JP2011164345A - Resist underlayer film material and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist underlayer film material for forming a resist underlayer film which is an underlayer of a resist film for a single layer resist process, a multilayer resist process, a side all spacer process or the like, with which the trailing of a resist pattern after developing is suppressed and further, the formation of an undercut shape or a reverse-tapered shape is restricted, and the pattern collapse is prevented, and to provide a method for forming a pattern on a substrate by lithography using the material. <P>SOLUTION: The resist underlayer film material contains a high molecular weight compound, having a repeating unit represented by general formula (1) and generating sulfonic acid by light and/or heat. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a resist underlayer film material for forming a resist underlayer film under a resist film used for microfabrication in a manufacturing process of a semiconductor element or the like, and in particular, far ultraviolet light, KrF excimer laser light (248 nm), ArF excimer. Resist suitable for exposure with laser light (193 nm), F ₂ laser light (157 nm), Kr ₂ laser light (146 nm), Ar ₂ laser light (126 nm), soft X-ray, electron beam, ion beam, X-ray, etc. The present invention relates to an underlayer film material. Furthermore, this invention relates to the method of forming a pattern in a board | substrate by lithography using this.

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

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

  In addition, as the thickness of the resist is reduced, a material having a much higher etching speed than that of the resist film is required as a normal organic antireflection film formed under the resist film. ) Organic antireflective coatings have been developed that have improved etching rates by changing the acrylic resin, polyester resin, and base resin.

  Here, with the progress of miniaturization, due to insufficient acidity at the resist interface, tailing at the base interface of the developed photoresist pattern has become a problem. In order to reduce the tailing, it is effective to add an acid generator that generates an acid by heat or light to the lower layer material composition. This is because, by adding the thermal acid generator, the surface of the lower layer film after application baking becomes acidic. In the addition of the photoacid generator, an acid is generated in the lower layer film in the exposed portion, and the deactivation of the acid at the resist interface is prevented. However, the acid generated from these additive-type acid generators diffuses into the resist layer, the resist shape becomes inversely tapered, and pattern collapse is induced. With the progress of miniaturization, pattern collapse has become serious at the same time as the bottom shape, and the development of a resist underlayer film that can solve both is desired.

In recent years, a side wall spacer process in which a SiO ₂ film is formed on a side wall of a resist pattern and a lower layer is processed using the SiO ₂ film as a mask has been studied. In order to use the SiO ₂ film as a mask, a carbon film is suitable as the lower layer film, and at this time, it is necessary to form a resist pattern on the carbon film. However, the reflectance of the carbon film with ArF light is high, and the problem of pattern collapse due to the bottoming of the resist pattern and undercut occurs due to the influence of the adsorbate on the surface of the carbon film.

  In addition, as a photoresist application, it has been proposed to introduce an acid generator into a polymer by copolymerizing an acid generator of an onium salt having a polymerizable olefin. Patent Document 1, Patent Document 2, and Patent Document 3 propose sulfonium salts and iodonium salts having a polymerizable olefin that generates a specific sulfonic acid. In this case, there is an effect that acid diffusion is reduced and edge roughness is reduced as compared with the case where an acid generator is added.

  However, as described above, as a resist underlayer film material for forming a resist underlayer film formed under the resist film, it solves both problems of the bottoming and pattern collapse of the resist pattern formed thereon There is a need for a resist underlayer film material that can be used.

JP-A-4-230645 JP 2005-84365 A JP 2006-045311 A

  The present invention has been made in view of such problems, and is a resist underlayer film material for forming a resist underlayer film under a resist film for a single layer resist process, a multilayer resist process, a sidewall spacer method, and the like. In addition, resist pattern bottoming after development is suppressed, undercut shape and reverse taper shape are suppressed, and resist underlayer film material that can prevent pattern collapse, and using this to the substrate by lithography An object is to provide a method of forming a pattern.

（式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は炭素数１〜２０の直鎖状、分岐状、環状のアルキレン基であり、エステル基、エーテル基、ラクトン環、フッ素原子、シアノ基、芳香族基、２重結合、及び３重結合のいずれかを有していてもよい。Ｒは水素原子又はフッ素原子である。０＜ａ≦１．０である。Ｍ^＋はスルホニウム、ヨードニウム、及びアンモニウムのいずれかである。） In order to solve the above-mentioned problems, according to the present invention, the polymer has a repeating unit represented by the following general formula (1) and includes a polymer compound that generates sulfonic acid by light and / or heat. A resist underlayer film material is provided.

