JP5741518B2 - Resist underlayer film material and pattern forming method - Google Patents

Description

The present invention relates to an antireflection film material used for microfabrication in a manufacturing process of a semiconductor element or the like and a resist underlayer film material effective as a hard mask, and in particular, far ultraviolet light, KrF excimer laser light (248 nm), ArF excimer laser light ( 193 nm), F ₂ laser beam (157 nm), Kr ₂ laser beam (146 nm), Ar ₂ laser beam (126 nm), soft X-ray (EUV, 13.5 nm), suitable for exposure with electron beam (EB), etc. The present invention relates to a resist underlayer film material of a multilayer resist film. Furthermore, the present invention relates to a method for forming a pattern on a substrate by lithography using the same.

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

  As a light source for lithography used in forming a resist pattern, immersion lithography using an ArF excimer laser is widely used, and double patterning for doubling the resolution of the pattern is being applied.

  On the other hand, conventionally, it is known that a multilayer film method is excellent for forming a pattern with a high aspect ratio on a stepped substrate, in particular, a carbon film on a substrate to be processed, and a silicon-containing intermediate film thereon. A three-layer resist film in which a photoresist film is laminated thereon is widely used.

  Since the carbon film serves as a mask for processing the substrate to be processed, it is required to have excellent etching resistance. Examples of the carbon film include amorphous carbon produced by a CVD method and a spin-on carbon film produced by a spin coating method. An amorphous carbon film has a high carbon density and excellent etching resistance, but has the disadvantages that it is difficult to increase the cost by introducing a CVD apparatus and to flatten the stepped substrate. The spin-on carbon film is slightly inferior in etching resistance but has a low process cost and has an advantage of excellent planarization.

  When the substrate to be processed is a silicon oxide film, the substrate to be processed is etched by dry etching using a fluorocarbon-based gas, and the volume of the film expands due to the fluorination of the carbon film during this etching, resulting in a line pattern. Problems with bending. In particular, when a spin-on carbon film having low etching resistance is applied, the phenomenon that the pattern is changed is remarkable, and there is a demand for the development of a lower layer film that does not cause the pattern during etching.

  As the miniaturization of semiconductors becomes increasingly difficult, devices having a three-dimensional structure that can increase the memory capacity by increasing the number of stacked layers are being studied. In the stacked NAND flash memory BiCS proposed by Toshiba, plate-shaped electrodes are stacked and connected by gate electrodes filled with through holes.

Since the hole pattern for BiCS is a gate electrode, variation in the hole size leads to variation in the response speed of the device, so the variation must be kept small. In addition, it is necessary to form deep holes that penetrate a large number of laminated films. In order to form a deep hole, a hard mask having excellent etching resistance is required. Inorganic hard masks such as Si, TiN, SiC, SiN, and C are excellent in etching resistance, but the cost is high because a dedicated apparatus is required to form them by CVD or sputtering. What can be formed at low cost is a hard mask that can be formed by spin coating and baking. Currently, a spin hard coatable carbon hard mask is used as the lower layer of the tri-layer process. However, this is insufficient in etching resistance for processing many laminated films by dry etching. It is desired to develop a hard mask material that has very high etching resistance and can be spin-coated.
The prior art related to the present invention is not particularly found.

  The present invention has been made in view of such problems, for example, for a multilayer resist process such as an intermediate film containing silicon under a resist film and a lower layer film having excellent etching resistance with fluorocarbon gas under the resist film, Is a resist underlayer film material for a three-layer resist process, and is an underlayer film material that is particularly excellent in etching resistance and functions as an antireflection film excellent for short-wavelength exposure. It is an object to provide a method of forming a film.

（式中、Ｒ¹、Ｘ、Ｍは前述の通り。Ｒ³、Ｒ⁸は水素原子又はメチル基である。Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷は置換又は非置換のヒドロキシ基又はカルボキシル基、−ＣＲ¹⁰Ｒ¹¹ＯＨ、又は−Ｏ−Ｒ¹²である。Ｒ¹⁰、Ｒ¹¹は水素原子、又は炭素数１〜４の直鎖状又は分岐状のアルキル基である。Ｒ⁹、Ｒ¹²は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基又はアシル基、又はオキシラン又はオキセタンを含有する炭素数３〜１２のアルキル基である。Ｙ¹は単結合、−Ｃ（＝Ｏ）−Ｏ−Ｒ¹³−、−Ｃ（＝Ｏ）−ＮＨ−Ｒ¹³−、又は−Ｏ−であり、Ｙ²は−Ｃ（＝Ｏ）−Ｏ−Ｒ¹⁴−、又は−Ｃ（＝Ｏ）−ＮＨ−Ｒ¹⁴−であり、Ｒ¹³、Ｒ¹⁴は単結合、炭素数１〜１２の直鎖状、分岐状又は環状のアルキレン基、炭素数６〜１０のアリーレン基、又は炭素数２〜１２のアルケニレン基である。Ｚはメチレン基、酸素原子、硫黄原子、又は−ＮＨ−である。ｍ、ｎ、ｐは１又は２、ｑは０、１又は２である。ａ、ｂ、ｃ、ｄ、ｅ、ｆは、それぞれ０＜ａ＜１．０、０≦ｂ≦０．９５、０≦ｃ≦０．９５、０≦ｄ≦０．９５、０≦ｅ≦０．９５、０≦ｆ≦０．９５、０＜ｂ＋ｃ＋ｄ＋ｅ＋ｆ＜１．０の範囲である。）
〔２〕
前記レジスト下層膜材料が、更に有機溶剤、酸発生剤、架橋剤のうちいずれか１つ以上を含有するものであることを特徴とする〔１〕に記載のレジスト下層膜材料。
〔３〕
〔１〕又は〔２〕に記載のレジスト下層膜形成材料を被加工基板上に適用し、得られた下層膜の上にレジスト組成物の層を適用し、このレジスト層の所用領域に放射線を照射し、現像液で現像してレジストパターンを形成し、次にドライエッチング装置でこのレジストパターン層をマスクにしてレジスト下層膜層及び被加工基板を加工することを特徴とするパターン形成方法。
〔４〕
〔１〕又は〔２〕に記載のレジスト下層膜形成材料を被加工基板上に適用し、得られた下層膜の上に珪素原子、チタン原子、ジルコニウム原子、ハフニウム原子、アルミニウム原子から選ばれる原子を１種以上含有する中間層を適用し、該中間層の上にレジスト組成物の層を適用し、このレジスト層の所用領域に放射線を照射し、現像液で現像してレジストパターンを形成し、ドライエッチング装置でこのレジストパターン層をマスクにして中間膜層を加工し、レジストパターン層を除去後、上記加工した中間膜層をマスクにして下層膜層、次いで被加工基板を加工することを特徴とする〔３〕に記載のパターン形成方法。
〔５〕
レジスト組成物が珪素原子を含有しないポリマーを含み、中間層膜をマスクにして下層膜を加工するドライエッチングを、一酸化炭素ガス、二酸化炭素ガス、水素ガス、酸素ガス、窒素ガス、塩素ガス、臭素ガス、塩化水素ガス、臭化水素ガス、二酸化硫黄ガス、二硫化炭素ガスから選ばれるエッチングガスを用いて行うことを特徴とする〔４〕に記載のパターン形成方法。 The present invention has been made to solve the above problems, and the present invention provides the following resist underlayer film material and pattern forming method.
[ 1 ]
A resist underlayer film material for a multilayer resist film used in lithography, comprising a repeating unit containing a cyclopentadienyl complex represented by the following general formula (1) and a substitution represented by the following general formula (2): unsubstituted hydroxy group or carboxyl group, oxirane, features and, Relais resist underlayer film material that comprises a polymer comprising recurring units of the crosslinkable selected from oxetane.

