GBL (550) Example 6Formula (a) (40)Formula (b-3) (40)PAG1 (1)TMMEA (0.12)PG / GBL (550) Example 7Formula (a) (40)Formula (c-2) (40)PAG1 (1)TMMEA (0.12)PG / GBL (550) Example 8Formula (a) (40)Formula (c-3) (40)PAG1 (1)TMMEA (0.12)PG / GBL (550) Example 9Formula (a-2) (40)Formula (b-2) (40)PAG1 (1)TMMEA (0.12)PG / GBL (550) Example 10Formula (a-2) (40)Formula (b-3) (40)PAG1 (1)TMMEA (0.12)PG / GBL (550) Comparative Example 5Formula (c-3) (80) PAG1 (1)TMMEA (0.12)PG / GBL (550) PG / GBL: Mixed solvent of propylene glycol methyl ether acetate (90 wt%) and γ-butylolactone (10 wt%) PAG1: Triphenylsulfonium nonafluorobutyl sulfonateTMMEA: Tris (2-methoxymethoxyethyl) In an amine * table | surface, the numerical value in parentheses shows a compounding quantity and is a weight part.
    [314] PB (℃)PEB (℃)500nm and 1200nm pitch sensitivity (mJ / cm 2 ) (500nm / 1200nm)Dimension / 1200nm pitch / dimension (nm) of 500nm pitch contact hole diameter after 145 degrees Celsius bakingEtching rateRms (nm) Example 513010052/58191/185/60.955.5 Example 613010058/64191/188/30.945.4 Example 713010055/71185/160/250.944.4 Example 813010056/73188/169/190.934.4 Example 913011052/57192/188/40.945.4 Example 1013011058/63193/189/40.945.3 Comparative Example 511011050/60120/71/491.107.2
    [315] According to the present invention, the degree of integration of the semiconductor LSI can be improved, that is, the degree of processing fineness can be improved.
    权利要求:
    Claims (4)
    [1" claim-type="Currently amended] (a) Applying a resist material containing a base resin which is a polymer or copolymer having a structural unit represented by the following formula (5) on the substrate and partially having an acid stabilizer on the side chain on the substrate, and an acid generator which generates an acid by radiation exposure A first step of forming a resist film,
    (b) a second step of prebaking the resist film,
    (c) a third step of subjecting the prebaked resist film to pattern exposure,
    (d) a fourth step of post-exposure baking the resist film exposed to the pattern,
    (e) a fifth step of forming the resist pattern by developing the post-exposure baked resist film, and
    and (f) a sixth step of thermally flowing the resist pattern by post-baking the resist pattern.
    <Formula 5>

    Wherein X 1 , X 2 is selected from -O-, -S-, -NR-, -PR-, or -CR 2- ; R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; m represents O or the integer of 1-3.
    [2" claim-type="Currently amended] The ring-opening metacete according to claim 1, wherein the base resin contains a structural unit [A] represented by the following general formula (1), a structural unit [B] represented by the following general formula (3) and / or a structural unit [C] represented by the following general formula (4). It is a hydrogenated substance of a sheath polymer, The resist pattern formation method characterized by the above-mentioned.
    <Formula 1>

    <Formula 3>

    <Formula 4>

    In the formula, at least one of R 1 to R 4 is a group having an acid labile group represented by the following formula (2), and others of R 1 to R 4 are hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. , A halogen atom, a linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms Alkyl group, C2-C20 linear, branched or cyclic alkyl carbonyl oxy group, C7-C20 aryl carbonyl oxy group, C1-C20 linear, branched or cyclic alkyl sulfonyl oxy group , An aryl sulfonyl oxy group having 6 to 20 carbon atoms, a straight, branched or cyclic alkoxy carbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxy carbonyl alkyl group having 3 to 20 carbon atoms Show; R 8 to R 11 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; R 13 to R 16 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; Y 1 and Y 2 are-(C = O)-on one side and -CR 18 2- (R 18 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms); j, n is O or an integer from 1 to 3; X 1 , X 2 and m represent the same meaning as in claim 1.
    <Formula 2>