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, such as an ester group, an ether group, a lactone ring, a fluorine atom, It may have any of a cyano group, an aromatic group, a double bond, and a triple bond, R is a hydrogen atom or a fluorine atom, 0 <a ≦ 1.0, and M ⁺ is a sulfonium. , Iodonium, or ammonium.)

  The resist underlayer film formed from such a resist underlayer film material has little tailing and undercut of the resist pattern after development, and less pattern collapse. Therefore, the resist pattern can be transferred with high accuracy, and a good pattern can be formed.

（式中、Ｒ^１、Ｒ^２、Ｒ、ａは前述の通りである。） In this case, the sulfonic acid generated by the light and / or heat can be a sulfonic acid having a repeating unit represented by the following general formula (2).

(In the formula, R ¹ , R ² , R, and a are as described above.)

  The sulfonic acid of the repeating unit represented by the general formula (2) is α fluorosulfonic acid bonded to the main chain, and the presence of this super strong acid α fluorosulfonic acid on the resist underlayer film surface allows Inactivation of the acid generated in the step can be prevented and occurrence of tailing after development and occurrence of scum in the space portion can be prevented. In addition, the α fluorosulfonic acid generated in the resist underlayer film does not diffuse into the resist film because it is bonded to the main chain, so the resist pattern does not become a reverse taper shape, and a vertical pattern Can be obtained.

（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、及び、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のいずれかを示し、これらの基の水素原子の一部又は全部がフッ素原子、トリフルオロメチル基、アルキル基、及びアルコキシ基のいずれか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。Ｒ^１０１ｄ、Ｒ^１０１ｅ、Ｒ^１０１ｆ、Ｒ^１０１ｇは、それぞれ水素原子、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、及び、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のいずれかを示し、これらの基の水素原子の一部又は全部がフッ素原子、トリフルオロメチル基、アルキル基、及びアルコキシ基のいずれかによって置換されていてもよい。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、Ｒ^１０１ｄとＲ^１０１ｅとＲ^１０１ｆは炭素数３〜１０のアルキレン基、又は、式中の窒素原子を環の中に有する複素芳香族環を示す。） Moreover, it is preferable that M ^<+> in the said General formula (1) is 1 type, or 2 or more types chosen from the following general formula (M-1), (M-2), and (M-3). .

(In the formula, 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 having 6 to 20 carbon atoms. An aryl group, and an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, and a part or all of hydrogen atoms of these groups are a fluorine atom, a trifluoromethyl group, an alkyl group, and an alkoxy group In addition, R ^101b and R ^101c may form a ring, and in the case of forming a ring, R ^101b and R ^101c are each an alkylene having 1 to 6 carbon atoms. ^.R 101d of the ^{proximal, R 101e, R 101f, 101g} R are each a hydrogen atom, the number 1 to 12 linear, branched or cyclic An alkyl group, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and a hydrogen atom of these groups R ^101d and R ^101e , R ^101d , R ^101e and R ^101f form a ring, part or all of which may be substituted by any of a fluorine atom, a trifluoromethyl group, an alkyl group and an alkoxy group. In the case of forming a ring, R ^101d and R ^101e , R ^101d , R ^101e and R ^{101f each} have an alkylene group having 3 to 10 carbon atoms or a nitrogen atom in the formula in the ring Represents a heteroaromatic ring.)

Thus, examples of the M ⁺ sulfonium, iodonium, and ammonium in the general formula (1) include the above general formulas (M-1), (M-2), and (M-3).

  The resist underlayer film material preferably has an antireflection film function.

  Since the resist underlayer film material of the present invention can have an antireflection function, it can also be used as an antireflection film material in photolithography. That is, since the resist underlayer film formed of the resist underlayer film material of the present invention also functions as an antireflection film, it is possible to form a good resist pattern while suppressing halation and standing waves caused by reflection during exposure. it can.

  Moreover, it is preferable that the polymer compound further includes a repeating unit having an epoxy group and / or a hydroxyl group.

  As described above, the polymer compound includes a repeating unit having the sulfonium salt, iodonium salt, or ammonium salt represented by the general formula (1) and a repeating unit having an epoxy group and / or a hydroxyl group. If so, the crosslinking efficiency can be improved.

  Moreover, it is preferable that the polymer compound further includes a repeating unit having a light-absorbing group containing an aromatic ring.

  The aromatic group has high light absorption, and if a resist underlayer film material containing such a polymer compound is used, a resist underlayer film (antireflection film) having an appropriate antireflection function can be formed.

  Moreover, it is preferable that the resist underlayer film material further contains one or more of an organic solvent, an acid generator, a basic compound, and a crosslinking agent.