(In the formula, R ¹ , X and M are as described above. R ³ and R ⁸ are hydrogen atoms or methyl groups. R ⁴ , R ⁵ , R ⁶ and R ⁷ are substituted or unsubstituted hydroxy groups or carboxyls. A group, —CR ¹⁰ R ¹¹ OH, or —O—R ¹² , wherein R ¹⁰ and R ¹¹ are a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁹ , R; ¹² is a linear, branched or cyclic alkyl group or acyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 12 carbon atoms containing oxirane or oxetane, Y ¹ is a single bond, —C ( ═O) —O—R ¹³ —, —C (═O) —NH—R ¹³ —, or —O—, and Y ² represents —C (═O) —O—R ¹⁴ —, or —C ( ═O) —NH—R ¹⁴ —, wherein R ¹³ and R ¹⁴ are a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, and an arylene having 6 to 10 carbon atoms. Or an alkenylene group having 2 to 12 carbon atoms, Z is a methylene group, oxygen atom, sulfur atom, or -NH-, m, n, p is 1 or 2, q is 0, 1 or 2. A, b, c, d, e, and f are 0 <a <1.0, 0 ≦ b ≦ 0.95, 0 ≦ c ≦ 0.95, 0 ≦ d ≦ 0.95, and 0 ≦, respectively. (e ≦ 0.95, 0 ≦ f ≦ 0.95, 0 <b + c + d + e + f <1.0.)
[ 2 ]
The resist underlayer film material according to [1 ], wherein the resist underlayer film material further contains at least one of an organic solvent, an acid generator, and a crosslinking agent.
[ 3 ]
The resist underlayer film forming material according to [1] or [2] is applied on a substrate to be processed, a layer of a resist composition is applied on the obtained underlayer film, and radiation is applied to a desired region of the resist layer. Irradiating, developing with a developing solution to form a resist pattern, and then processing the resist underlayer film layer and the substrate to be processed using the resist pattern layer as a mask in a dry etching apparatus.
[ 4 ]
Applying the resist underlayer film forming material according to [1] or [2] on a substrate to be processed, an atom selected from a silicon atom, a titanium atom, a zirconium atom, a hafnium atom, and an aluminum atom on the obtained underlayer film An intermediate layer containing one or more of the above is applied, a layer of a resist composition is applied on the intermediate layer, a desired region of the resist layer is irradiated with radiation, and developed with a developer to form a resist pattern. The intermediate film layer is processed using the resist pattern layer as a mask in a dry etching apparatus, and after removing the resist pattern layer, the lower film layer and then the substrate to be processed are processed using the processed intermediate film layer as a mask. The pattern forming method as described in [ 3 ], which is characterized by the following.
[ 5 ]
The resist composition includes a polymer containing no silicon atom, and dry etching for processing the lower layer film using the intermediate layer film as a mask is performed by carbon monoxide gas, carbon dioxide gas, hydrogen gas, oxygen gas, nitrogen gas, chlorine gas, [ 4 ] The pattern forming method according to [ 4 ], which is performed using an etching gas selected from bromine gas, hydrogen chloride gas, hydrogen bromide gas, sulfur dioxide gas, and carbon disulfide gas.

  According to the present invention, it is an underlayer film material for a multi-layer resist process, particularly for a three-layer resist process, and functions as an excellent antireflection film particularly for exposure at a short wavelength, that is, polyhydroxystyrene, cresol It is possible to obtain a resist underlayer film material that is extremely superior in etching resistance in substrate processing than novolak, naphthol novolak, and the like.

It is explanatory drawing of a 3 layer resist processing process.

Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to these.
As a result of intensive studies to achieve the above object, the present inventors have found that a polymer containing a cyclopentadienyl complex has excellent etching resistance and a multilayer resist such as a three-layer resist process using a silicon-containing intermediate layer. The inventors have found that this is a promising material as a resist underlayer film for a process, and have made the present invention.

  The resist underlayer film formed from the resist underlayer film material of the present invention is a novel resist underlayer film applicable to a multilayer resist process such as a three-layer resist process having a silicon-containing intermediate layer. In particular, it is excellent in antireflection effect in exposure at a short wavelength such as 193 nm and extremely excellent in etching resistance under substrate etching conditions.

  Further, by adding any one or more of an organic solvent, a crosslinking agent, and an acid generator to the resist underlayer film material, it is possible to improve the coating property of the material on a substrate or the like. The crosslinking reaction in the resist underlayer film can be promoted by baking or the like after coating. Therefore, such a resist underlayer film has good film thickness uniformity, is less likely to be intermixed with the resist upper layer film, and has low diffusion of low molecular components into the resist upper layer film.

（式中、Ｒ¹は水素原子又はメチル基、Ｘは単結合、メチレン基、−Ｃ（＝Ｏ）−Ｏ−Ｒ²−、−Ｏ−Ｒ²−、−Ｏ−Ｃ（＝Ｏ）−Ｒ²−、又は−Ａｒ−Ｒ²−であり、Ａｒはフェニレン基又はナフチレン基であり、Ｒ²は同一又は異種の単結合、炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基、炭素数６〜１０のアリーレン基、又は炭素数２〜１０のアルケニレン基であり、エステル基又はエーテル基を有していてもよい。ＭはＦｅ、Ｃｏ、Ｎｉ、Ｃｒ又はＲｕである。） That is, the resist underlayer film material of the present invention is a resist underlayer film material of a multilayer resist film used in lithography, and is an olefin polymer containing at least a cyclopentadienyl complex represented by the following general formula (1). An underlayer film is provided.