    Wherein the dashed line represents the number of bonds; R 5 is a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxy alkyl group having 2 to 10 carbon atoms, or a straight, branched or cyclic ring having 1 to 10 carbon atoms An acyl group of; W 1 represents a single bond or a (k + 2) valent hydrocarbon group having 1 to 10 carbon atoms; R AL represents an acid labile group; k is 0 or 1;
    [3" claim-type="Currently amended] (a) A resist film is formed by applying a resist material containing a base resin, which is a mixture of a hydrogenated ring of a ring-opening metathesis polymer and a poly (meth) acrylic acid derivative, and an acid generator that generates an acid by radiation exposure on a substrate. 1st process,
    (b) a second step of prebaking the resist film,
    (c) a third step of subjecting the prebaked resist film to pattern exposure,
    (d) a fourth step of post-exposure baking the resist film exposed to the pattern,
    (e) a fifth step of developing the resist film subjected to post exposure baking to form a resist pattern, and
    and (f) a sixth step of thermally flowing the resist pattern by post-baking the resist pattern.
    [4" claim-type="Currently amended] The method according to claim 3, wherein the hydrogenated substance of the ring-opening metathesis polymer is a polymer compound having a weight average molecular weight of 500 to 200,000 having a repeating unit represented by the following formula (6).
    <Formula 6>

    In the formula, R 101 represents a hydrogen atom, a methyl group or CH 2 CO 2 R 103 ; R 102 represents a hydrogen atom, a methyl group or CO 2 R 103 ; R 103 represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may be the same or different at R 101 and R 102 ; R 104 represents an acid labile group; R 105 is a halogen atom, a hydroxyl group, a straight, branched or cyclic alkoxy group having 1 to 15 carbon atoms, an acyl oxy or alkyl sulfonyl oxy group, or a straight, branched or cyclic alkoxy carbon having 2 to 15 carbon atoms A carbonyl oxy group or an alkoxy alkoxy group, wherein some or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms; At least one of R 106 to R 109 represents a monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Represent; R 106 and R 107 , R 107 and R 108 , or R 108 and R 109 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case R 106 and R 107 , R 107 and One of R 108 or R 108 and R1 09 represents a divalent hydrocarbon group containing a carboxy group or hydroxyl group having 1 to 15 carbon atoms, and the other is a single bond or a linear, branched or cyclic alkylene having 1 to 15 carbon atoms. Group; At least one of R 110 to R 113 represents a monovalent hydrocarbon group containing at least one substructure selected from ethers, aldehydes, ketones, esters, carbonates, acid anhydrides, amides, imides having 2 to 15 carbon atoms, The remainder each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and R 110 and R 111 , R 111 and R 112 , or R 112 and R 113 are each bonded to each other; A ring may be formed together with the carbon atom to be bonded, in which case one of R 110 and R 111 , R 111 and R 112 , or one of R 112 and R 113 is an ether, aldehyde, ketone, ester, having 1 to 15 carbon atoms, A divalent hydrocarbon group containing at least one substructure selected from carbonates, acid anhydrides, amides, and imides, the other being a single bond or a straight, branched or cyclic ring having 1 to 15 carbon atoms. It represents an alkylene group; X 11 to X 13 each independently represent a methylene group or an oxygen atom, but not all of X 11 to X 13 can be a methylene group at the same time; W represents a single bond or a linear, branched or cyclic (t + 2) valent hydrocarbon group having 1 to 5 carbon atoms, and in the case of a hydrocarbon group, one or more methylene groups are substituted with an oxygen atom to form a chain or cyclic ether. Two hydrogen atoms on the same carbon may be substituted with an oxygen atom to form a ketone; k 1 to k 3 are each independently O or 1; t is 0, 1 or 2; a, b, c represent the composition ratio of each repeating unit, a is more than 0 and less than 1, b, c is 0 or more and less than 1, and satisfies a + b + c = 1, a, b, c A plurality of repeating units introduced at each composition ratio of may be present.
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    同族专利:
    公开号 | 公开日
    US20030108819A1|2003-06-12|
    US6878508B2|2005-04-12|
    TWI282036B|2007-06-01|
    KR100636067B1|2006-10-20|
    EP1276012B1|2016-03-23|
    EP1276012A3|2003-03-19|
    EP1276012A2|2003-01-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-07-13|Priority to JP2001213015
    2001-07-13|Priority to JPJP-P-2001-00213015
    2001-09-27|Priority to JPJP-P-2001-00295653
    2001-09-27|Priority to JP2001295653
    2002-02-22|Priority to JP2002045588
    2002-02-22|Priority to JPJP-P-2002-00045588
    2002-07-12|Application filed by 신에쓰 가가꾸 고교 가부시끼가이샤
    2003-04-26|Publication of KR20030032825A
    2006-10-20|Application granted
    2006-10-20|Publication of KR100636067B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2001213015|2001-07-13|
    JPJP-P-2001-00213015|2001-07-13|
    JPJP-P-2001-00295653|2001-09-27|
    JP2001295653|2001-09-27|
    JP2002045588|2002-02-22|
    JPJP-P-2002-00045588|2002-02-22|
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