  Thus, if the said resist underlayer film material contains an organic solvent further, the applicability | paintability of a resist underlayer film material can be improved more. Further, if the resist underlayer film material further contains one or more of an acid generator and a crosslinking agent, the crosslinking reaction in the resist underlayer film is promoted by baking after coating on the substrate. Can do so. Therefore, a dense film can be obtained, there is less risk of intermixing with the resist film, and low molecular component diffusion into the resist film or the like is reduced. As a result, a good resist pattern can be obtained, and a good pattern can be formed on the substrate. Furthermore, if it contains a basic compound, the storage stability of the resist underlayer film material during storage can be improved.

  Further, the present invention is a method for forming a pattern on a substrate by lithography, wherein at least a resist underlayer film is formed on the substrate using the resist underlayer film material, and a photoresist composition is formed on the resist underlayer film. After forming a photoresist film, exposing a pattern circuit region of the photoresist film, developing with a developer to form a resist pattern on the photoresist film, and using the obtained resist pattern as a mask, the resist underlayer A pattern forming method is provided, wherein a film and the substrate are etched to form a pattern on the substrate.

  In this way, by placing the resist underlayer film formed using the resist underlayer film material between the substrate and the photoresist film, skirting of the resist pattern and pattern collapse are suppressed, so a good pattern on the substrate Can be formed.

  The present invention is also a method for forming a pattern on a substrate by lithography, wherein at least an organic film is formed on the substrate, a silicon-containing film is formed on the organic film, and the silicon-containing film is formed. A resist underlayer film is formed using the resist underlayer film material, a photoresist film made of a photoresist composition is formed on the resist underlayer film, a pattern circuit region of the photoresist film is exposed, and a developer The resist film is developed to form a resist pattern, the resist underlayer film and the silicon-containing film are etched using the resist pattern as a mask, and the organic film is formed using the silicon-containing film on which the pattern is formed as a mask. Etching the film and etching the substrate using the organic film on which the pattern is formed as a mask to form a pattern on the substrate Providing a pattern forming method.

  Thus, an organic film and a silicon-containing film are formed on a substrate, and a resist underlayer film formed using the resist underlayer film material is placed between the silicon-containing film and a photoresist film, and a pattern is formed on the substrate. It may be formed.

  The present invention is also a method of forming a pattern on a substrate by lithography, wherein at least a carbon film is formed on the substrate, and a resist underlayer film is formed on the carbon film using the resist underlayer film material. Forming a photoresist film on the resist underlayer film, exposing a pattern circuit region of the photoresist film, developing with a developing solution to form a resist pattern on the photoresist film, and forming sidewalls of the resist pattern; A silicon-containing film is formed, and the resist underlayer film and the carbon film are etched using the silicon-containing film as a mask, and the substrate is etched using the carbon film formed with the pattern as a mask to form a pattern on the substrate. A pattern forming method is provided.

When such a sidewall spacer method is used, a resist underlayer film can be laminated on the carbon film using the resist underlayer film material of the present invention. In other words, a photoresist pattern is formed on a resist underlayer film laminated on a carbon film, a sidewall spacer is formed on the sidewall of the photoresist pattern, and the carbon film is processed using the sidewall spacer as a mask. .
Conventionally, there has been a problem of pattern collapse due to skirting or undercut of the resist pattern formed on the carbon film, but by forming the resist underlayer film on the carbon film using the resist underlayer film material of the present invention. Further, the bottoming of the resist pattern and the pattern collapse are suppressed, and even when the sidewall spacer method as described above is used, a good pattern can be formed on the substrate.

  As described above, the resist underlayer film material of the present invention repeats the (meth) acrylic ester represented by the general formula (1) in which α-fluorosulfonic acid bonded to at least the main chain is generated by light and / or heat. A polymer compound having a unit is included as a base resin. As a result, the occurrence of tailing, undercut and pattern collapse on the resist pattern after development is suppressed, and a vertical resist pattern can be obtained. Therefore, a good pattern can be formed on the substrate. Moreover, since the resist underlayer film formed from the resist underlayer film material of the present invention can have an antireflection film function, it can be suitably used as a material for forming the antireflection film.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these.
As described above, as a resist underlayer film material for forming a resist underlayer film formed in the lower layer of the resist film, the pattern resulting from the tailing of the resist pattern formed in the upper layer, the undercut shape and the reverse taper shape There has been a demand for a resist underlayer film material that can solve both problems of collapse.
The inventors of the present invention have made extensive studies to develop a resist underlayer film material capable of suppressing the pattern collapse due to the bottoming and undercut of the resist pattern after development.