(Wherein, R ¹ represents a hydrogen atom or a methyl group, X is a single bond, a methylene group, -C (= O) -O- R 2 -, - O-R 2 -, - O-C (= O) - R ² — or —Ar—R ² —, Ar is a phenylene group or a naphthylene group, R ² is the same or different single bond, a linear, branched or cyclic alkylene having 1 to 6 carbon atoms. Group, an arylene group having 6 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms, and may have an ester group or an ether group, and M is Fe, Co, Ni, Cr, or Ru. )

  Here, examples of the metal M of the olefin polymer containing the cyclopentadienyl complex represented by the general formula (1) include Fe, Co, Ni, Cr, and Ru. Among these metals, Fe and Ru can be most preferably used. Other metal vinylcyclopentadienyl metallocenes are unstable in the atmosphere and must be handled in nitrogen or in an inert gas. When the metal M is Fe, the name is ferrocene, and when the metal M is Ru, the name is ruthenocene. In both cases, the complex has 18 valence electrons and exists stably. On the other hand, when the metal M is Co, it is easily oxidized, and Ni, Mn, Cr, and V are unstable in the atmosphere.

（式中、Ｒ¹、Ｘ、Ｍは前述の通り。Ｒ³、Ｒ⁸は水素原子又はメチル基である。Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷は置換又は非置換のヒドロキシ基又はカルボキシル基、−ＣＲ¹⁰Ｒ¹¹ＯＨ、又は−Ｏ−Ｒ¹²である。Ｒ¹⁰、Ｒ¹¹は水素原子、又は炭素数１〜４の直鎖状又は分岐状のアルキル基である。Ｒ⁹、Ｒ¹²は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基又はアシル基、又はオキシラン又はオキセタンを含有する炭素数３〜１２のアルキル基である。Ｙ¹は単結合、−Ｃ（＝Ｏ）−Ｏ−Ｒ¹³−、−Ｃ（＝Ｏ）−ＮＨ−Ｒ¹³−、又は−Ｏ−であり、Ｙ²は−Ｃ（＝Ｏ）−Ｏ−Ｒ¹⁴−、又は−Ｃ（＝Ｏ）−ＮＨ−Ｒ¹⁴−であり、Ｒ¹³、Ｒ¹⁴は単結合、炭素数１〜１２の直鎖状、分岐状又は環状のアルキレン基、炭素数６〜１０のアリーレン基、又は炭素数２〜１２のアルケニレン基である。Ｚはメチレン基、酸素原子、硫黄原子、又は−ＮＨ−である。ｍ、ｎ、ｐは１又は２、ｑは０、１又は２である。） The crosslinkable repeating unit copolymerized with the repeating unit a containing a cyclopentadienyl complex can be represented by b to f in the following general formula (2). By copolymerizing the crosslinkable repeating units, a strong film is formed by spin coating and baking, and it becomes possible to prevent mixing when spin-coating with the silicon-containing intermediate layer film material thereon.

(In the formula, R ¹ , X and M are as described above. R ³ and R ⁸ are hydrogen atoms or methyl groups. R ⁴ , R ⁵ , R ⁶ and R ⁷ are substituted or unsubstituted hydroxy groups or carboxyls. A group, —CR ¹⁰ R ¹¹ OH, or —O—R ¹² , wherein R ¹⁰ and R ¹¹ are a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁹ , R; ¹² is a linear, branched or cyclic alkyl group or acyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 12 carbon atoms containing oxirane or oxetane, Y ¹ is a single bond, —C ( ═O) —O—R ¹³ —, —C (═O) —NH—R ¹³ —, or —O—, and Y ² represents —C (═O) —O—R ¹⁴ —, or —C ( ═O) —NH—R ¹⁴ —, wherein R ¹³ and R ¹⁴ are a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, and an arylene having 6 to 10 carbon atoms. Or an alkenylene group having 2 to 12 carbon atoms, Z is a methylene group, oxygen atom, sulfur atom, or -NH-, m, n, p is 1 or 2, q is 0, 1 or 2. is there.)

  In the above formulas (1) and (2), the repeating unit a alone can constitute an olefin polymer without copolymerizing with other repeating units. In this case, a = 1.0. Thus, it is preferable to copolymerize with any one or more of the repeating units b to f, and a to f in the case of copolymerizing the repeating unit a and one or more of the repeating units b to f in this way. The values of 0 <a <1.0, 0 ≦ b ≦ 0.95, 0 ≦ c ≦ 0.95, 0 ≦ d ≦ 0.95, 0 ≦ e ≦ 0.95, 0 ≦ f ≦ 0 .95, preferably 0 <b + c + d + e + f <1.0.

Specific examples of the monomer for obtaining the repeating unit a of olefin containing a cyclopentadienyl complex can be given below.

The monomer for obtaining the repeating unit b can be specifically exemplified below.

Specific examples of the monomer for obtaining the repeating unit c include the following.

Specific examples of the monomer for obtaining the repeating unit d can be given below.

The monomer for obtaining the repeating unit e can be specifically exemplified below.

The monomer for obtaining the repeating unit f can be specifically exemplified below.

  Here, a to f are as described above, but 0 <a ≦ 1.0, preferably 0 <a <1.0, 0 ≦ b ≦ 0.95, 0 ≦ c ≦ 0.95, 0 ≦ d ≦ 0.95, 0 ≦ e ≦ 0.95, 0 ≦ f ≦ 0.95, 0 ≦ b + c + d + e + f <1.0, more preferably 0.1 ≦ a ≦ 0.9, 0 ≦ b ≦ 0 0.7, 0 ≦ c ≦ 0.7, 0 ≦ d ≦ 0.7, 0 ≦ e ≦ 0.7, 0 ≦ f ≦ 0.9, 0.1 ≦ b + c + d + e + f ≦ 0.9, more preferably 0. 15 ≦ a ≦ 0.8, 0 ≦ b ≦ 0.6, 0 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 0.6, 0 ≦ f ≦ 0.8, 0. 2 ≦ b + c + d + e + f ≦ 0.85.

  As a copolymerization monomer other than a to f, a monomer g that improves the proportion of carbon can be copolymerized. Specific examples of the monomer g include styrene, vinyl naphthalene, indene, acenaphthylene, vinyl anthracene, vinyl pyrene, and vinyl carbazole. The copolymerization ratio of the repeating unit g is 0 or more and 0.6 or less with respect to the entire repeating unit.

  It is preferable that a + b + c + d + e + f + g = 1. However, a + b + c + d + e + f + g = 1 means that in the polymer compound (copolymer) containing the repeating units a, b, c, d, e, f, g, the repeating units a, b , C, d, e, f, and g are 100 mol% with respect to the total amount of all repeating units.