  In the resist underlayer film blended with additive type acid generator, the acid generated from the acid generator diffuses into the resist film, and the resist pattern becomes undercut shape or reverse taper shape. was there. On the other hand, in the case where the acid generator is not added, the resist underlayer film after baking causes poor curing, or causes the tailing due to insufficient acidity of the resist underlayer film surface. When the resist underlayer film is not sufficiently cured, mixing between the underlayer film and the resist film material occurs when the resist solution thereon is dispensed.

  In view of the above, the present inventors have developed a crosslinkable polymer compound in which a sulfonic acid bonded to the main chain is generated in order to keep the resist underlayer film surface acidic and prevent the acid from diffusing into the resist film. In other words, a resist underlayer film material comprising a polymer (polymer compound) having at least a (meth) acrylic ester of an α-fluorosulfonic acid sulfonium salt, iodonium salt, or ammonium salt as a repeating unit. If present, the resist underlayer film formed from the resist underlayer film material has no tailing or undercut at the resist interface, can obtain a vertical pattern shape, and has excellent transfer performance of a photoresist pattern by etching. The present invention has been completed.

（式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は炭素数１〜２０の直鎖状、分岐状、環状のアルキレン基であり、エステル基、エーテル基、ラクトン環、フッ素原子、シアノ基、芳香族基、２重結合、及び３重結合のいずれかを有していてもよい。Ｒは水素原子又はフッ素原子である。０＜ａ≦１．０である。Ｍ^＋はスルホニウム、ヨードニウム、及びアンモニウムのいずれかである。） That is, the resist underlayer film material of the present invention has a repeating unit of (meth) acrylic acid ester represented by the following general formula (1), a sulfonium salt that generates sulfonic acid by light and / or heat, an iodonium salt, It contains an ammonium salt polymer compound.

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, such as an ester group, an ether group, a lactone ring, a fluorine atom, It may have any of a cyano group, an aromatic group, a double bond, and a triple bond, R is a hydrogen atom or a fluorine atom, 0 <a ≦ 1.0, and M ⁺ is a sulfonium. , Iodonium, or ammonium.)

（式中、Ｒ^１、Ｒ^２、Ｒ、ａは前述の通りである。） The sulfonic acid generated by light and / or heat is α-fluorosulfonic acid having a repeating unit represented by the following general formula (2).

(In the formula, R ¹ , R ² , R, and a are as described above.)

  In the resist underlayer film material of the present invention, α-fluorosulfonic acid having a repeating unit represented by the general formula (2) is generated by light and / or heat. Therefore, the deactivation of the acid generated in the resist film is prevented, and the trailing after development and the occurrence of scum in the space portion are prevented. In addition, the α fluorosulfonic acid generated in the resist underlayer film does not diffuse into the resist film because it is bonded to the main chain, so the resist pattern does not become a reverse taper shape, and a vertical pattern Can be obtained.

  Since the resist underlayer film material of the present invention can obtain a vertical pattern without causing tailing, the resist pattern can be transferred by etching with high accuracy, and a good pattern can be formed even after etching. it can.

  The resist underlayer film material of the present invention can have an anti-reflection film function for preventing halation and standing waves in photolithography, and the resist pattern can be tailed in electron beam exposure and EUV exposure. It can also be used to form a resist underlayer film for preventing undercutting.

A method for synthesizing the polymer compound having the repeating unit represented by the general formula (1) is not particularly limited, and can be performed by a conventional method.
Although the anion part of the monomer for obtaining the repeating unit a shown by the said General formula (1) is not specifically limited, For example, it can illustrate below.

（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、及び、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のいずれかを示し、これらの基の水素原子の一部又は全部がフッ素原子、トリフルオロメチル基、アルキル基、及びアルコキシ基のいずれか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。Ｒ^１０１ｄ、Ｒ^１０１ｅ、Ｒ^１０１ｆ、Ｒ^１０１ｇは、それぞれ水素原子、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、及び、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のいずれかを示し、これらの基の水素原子の一部又は全部がフッ素原子、トリフルオロメチル基、アルキル基、及びアルコキシ基のいずれかによって置換されていてもよい。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、Ｒ^１０１ｄとＲ^１０１ｅとＲ^１０１ｆは炭素数３〜１０のアルキレン基、又は、式中の窒素原子を環の中に有する複素芳香族環を示す。） As the sulfonium, iodonium, and ammonium of the cation moiety M ⁺ of the monomer for obtaining the repeating unit a represented by the general formula (1), the following general formulas (M-1), (M-2), (M-3) 1 type or 2 types or more selected from.

(In the formula, 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 having 6 to 20 carbon atoms. An aryl group, and an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, and a part or all of hydrogen atoms of these groups are a fluorine atom, a trifluoromethyl group, an alkyl group, and an alkoxy group In addition, R ^101b and R ^101c may form a ring, and in the case of forming a ring, R ^101b and R ^101c are each an alkylene having 1 to 6 carbon atoms. ^.R 101d of the ^{proximal, R 101e, R 101f, 101g} R are each a hydrogen atom, the number 1 to 12 linear, branched or cyclic An alkyl group, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and a hydrogen atom of these groups R ^101d and R ^101e , R ^101d , R ^101e and R ^101f form a ring, part or all of which may be substituted by any of a fluorine atom, a trifluoromethyl group, an alkyl group and an alkoxy group. In the case of forming a ring, R ^101d and R ^101e , R ^101d , R ^101e and R ^{101f each} have an alkylene group having 3 to 10 carbon atoms or a nitrogen atom in the formula in the ring Represents a heteroaromatic ring.)

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f , and R ^101g in the formula may be the same or different from each other. Specifically, as an alkyl group, a methyl group, an ethyl group, Propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4- Examples thereof include a methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, 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.

When R ^101d , R ^101e, and R ^101f form a ring, R ^101d , R ^101e, and R ^101f represent a heteroaromatic ring having a nitrogen atom in the formula. Heteroaromatic rings having a nitrogen atom in the formula are imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg, pyrroline). 2-methyl-1-pyrroline), 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-phenylpyridine, 4-tert-butylpyridine, diph Nylpyridine, 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, phthalazine derivatives, purine derivatives, pteridine derivatives Body, 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.

When at least one of R ^101a , R ^101b and R ^{101c in} the general formula (M-1) and the general formula (M-2) is an aromatic group, the effects of both a photoacid generator and a thermal acid generator However, all of them have no aromatic group, or the above general formula (M-3) acts as a thermal acid generator.

  The resist underlayer film material of the present invention is based on a polymer compound that essentially includes the repeating unit a of (meth) acrylic ester having the α-fluorosulfonate salt represented by the general formula (1). The compound is preferably a copolymer containing a repeating unit a and a repeating unit b having a crosslinkable epoxy group and / or hydroxy group. The monomer for obtaining the repeating unit b which has an epoxy group and / or a hydroxy group is shown below.

  The hydroxy group may be substituted with an acid labile group during polymerization. The acid labile group is deprotected by the acid generated during baking after spin coating, and the hydroxy group undergoes a crosslinking reaction.

  In order to function as an antireflection film, the polymer compound preferably further includes a repeating unit c having an aromatic group with high light absorption. Specific examples of the light-absorbing monomer c to be copolymerized include the following.

  Further, the polymer compound may include a repeating unit d for preventing adhesion with the resist and diffusion movement of acid and amine from the resist. The monomer for obtaining the repeating unit d is a monomer having a hydroxy group, a lactone ring, an ester group, an ether group, a cyano group, a carboxyl group, a sulfo group, an acid anhydride, and a maleimide used as an adhesive group of the resist, Specific examples are shown below.

  Here, the specific structure of the monomer for obtaining the repeating units a to d is as described above, and the copolymerization ratio is preferably 0 <a ≦ 1.0, 0 ≦ b ≦ 0.8, 0 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.8, 0.05 ≦ b + c + d ≦ 0.9, more preferably 0.01 ≦ a ≦ 0.9, 0 ≦ b ≦ 0.7, 0 ≦ c ≦ 0.7, 0 ≦ d ≦ 0.7, 0.1 ≦ b + c + d ≦ 0.9, more preferably 0.02 ≦ a ≦ 0.8, 0 ≦ b ≦ 0.6, 0 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.6, 0.2 ≦ b + c + d ≦ 0.8.

  Note that a + b + c + d = 1 is preferable, but a + b + c + d = 1 is the sum of repeating units a, b, c, and d in a polymer compound (copolymer) including repeating units a, b, c, and d. It shows that the amount is 100 mol% with respect to the total amount of all repeating units.

In order to synthesize the polymer compound (copolymer) contained in the resist underlayer film material of the present invention, as one method, (meth) acrylic ester having α-fluorosulfonate and antireflection function are included. For example, a radical initiator or a cationic polymerization initiator is added to an olefin monomer having a light-absorbing group in an organic solvent and subjected to heat polymerization. When used as an underlayer film for EB and EUV exposure, the light-absorbing group is not particularly required. 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 other Friedel-Crafts catalyst such _{as, I 2, (C 6 H} 5) 3 generated material susceptible to cationic as CCl are used.