  When the hydrogen atom of the hydroxy group for obtaining the repeating units b to d represented by the general formula (2) is polymerized, an acetyl group, a formyl group, a pivaloyl group, an acetal group, a tertiary alkyl group having 4 to 16 carbon atoms, It may be substituted with a trimethylsilyl group or the like.

In order to synthesize a copolymer contained in the resist underlayer film material of the present invention, one method is to combine a cyclopentadienyl complex having a polymerizable olefin and another olefin monomer in an organic solvent, a radical polymerization initiator or Heat polymerization is carried out by adding a cationic polymerization initiator. As described in JP-A-7-309915, vinyl ferrocene can be polymerized by adding an initiator and heating. The hydroxy group of the monomer containing a hydroxy group can be substituted with an acetyl group, and the resulting polymer compound can be subjected to alkaline hydrolysis in an organic solvent to deprotect the acetyl group. Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropio). Nate), benzoyl peroxide, lauroyl peroxide, and the like, preferably polymerized by heating to 50 to 80 ° C. Examples of the cationic polymerization initiator include sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, hypochlorous acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, tosylic acid and the like, BF ₃ , AlCl _3, TiCl _4, SnCl ₄ Friedel-Crafts addition of a catalyst such _{as, I 2, (C 6 H} 5) 3 substance which easily generates a cation as CCl are used.

  The reaction time is 2 to 100 hours, preferably 5 to 20 hours. Ammonia water, triethylamine, etc. can be used as the base during the alkali hydrolysis. The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

  The polystyrene-converted weight average molecular weight of the copolymer according to the present invention by gel permeation chromatography (GPC) is preferably in the range of 1,500 to 200,000, more preferably in the range of 2,000 to 100,000. . The molecular weight distribution is not particularly limited, and low molecular weight and high molecular weight substances can be removed by fractionation to reduce the degree of dispersion. The weight of two or more general formulas (1) having different molecular weights and degrees of dispersion can be reduced. Mixtures of blends or two or more polymers of the general formula (1) having different composition ratios may be mixed.

  In order to further improve the transparency at a wavelength of 193 nm of the copolymer contained in the resist underlayer film material of the present invention, particularly the copolymer having the repeating unit a represented by the general formula (1), hydrogenation is performed. Can do. A preferable hydrogenation ratio is 80 mol% or less, more preferably 60 mol% or less of the aromatic group.

  The base resin for the resist underlayer film material of the present invention is characterized by containing a repeating unit of a cyclopentadienyl complex having a polymerizable olefin, and the conventional polymer cited as the antireflection film material described above. It can also be blended. A polymer that lowers the glass transition point can be blended to improve the embedding property (see, for example, JP 2000-294504 A). Polymers having a low glass transition point, especially polymers having a glass transition point of 180 ° C. or lower, particularly 100 to 170 ° C., such as acrylic derivatives, vinyl alcohol, vinyl ethers, allyl ethers, styrene derivatives, allylbenzene derivatives, ethylene, propylene, butadiene Blends with one or more copolymer selected from olefins such as, polymers by metathesis ring-opening polymerization, novolak resins, dicyclopentadiene resins, phenolic low nuclei, calixarenes, fullerenes As a result, the glass transition point can be lowered, and the via hole filling characteristics can be improved.

  As performance required for the resist lower layer film, there is no intermixing with the resist upper layer film, and there is no diffusion of low molecular components into the resist upper layer film (for example, “Proc. SPIE vol. 2195”). P225-229 (1994). In order to prevent these problems, a method is generally employed in which a resist underlayer film is formed on a substrate by spin coating or the like and then thermally crosslinked by baking. Therefore, there are a method of adding a crosslinking agent as a component of the resist underlayer film material and a method of introducing a crosslinkable substituent into the polymer. Examples of the method for introducing a crosslinkable substituent into the polymer include a method of copolymerizing crosslinkable repeating units represented by b to f represented by the general formula (2).

  Specific examples of the crosslinking agent that can be used in the present invention include a melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Examples include compounds containing double bonds such as epoxy compounds, isocyanate compounds, azide compounds, and alkenyl ether groups. These may be used as additives, but may be introduced as pendant groups in the polymer side chain. A compound containing a hydroxy group can also be used as a crosslinking agent.

Among specific examples of the crosslinking agent, when an epoxy compound is further exemplified, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether and the like Illustrated. Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, Examples thereof include compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof. Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, and tetramethylolguanamine. A compound in which ˜4 methylol groups are acyloxymethylated or a mixture thereof may be mentioned. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, and tetramethylolglycoluril methylol. Examples thereof include compounds in which 1 to 4 of the groups are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 4 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. Examples of the azide compound include 1,1′-biphenyl-4,4′-bisazide and 4,4′-methylidenebis. Examples include azide and 4,4′-oxybisazide.

  Examples of the compound containing an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, Examples include trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

When the hydroxy group of a polymer contained in the resist underlayer film material of the present invention, for example, a polymer having a repeating unit represented by the general formula (2) is substituted with a glycidyl group, addition of a compound containing a hydroxy group It is valid. Particularly preferred are compounds containing two or more hydroxy groups in the molecule. Examples of the compound containing a hydroxy group include naphthol novolak, m- and p-cresol novolak, naphthol-dicyclopentadiene novolak, m- and p-cresol-dicyclopentadiene novolak, 4,8-bis (hydroxymethyl) tricyclo. [5.2.1.0 ^2,6 ] -decane, pentaerythritol, 1,2,6-hexanetriol, 4,4 ′, 4 ″ -methylidenetriscyclohexanol, 4,4 ′-[1- [4- [1- (4-Hydroxycyclohexyl) -1-methylethyl] phenyl] ethylidene] biscyclohexanol, [1,1′-bicyclohexyl] -4,4′-diol, methylenebiscyclohexanol, decahydro Naphthalene-2,6-diol, [1,1′-bicyclohexyl] -3,3 ′, 4,4 Alcohol group-containing compounds such as '-tetrahydroxy, bisphenol, methylenebisphenol, 2,2'-methylenebis [4-methylphenol], 4,4'-methylidene-bis [2,6-dimethylphenol], 4,4' -(1-methyl-ethylidene) bis [2-methylphenol], 4,4'-cyclohexylidenebisphenol, 4,4 '-(1,3-dimethylbutylidene) bisphenol, 4,4'-(1- Methylethylidene) bis [2,6-dimethylphenol], 4,4′-oxybisphenol, 4,4′-methylenebisphenol, bis (4-hydroxyphenyl) methanone, 4,4′-methylenebis [2-methylphenol] 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 4,4 ′-(1,2- Tandiyl) bisphenol, 4,4 ′-(diethylsilylene) bisphenol, 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol, 4,4 ′, 4 ″- Methylidenetrisphenol, 4,4 ′-[1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl]- 4-methylphenol, 4,4 ′, 4 ″ -ethylidene tris [2-methylphenol], 4,4 ′, 4 ″ -ethylidene trisphenol, 4,6-bis [(4-hydroxyphenyl) Methyl] 1,3-benzenediol, 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4 ′, 4 ″, 4 ′ ″-( , 2-ethanediylidene) tetrakisphenol, 4,4 ′, 4 ″, 4 ′ ″-(ethanediylidene) tetrakis [2-methylphenol], 2,2′-methylenebis [6-[(2-hydroxy-5- Methylphenyl) methyl] -4-methylphenol], 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidyne) tetrakisphenol, 2,4,6-tris (4-hydroxyphenyl) Methyl) 1,3-benzenediol, 2,4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′, 4 ′ ″-(3-methyl-1-propanyl-3-ylidene) trisphenol, 2 , 6-bis [(4-hydroxy-3-fluorophenyl) methyl] -4-fluorophenol, 2,6-bis [4-hydroxy-3-fluorophenyl] methyl] -4-fluorophenol, 3,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] 1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] 1,3 Benzenediol, p-methylcalix [4] arene, 2,2′-methylenebis [6-[(2,5 / 3,6-dimethyl-4 / 2-hydroxyphenyl) methyl] -4-methylphenol, 2 , 2′-methylenebis [6-[(3,5-dimethyl-4-hydroxyphenyl) methyl] -4-methylphenol, 4,4 ′, 4 ″, 4 ′ ″-tetrakis [(1-methylethylidene ) Bis (1,4-cyclohexylidene)] phenol, 6,6′-methylenebis [4- (4-hydroxyphenylmethyl) -1,2,3-benzenetriol, 3,3 ′, 5,5′- Tetrakis [ 5-methyl-2-hydroxyphenyl) methyl] - [(1,1'-biphenyl) -4,4'-diol] phenol low nuclear bodies and the like.

  The blending amount of the crosslinking agent in the resist underlayer film material of the present invention is preferably 5 to 50 parts, particularly preferably 10 to 40 parts, relative to 100 parts (parts by mass, the same applies hereinafter) of the base polymer (total resin). If it is less than 5 parts, it may cause mixing with the resist film, and if it exceeds 50 parts, the antireflection effect may be reduced, or the film after crosslinking may be cracked.

  In the resist underlayer film material of the present invention, an acid generator for further promoting the crosslinking reaction by heat or the like can be added. There are acid generators that generate an acid by thermal decomposition and those that generate an acid by light irradiation, and any of them can be added.

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

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。Ｒ^101d、Ｒ^101e、Ｒ^101f、Ｒ^101gは、Ｒ^101a、Ｒ^101b、Ｒ^101cと同様の基又は水素原子である。Ｒ^101dとＲ^101e、Ｒ^101dとＲ^101eとＲ^101fとは環を形成してもよく、環を形成する場合には、Ｒ^101dとＲ^101e及びＲ^101dとＲ^101eとＲ^101fは炭素数３〜１０のアルキレン基、又は（Ｐｌａ−３）中の窒素原子を環の中に有する複素芳香族環を示す。）

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, part or all of hydrogen atoms of these groups may be substituted by an alkoxy group, etc. R ^101b and R ^{101c May} form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, K ⁻ represents a non-nucleophilic counter ion, R ^101d , R ^101e , R ^101f and R ^101g are the same groups or hydrogen atoms as R ^101a , R ^101b and R ^101c , R ^101d and R ^101e , R ^101d , R ^101e and R ^101f may form a ring. When forming a ring, R ^101d and R ^101e and R ^101d and R ^101e and R ^101f represent a C3-C10 alkylene group or a heteroaromatic ring having a nitrogen atom in (Pla-3) in the ring.

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f and R ^101g may be the same as or different from each other. Specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl Group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, alkylsulfonates such as mesylate and butanesulfonate, bis (trifluoromethylsulfonyl) imide, bis (perfluoroethylsulfonyl) ) Imido acids such as imide and bis (perfluorobutylsulfonyl) imide, methide acids such as tris (trifluoromethylsulfonyl) methide and tris (perfluoroethylsulfonyl) methide, and Sulfonate position alpha of the formula (K-1) is fluoro substituted, alpha represented by (K-2), β-position include sulfonates fluorine substituted.

（上記式（Ｋ−１）中、Ｒ¹⁰²は水素原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアシル基、炭素数２〜２０のアルケニル基、又は炭素数６〜２０のアリール基又はアリーロキシ基である。式（Ｋ−２）中、Ｒ¹⁰³は水素原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、炭素数２〜２０のアルケニル基、又は炭素数６〜２０のアリール基である。）

(In the above formula (K-1), ^R102 is a hydrogen atom, a linear, branched or cyclic alkyl group or acyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 6 carbon atoms. An aryl group or an aryloxy group of -20, wherein R ¹⁰³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms; Group or an aryl group having 6 to 20 carbon atoms.)

The heteroaromatic ring in which R ^101d , R ^101e , R ^101f and R ^101g have a nitrogen atom in the formula is an imidazole derivative (for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole). Etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.), imidazoline derivatives, imidazolidine Derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridy 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1 -Ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives , Indoline derivatives, quinoline derivatives (eg quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazi Derivatives, purine 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, etc. Is done.

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

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

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

Specific examples of the alkyl group for R ^102a and R ^102b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl group, cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. As the alkylene group for R ¹⁰³ , methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2- Examples include cyclohexylene group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^Examples of the 2-oxoalkyl group of R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is the formula (P1a-1), can be exemplified the same ones as described in (P1a-2) and (P1a-3).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

(In the formula, R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 20 carbon atoms, or carbon atoms. 7 to 12 aralkyl groups are shown.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を示す。Ｒ¹⁰⁵は（Ｐ２）式のものと同様である。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. And R ¹⁰⁵ is the same as in the formula (P2).

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

（式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

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

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

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

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

  Specific examples of the acid generator include onium salts such as tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, triethylammonium nonafluorobutanesulfonate, pyridinium nonafluorobutanesulfonate, camphorsulfone. Triethylammonium acid, pyridinium camphorsulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid ( p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodo , P-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert -Butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluene Bis (p-tert-butoxyphenyl) sulfonic acid phenylsulfonium, Tris (p-tert-butoxyphenyl) p-toluenesulfonic acid Sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, p-toluene Cyclohexylmethyl (2-oxocyclohexyl) sulfonium sulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trifluoromethanesulfonic acid Trinaphthylsulfoni , Trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium trif And onium salts such as triethylammonium nonaflate, tributylammonium nonaflate, tetraethylammonium nonaflate, tetrabutylammonium nonaflate, triethylammonium bis (trifluoromethylsulfonyl) imide, triethylammonium tris (perfluoroethylsulfonyl) methide be able to.