  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 equivalent mass average molecular weight of the polymer compound 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 and the degree of dispersion can be reduced. Repeating two or more general formulas (1) having different molecular weights and degrees of dispersion is possible. You may mix the polymer compound which has a repeating unit of 2 or more types of general formula (1) from which mixing of the polymeric compound which has a unit, or a composition ratio differs. A polymer compound having a repeating unit of the general formula (1) and a polymer compound not containing the general formula (1) can also be blended. In this case, the target characteristic can be brought out by orienting the polymer compound containing the repeating unit of the general formula (1) on the surface after spin coating. In order to orient the polymer compound containing the repeating unit of the general formula (1) on the surface, it is desirable to copolymerize the repeating unit having fluorine.

The base resin for resist underlayer film material of the present invention is characterized by containing a polymer (polymer compound) obtained by polymerizing (meth) acrylic ester having at least α-fluorosulfonate, and further described below. It can also be blended with the polymeric compounds shown. For example, in order to embed holes without generating voids, a method is used in which a polymer having a low glass transition point is used and resin is embedded to the bottom of the holes while heat-flowing at a temperature lower than the crosslinking temperature (for example, a special technique). No. 2000-294504). 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 Copolymers selected from olefins such as olefins, polymers by metathesis ring-opening polymerization, novolak resins, dicyclopentadiene resins, phenolic low nuclei, cyclodextrins, steroids such as cholic acid It is possible to reduce the glass transition point and improve the via hole embedding characteristics by blending with saccharides, monosaccharides, polysaccharides, calixarenes, and fullerenes.
The blending amount of the blending polymer is 0 to 10,000 parts by weight, preferably 0 to 5000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

The resist underlayer film material of the present invention preferably further contains one or more of an organic solvent, an acid generator, a basic compound, and a crosslinking agent.
If the resist underlayer film material further contains an organic solvent, the applicability of the resist underlayer film material can be further improved. Further, if the resist underlayer film material further contains one or more of an acid generator and a crosslinking agent, the crosslinking reaction in the resist underlayer film is promoted by baking after coating on the substrate. You can do that. Accordingly, a dense film can be obtained, and there is less risk of intermixing with the resist film, and diffusion of low molecular components into the resist film or the like is reduced. As a result, a good resist pattern can be obtained, and a good pattern can be formed on the substrate. Moreover, if it contains a basic compound, the storage stability of the resist underlayer film material during storage of the resist underlayer film material can be improved.

  As performance required for the resist underlayer film, there is no intermixing with the resist film, and there is no diffusion of low molecular components into the resist 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 repeating unit having a crosslinkable substituent into the polymer.

  Specific examples of additive crosslinking agents that can be used in the present invention include melamine compounds, guanamine compounds, glycoluril compounds 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 urea compounds, 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. Examples thereof include compounds in which 1 to 4 methylol groups are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, a mixture thereof, tetramethoxyethyl urea, and the like.

  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.

In order to increase the crosslinking efficiency of the polymer contained in the resist underlayer film material of the present invention, it is effective to add a compound containing a hydroxy group. 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-methyl Phenyl) methyl] -4-methylphenol], 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidyne) tetrakisphenol, 2,4,6-tris (4-hydroxyphenylmethyl) ) 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 [( - 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, more preferably 10 to 40 parts, with respect to 100 parts (parts by mass, the same applies hereinafter) of the base resin (total resin). If it is 5 parts or more, there is little possibility of causing mixing with the resist film, and if it is 50 parts or less, the antireflection effect is reduced or the film after crosslinking is less likely to crack.

  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), (2) 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、及び、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のいずれかを示し、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。Ｒ^１０１ｄ’、Ｒ^１０１ｅ’、Ｒ^１０１ｆ’、Ｒ^１０１ｇ’は、水素原子、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、及び、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のいずれかを示し、これらの基の水素原子の一部又は全部がアルコキシ基によって置換されていてもよい。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’、Ｒ^１０１ｄ’とＲ^１０１ｅ’とＲ^１０１ｆ’は炭素数３〜１０のアルキレン基、又は式中の窒素原子を環の中に有する複素芳香族環を示す。Ｋ⁻は非求核性対向イオンを表す。）

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 6 to 6 carbon atoms. 20 aryl groups and any of aralkyl groups or aryloxoalkyl groups having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by alkoxy groups or the like. well and ^{R 101b} 'and ^{R 101c'} may form a ring, when they form a ^{ring, R 101b ', R 101c'} is ^{.R 101d} to an alkylene group having 1 to 6 carbon atoms, respectively ', ^{R 101e ', R 101f',} R 101g ' is a hydrogen atom, C1-12 straight, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or Okisoaruke Or an aryl group having 6 to 20 carbon atoms, and an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and a part or all of the hydrogen atoms of these groups are substituted with alkoxy groups. R ^101d ′ and R ^101e ′, R ^101d ′ and R ^101e ′ and R ^101f ′ may form a ring, and in the case of forming a ring, R ^101d ′ and R ^101e ′, R ^101d ′, R ^101e ′ and R ^101f ′ represent an alkylene group having 3 to 10 carbon atoms or a heteroaromatic ring having a nitrogen atom in the formula in the ring, and K ⁻ represents a non-nucleophilic counter ion. To express.)

R ^101a ′, R ^101b ′, R ^101c ′, R ^101d ′, R ^101e ′, R ^101f ′, R ^101g ′ may be the same as or different from each other. Group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropyl Examples include a methyl 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 represented by the formula (K-1) is fluoro substituted, represented by the following general formula (K-2), α, β-position include sulfonates fluorine substituted.

In General Formula (K-1), ^R102 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an acyl group, an alkenyl group having 2 to 20 carbon atoms, and 6 carbon atoms. Or an aryl group or an aryloxy group of ˜20. In general formula (K-2), ^R103 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. Any of aryl groups.
As the non-nucleophilic counter ion of K ⁻ , a sulfonate substituted at the α-position with fluorine has the strong acid strength and can be most preferably used because of a high crosslinking reaction rate.

In addition, when R ^101d ′, R ^101e ′ and R ^101f ′ form a ring, R ^101d ′, R ^101e ′ and R ^101f ′ are heteroaromatics having a nitrogen atom in the formula in the ring. A heteroaromatic ring having a nitrogen atom in the formula in the formula is an imidazole derivative (for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivative, furazane derivative, 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, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butyl Rupentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl 2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), 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 ( Quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10- Examples include phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Although (P1a-1) and (P1a-2) have the effects of both a photoacid generator and a thermal acid generator, (2) 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。Ｒ^１０３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。）

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

  Among the onium salts of (P1a-1), (P1a-2), (2) or (P1b), (P1a-1), (P1a-2) and (P1b) generate an acid by light or heat. , (2) generates an acid by heat. Among the onium salts of (P1a-1), (P1a-2), (2) or (P1b), the ammonium salt represented by (2) is most preferable as the acid generator contained in the resist underlayer film material of the present invention. Can be used. In the ammonium salt represented by (2), since the substances generated by thermal decomposition are amine and acid, they are less likely to evaporate by heat and become a generation source of particles. Therefore, there is little risk of contaminating the substrate during pattern formation, and a highly clean substrate can be obtained.

（式中、Ｒ^１０５、Ｒ^１０６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、及び炭素数７〜１２のアラルキル基のいずれかを示す。）

(In the formula, R ¹⁰⁵ and R ^{106 each} represent 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, and the number of carbon atoms. Any one of 7-12 aralkyl groups is 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、Ｒ^１０７、Ｒ^１０８、Ｒ^１０９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、炭素数７〜１２のアラルキル基を示す。Ｒ^１０８、Ｒ^１０９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、Ｒ^１０８、Ｒ^１０９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。Ｒ^１０５は前述した（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, 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; Represents a linear or branched alkylene group, and R ¹⁰⁵ is the same as that in formula (P2) described above.)

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、Ｒ^１１０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、及び、炭素数２〜６のアルケニレン基のいずれかを示し、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。Ｒ^１１１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、及び、ナフチル基のいずれかを示し、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。）

(Wherein R ¹¹⁰ represents any of an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, and an alkenylene group having 2 to 6 carbon atoms, and a part of hydrogen atoms of these groups) Alternatively, all may be further substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, an nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ has 1 to 8 carbon atoms. A linear, branched or substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, and a naphthyl group are shown, and some or all of the hydrogen atoms of these groups further have 1 to An alkyl group or an alkoxy group having 4 carbon atoms; a phenyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group, or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom, Fluorine It may be substituted with a child.)

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 of 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 -An octenyl group or the like is an alkoxyalkyl group such as a methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl Group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl Group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group, methoxyhexyl group, methoxyheptyl group and the like.

  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-ketosulfone derivatives include β-ketosulfone 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 by mass, more preferably 0.5 to 40 parts by mass with respect to 100 parts by mass of the base resin. If the amount is 0.1 parts by mass or more, the amount of acid generated is sufficient and a sufficient crosslinking reaction occurs. If the amount is 50 parts by mass or less, there is little possibility of mixing phenomenon due to the acid moving to the upper resist film.