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

  Examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, Bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- ( -Butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis -O- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl)- α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α- Dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) α- dimethylglyoxime, bis -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, and bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

  Examples of bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane. Bissulfone derivatives can be mentioned.

  Examples of β-ketosulfonic acid derivatives include β-ketosulfonic acid derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

  Examples of the disulfone derivative include disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

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

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Mention may be made of sulfonic acid ester derivatives such as benzene.

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

In particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p -Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonyl trifluoromethanesulfonate Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O -Glyoxime derivatives such as-(p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bisnaphthyl Bissulfone derivatives such as sulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N- Hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Derivatives are preferably used.
In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types.

  The addition amount of the acid generator is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts with respect to 100 parts of the base polymer. If the amount is less than 0.1 part, the amount of acid generated is small and the crosslinking reaction may be insufficient. If the amount exceeds 50 parts, a mixing phenomenon may occur due to the acid moving to the upper resist.

Furthermore, the resist underlayer film material of the present invention can be blended with a basic compound for improving storage stability.
The basic compound serves as a quencher for the acid to prevent the acid generated in a trace amount from the acid generator during storage and the like from causing the crosslinking reaction to proceed.

  Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

  Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinoline carbo Nitriles), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Examples include derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated.

Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.
Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

  The compounding amount of the basic compound is suitably 0.001 to 2 parts, particularly 0.01 to 1 part, relative to 100 parts of the base polymer. If the blending amount is less than 0.001 part, the blending effect is small, and if it exceeds 2 parts, all of the acid generated by heat may be trapped and not crosslinked.

  The organic solvent that can be used in the resist underlayer film material of the present invention is not particularly limited as long as it dissolves the base polymer, acid generator, crosslinking agent, and other additives. Specific examples thereof include ketones such as cyclohexanone and methyl-2-amyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and the like. Alcohols: ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, lactic acid Ethyl, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , Tert-butyl acetate, tert-butyl propionate, propylene glycol monomethyl ether acetate, propylene glycol mono tert-butyl ether acetate and the like, and one or more of these can be used in combination. It is not limited. Among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, ethyl lactate, propylene glycol monomethyl ether acetate and mixed solvents thereof are preferably used in the resist underlayer film material of the present invention.

  The blending amount of the organic solvent is preferably 200 to 10,000 parts, particularly preferably 300 to 5,000 parts with respect to 100 parts of the total base polymer.

  Furthermore, the present invention is a method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film material of the present invention is used to form a resist underlayer film on the substrate, and a photoresist is formed on the underlayer film. The resist upper layer film of the composition is formed to form a multilayer resist film, the pattern circuit region of the multilayer resist film is exposed, and then developed with a developing solution to form a resist pattern on the resist upper layer film. A pattern forming method is provided, in which a resist underlayer film is etched using a resist upper layer film as a mask, and a substrate is etched using a multilayer resist film having a pattern formed as a mask to form a pattern on the substrate. .

  In this case, a photoresist underlayer film forming material is applied on the substrate to be processed, an intermediate layer containing silicon atoms is applied on the obtained underlayer film, and a layer of the photoresist composition is formed on the intermediate layer. Apply, irradiate the desired area of this photoresist layer with radiation, develop with a developing solution to form a photoresist pattern, and process the intermediate film layer with this photoresist pattern layer as a mask with a dry etching device, After removing the resist pattern layer, the lower film layer and then the substrate to be processed can be processed using the processed intermediate film layer as a mask.

Hereinafter, the pattern forming method of the present invention will be described with reference to FIG.
FIG. 1 is an explanatory diagram of a three-layer resist processing process.
The substrate 11 to be processed may be composed of a layer to be processed 11a and a base layer 11b, as shown. The base layer 11b of the substrate 11 is not particularly limited, and Si, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, etc. Different materials may be used. The layer to be processed _{11a, Si, SiO 2, SiON} , SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si , etc. and various low dielectric films and etching stopper film It is usually used and can be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.

In the three-layer resist processing process, as shown in FIG. 1, an intermediate layer 14 containing silicon atoms is interposed between the resist lower layer film 12 and the resist upper layer film 13 (see FIG. 1A). In this case, the material for forming the intermediate layer 14 may be a film made by spin coating such as a silicone polymer based on polysilsesquioxane or tetraorthosilicate glass (TEOS), or SiO produced by CVD. ₂ , SiN, SiON films can be used.
The thickness of the intermediate layer 14 is preferably 10 to 1,000 nm.

Next, a resist pattern is formed by exposure and development (see FIGS. 1B and 1C). Bake (PEB) may be performed between exposure and development. When the resist is a chemically amplified resist, high dissolution contrast in development can be obtained by causing a deprotection reaction in the case of a positive resist by PEB and a crosslinking reaction in the case of a negative resist. Next, the intermediate layer 14 is etched by dry etching mainly using chlorofluorocarbon gas, using the resist upper layer film 13 on which the resist pattern is formed as a mask (see FIG. 1D). This etching can be performed by a conventional method. In the case of dry etching mainly using a chlorofluorocarbon gas, CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F _{10 and the} like can be generally used.

  Further, after etching the intermediate layer 14, carbon monoxide gas, carbon dioxide gas, hydrogen gas, oxygen gas, nitrogen gas, chlorine gas, bromine gas, hydrogen chloride gas, hydrogen bromide gas, sulfur dioxide gas, carbon disulfide. Etching of the resist underlayer film 12 is performed by an etching gas selected from gases, such as dry etching (see FIG. 1E). These gases can be coordinated to the cyclopentadienyl complex metal to gasify the metal, thereby allowing etching to proceed.

Etching of the next substrate 11 can also be performed by a conventional method. For example, if the substrate is SiO ₂ or SiN, etching mainly using a chlorofluorocarbon gas, polysilicon (p-Si), Al, or W is chlorine, Etching mainly using bromine-based gas is performed (see FIG. 1F). The resist underlayer film of the present invention is characterized by excellent etching resistance when etching these substrates. At this time, if necessary, the resist upper layer film may be removed and then the substrate may be etched, or the substrate may be etched while leaving the resist upper layer film as it is.

EXAMPLES Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by these description.
In the following examples, the weight average molecular weight Mw and the number average molecular weight Mn are measured values based on polystyrene by gel permeation chromatography (GPC).

[Synthesis Example 1]
To a 200 mL flask, 10.6 g of vinylferrocene, 9.5 g of 4-tert-amyloxystyrene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN (2,2′-azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 16.1 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinyl ferrocene: 4-tert-amyloxystyrene = 50: 50
Weight average molecular weight (Mw) = 9,100
Molecular weight distribution (Mw / Mn) = 1.88
This polymer is referred to as polymer 1.

[Synthesis Example 2]
To a 200 mL flask, 10.6 g of vinylferrocene, 11.3 g of 6-tert-butoxy-2-vinylnaphthalene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 17.5 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinyl ferrocene: 6-tert-butoxy-2-vinylnaphthalene = 50: 50
Weight average molecular weight (Mw) = 5,400
Molecular weight distribution (Mw / Mn) = 1.79
This polymer is designated as Polymer 2.

[Synthesis Example 3]
To a 200 mL flask, 12.9 g of vinyl ruthenocene, 11.3 g of 6-tert-butoxy-2-vinylnaphthalene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 18.2 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinyl ruthenocene: 6-tert-butoxy-2-vinylnaphthalene = 50: 50
Weight average molecular weight (Mw) = 6,100
Molecular weight distribution (Mw / Mn) = 1.61
This polymer is designated as Polymer 3.

[Synthesis Example 4]
To a 200 mL flask, 12.9 g of vinylferrocene, 9.2 g of 6-hydroxymethyl-2-vinylnaphthalene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 17.7 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinyl ferrocene: 6-hydroxymethyl-2-vinylnaphthalene = 50: 50
Weight average molecular weight (Mw) = 6,100
Molecular weight distribution (Mw / Mn) = 1.61
This polymer is designated as polymer 4.

[Synthesis Example 5]
Into a 200 mL flask, 12.9 g of vinylferrocene, 3.5 g of 6-acetoxyindene, 5.7 g of 4-tert-amyloxystyrene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 16.6 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinylferrocene: 6-acetoxyindene: 4-tert-amyloxystyrene = 50: 20: 30
Weight average molecular weight (Mw) = 5,700
Molecular weight distribution (Mw / Mn) = 1.66
This polymer is designated as polymer 5.

[Synthesis Example 6]
To a 200 mL flask, 12.9 g of vinylferrocene, 8.4 g of 4-hydroxyacenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 16.0 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinylferrocene: 4-hydroxyacenaphthylene = 50: 50
Weight average molecular weight (Mw) = 6,700
Molecular weight distribution (Mw / Mn) = 1.67
This polymer is designated as polymer 6.

[Synthesis Example 7]
Into a 200 mL flask, 9.1 g of vinylferrocene, 9.1 g of 4-hydroxymethylacenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 13.6 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinylferrocene: 4-hydroxymethylacenaphthylene = 50: 50
Weight average molecular weight (Mw) = 6,700
Molecular weight distribution (Mw / Mn) = 1.67
This polymer is designated as polymer 7.

[Synthesis Example 8]
To a 200 mL flask, 8.5 g of vinylferrocene, 6.9 g of 2,5-norbornadiene-2-carboxylic acid, 5.7 g of 4-tert-amyloxystyrene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 13.7 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Vinylferrocene: 2,5-norbornadiene-2-carboxylic acid: 4-tert-amyloxystyrene = 40: 30: 30
Weight average molecular weight (Mw) = 4,600
Molecular weight distribution (Mw / Mn) = 1.55
This polymer is designated as polymer 8.

[Synthesis Example 9]
To a 200 mL flask, 14.2 g of ferrocene methyl methacrylate, 7.1 g of glycidyl methacrylate, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 17.0 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Ferrocene methyl methacrylate: glycidyl methacrylate = 50: 50
Weight average molecular weight (Mw) = 9,300
Molecular weight distribution (Mw / Mn) = 2.05
This polymer is designated as polymer 9.

[Comparative Synthesis Example 1]
To a 500 mL flask, 40 g of 4-hydroxystyrene, 160 g of 2-methacrylic acid-1-adamantane, and 40 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 4.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C. and reacted for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 188 g of a white polymer.

When the obtained polymer was measured by ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
4-hydroxystyrene: 2-methacrylic acid-1-adamantane = 32: 68
Weight average molecular weight (Mw) = 10,900
Molecular weight distribution (Mw / Mn) = 1.77
This polymer is referred to as comparative polymer 1.

[Comparative Synthesis Example 2]
To a 500 mL flask, 45 g of 5-hydroxy-1-vinylnaphthalene and 40 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 4.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C. and reacted for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 36.9 g of a white polymer.

When the obtained polymer was measured by ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
5-hydroxy-1-vinylnaphthalene = 100
Weight average molecular weight (Mw) = 10,500
Molecular weight distribution (Mw / Mn) = 1.66
This polymer is referred to as comparative polymer 2.

[Examples and Comparative Examples]
[Preparation of resist underlayer film material]
Resins represented by the above polymers 1 to 9, resins represented by comparative polymers 1 and 2, blend polymers 1 and 2, blend oligomer 1, acid generators represented by AG 1 and 2, crosslinks represented by CR 1 and 2, The resist underlayer film material is obtained by dissolving the agent in an organic solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M) at a ratio shown in Table 1 and filtering with a 0.1 μm fluororesin filter. (Examples 1 to 12, Comparative Examples 1 and 2) were prepared.
Polymers 1 to 9: Polymers obtained in Synthesis Examples 1 to 9 Comparative polymers 1 and 2: Polymers obtained in Comparative Synthesis Examples 1 and 2

Blend polymer 1, 2, Blend oligomer 1 (see the following structural formula)

Acid generator: AG1, 2 (see structural formula below)

有機溶剤：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）
ＣｙＨ（シクロヘキサノン） Cross-linking agent: CR1, 2 (see structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
CyH (cyclohexanone)

The resist underlayer film materials (Examples 1 to 12 and Comparative Examples 1 and 2) prepared above were applied onto a silicon substrate, baked at 280 ° C. for 60 seconds, and each 100 nm thick resist underlayer film (UDL1). ~ 12, comparative UDL1, 2) were formed.
After formation of the resist underlayer film, J.P. A. The refractive index (n, k) at a wavelength of 193 nm was determined using a spectroscopic ellipsometer (VASE) with variable incident angle from Woollam, and the results are shown in Table 1.

Next, a dry etching resistance test was performed. First, the same lower layer films (UDL 1 to 12, Comparative UDLs 1 and 2) used for the refractive index measurement are prepared, and the etching test of these lower layer films with CF ₄ / CHF ₃ gas is as follows (1). Tested under conditions. In this case, the difference in film thickness between the lower layer film and the resist before and after etching was measured using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Ltd. The results are shown in Table 2.
(1) Etching test with CF ₄ / CHF ₃ gas Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,000W
Gearup 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec

[Preparation of resist upper layer film material]
ArF resist material (SL resist for ArF) having the composition shown in Table 3 was dissolved in an organic solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M) at a ratio shown in Table 3, and 0.1 μm fluorine An ArF resist material was prepared by filtering through a resin filter.

An underlayer film forming material solution (UDL1-12, comparative UDL1,2) is applied on a 100 nm thick SiO ₂ film prepared on a Si substrate and baked at 280 ° C. for 60 seconds to form a lower layer film having a thickness of 100 nm. Formed.
A silicon-containing intermediate layer solution SOG (manufactured by Shin-Etsu Chemical Co., Ltd .; SHB-A940) is applied thereon and baked at 220 ° C. for 60 seconds to form an intermediate layer having a thickness of 35 nm. The solution was applied and baked at 100 ° C. for 60 seconds to form a 90 nm-thick photoresist layer.
Next, exposure using an ArF excimer laser immersion scanner (Nikon Corporation, NSR-610C, NA 1.30, σ 0.98 / 0.78, dipole aperture 35 degrees, azimuthally polarized illumination, 6% halftone phase shift mask) Exposure was performed while changing the amount, baking (PEB) at 80 ° C. for 60 seconds, and development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds to obtain a positive pattern. The 45 nm line and space pattern shape of the pattern was observed and the results are shown in Table 4.

Next, processing of silicon-containing resist intermediate layer film (SOG) using the resist pattern by dry etching as a mask using Tokyo Electron etching apparatus Telius, resist underlayer film using the silicon-containing resist intermediate layer film as a mask, and the obtained resist The SiO ₂ film was processed using the lower layer film pattern as a mask. Etching conditions are as shown below.

Transfer conditions of resist pattern to resist interlayer film.
Chamber pressure 10.0Pa
RF power 1,500W
CF ₄ gas flow rate 75ml / min
O ₂ gas flow rate 15ml / min
Time 15sec
Time 120sec

Transfer conditions of resist interlayer film pattern to resist underlayer film.
Chamber pressure 2.0Pa
RF power 500W
Ar gas flow rate 75ml / min
CO gas flow rate 45ml / min
Time 120sec

Transfer conditions of resist underlayer film pattern to SiO ₂ film.
Chamber pressure 2.0Pa
RF power 2,200W
C ₅ F ₁₂ gas flow rate 20 ml / min
C ₂ F ₆ gas flow rate 10ml / min
Ar gas flow rate 300ml / min
O ₂ 60ml / min
Time 30sec

  The cross sections of the patterns were observed with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared and summarized in Table 4.

As shown in Table 2, the CF ₄ / CHF ₃ gas etching rate of the lower layer film of the present invention is sufficiently slower than that of Comparative Examples 1 and 2. As shown in Table 4, it was confirmed that the resist shape after development, the shape of the lower layer film after the oxygen etching and the substrate processing etching were also good.

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

11 Substrate 11a Processed layer 11b Base layer 12 Lower layer film 13 Upper layer film 13 'Exposed portion 14 Intermediate layer

Claims (5)

A resist underlayer film material for a multilayer resist film used in lithography, comprising a repeating unit containing a cyclopentadienyl complex represented by the following general formula (1) and a substitution represented by the following general formula (2): unsubstituted hydroxy group or carboxyl group, oxirane, features and, Relais resist underlayer film material that comprises a polymer comprising recurring units of the crosslinkable selected from oxetane.

(In the formula, R ¹ , X and M are as described above. R ³ and R ⁸ are hydrogen atoms or methyl groups. R ⁴ , R ⁵ , R ⁶ and R ⁷ are substituted or unsubstituted hydroxy groups or carboxyls. A group, —CR ¹⁰ R ¹¹ OH, or —O—R ¹² , wherein R ¹⁰ and R ¹¹ are a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁹ , R; ¹² is a linear, branched or cyclic alkyl group or acyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 12 carbon atoms containing oxirane or oxetane, Y ¹ is a single bond, —C ( ═O) —O—R ¹³ —, —C (═O) —NH—R ¹³ —, or —O—, and Y ² represents —C (═O) —O—R ¹⁴ —, or —C ( ═O) —NH—R ¹⁴ —, wherein R ¹³ and R ¹⁴ are a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, and an arylene having 6 to 10 carbon atoms. Or an alkenylene group having 2 to 12 carbon atoms, Z is a methylene group, oxygen atom, sulfur atom, or -NH-, m, n, p is 1 or 2, q is 0, 1 or 2. A, b, c, d, e, and f are 0 <a <1.0, 0 ≦ b ≦ 0.95, 0 ≦ c ≦ 0.95, 0 ≦ d ≦ 0.95, and 0 ≦, respectively. (e ≦ 0.95, 0 ≦ f ≦ 0.95, 0 <b + c + d + e + f <1.0.) The resist underlayer film material according to claim 1 , wherein the resist underlayer film material further contains one or more of an organic solvent, an acid generator, and a crosslinking agent. The resist underlayer film forming material according to claim 1 or 2 is applied onto a substrate to be processed, a layer of a resist composition is applied onto the obtained underlayer film, and radiation is applied to a desired region of the resist layer. A pattern forming method comprising: developing with a developing solution to form a resist pattern, and then processing the resist underlayer film layer and the substrate to be processed using the resist pattern layer as a mask with a dry etching apparatus. 3. The resist underlayer film forming material according to claim 1 or 2 is applied on a substrate to be processed, and an atom selected from a silicon atom, a titanium atom, a zirconium atom, a hafnium atom, and an aluminum atom is formed on the obtained underlayer film. An intermediate layer containing at least seeds is applied, a layer of a resist composition is applied on the intermediate layer, radiation is applied to a desired region of the resist layer, and development is performed with a developer to form a resist pattern. Processing the intermediate film layer using the resist pattern layer as a mask with an etching apparatus, removing the resist pattern layer, and processing the lower film layer and then the substrate to be processed using the processed intermediate film layer as a mask. The pattern forming method according to claim 3 . The resist composition includes a polymer containing no silicon atom, and dry etching for processing the lower layer film using the intermediate layer film as a mask is performed by carbon monoxide gas, carbon dioxide gas, hydrogen gas, oxygen gas, nitrogen gas, chlorine gas, The pattern forming method according to claim 4 , wherein the pattern forming method is performed using an etching gas selected from bromine gas, hydrogen chloride gas, hydrogen bromide gas, sulfur dioxide gas, and carbon disulfide gas.

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