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 preferably 0.001 to 2 parts by mass, particularly 0.01 to 1 part by mass with respect to 100 parts by mass of the total base resin. If the blending amount is 0.001 part by mass or more, a sufficient blending effect is obtained, and if it is 2 parts by mass or less, there is little possibility that all the acid generated by heat will 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 resin, acid generator, crosslinking agent, basic compound, 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 by mass, and particularly preferably 300 to 5,000 parts by mass with respect to 100 parts by mass of the total base resin.

Furthermore, the present invention is a method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film is formed on the substrate using the resist underlayer film material, and a photoresist composition is formed on the resist underlayer film. After forming a photoresist film, exposing a pattern circuit region of the photoresist film, developing with a developer to form a resist pattern on the photoresist film, and using the obtained resist pattern as a mask, the resist underlayer A pattern forming method is provided, wherein a film and the substrate are etched to form a pattern on the substrate.
As described above, the resist underlayer film material of the present invention is used for forming a resist underlayer film formed under a photoresist film.

In the lower layer of the resist underlayer film formed from the resist underlayer film material of the present invention, Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu serving as a substrate to be processed are formed. Al-Si and the like and various low dielectric films and etching stopper films thereof are used, and can be formed to a thickness of usually 10 to 10,000 nm, particularly 20 to 5,000 nm.

Further, a hard mask for processing the substrate to be processed may be laid on the substrate to be processed. As the hard mask, when the substrate to be processed is an SiO ₂ -based insulating film substrate, SiN, SiON, p-Si. P-Si, α-Si, W, W-Si, TiN, carbon and the like are used. The substrate to be processed is p-Si, W-Si, SiO 2 in the case of the gate electrode such as Al-Si, SiN, SiON, TiN, carbon or the like is used.
In this case, a resist underlayer film can be formed on the hard mask using the resist underlayer film material of the present invention.

Further, as described above, an organic film having a high carbon ratio may be formed on the substrate to be processed, and a silicon-containing film may be formed on the organic film. In this case, a resist underlayer film can be formed on the silicon-containing film using the resist underlayer film material of the present invention. Furthermore, after forming a photoresist film on the resist underlayer film, exposing a pattern circuit region of the photoresist film, developing with a developer, a resist pattern is formed on the photoresist film, and the resist pattern is formed. Etching the resist underlayer film and the silicon-containing film using as a mask, etching the organic film using the silicon-containing film on which the pattern is formed as a mask, and further using the organic film on which the pattern is formed as a mask as a substrate Can be etched to form a pattern on the substrate. Examples of silicon-containing films include SiO ₂ films, SiN films, SiON films, and SiC films formed by CVD or ALD. The spin-on silicon-containing film preferably contains a silsesquioxane-based silicon compound disclosed in JP-A-2004-310019 and has an antireflection function.

  The present invention is also a method for forming a pattern on a substrate by lithography, wherein at least a carbon film is formed on the substrate, and a resist underlayer film is formed on the carbon film using the resist underlayer film material described above. And forming a photoresist film on the resist underlayer film, exposing the pattern circuit region of the photoresist film, and developing with a developer to form a resist pattern on the photoresist film. A silicon-containing film is formed on the sidewall, the resist underlayer film and the carbon film are etched using the silicon-containing film as a mask, and the substrate is etched using the carbon film on which the pattern is formed as a mask to form a pattern on the substrate. A pattern forming method is provided.

Thus, in the sidewall spacer process in which the SiO ₂ film is formed directly on the sidewall of the resist pattern, a carbon film is applied to the lower layer of the resist. Examples of the carbon film include an amorphous carbon film formed by CVD, and a spin-on carbon film formed by spin coating by dissolving a high carbon material in an organic solvent. Examples of the spin-on carbon film include a nortricyclene copolymer, a hydrogenated naphthol novolak resin, a naphthol dicyclopentadiene copolymer, a phenol dicyclopentadiene copolymer, a fluorene bisphenol novolak described in 2005-128509, and 2005-250434. Acenaphthylene copolymer, indene copolymer, fullerene having a phenol group described in JP-A-2006-227391, bisphenol compound and this novolak resin, dibisphenol compound and this novolak resin, novolak resin of adamantane phenol compound, hydroxyvinylnaphthalene copolymer Bisnaphthol compounds described in JP-A-2007-199653, and these novolak resins, ROMP, tricyclopentadiene copolymers It includes resins compound represented. If an attempt is made to form a resist pattern directly on the carbon film, a standing wave is generated due to the reflection of exposure light from the carbon film, irregularities are formed on the side walls of the resist pattern, or the resist is caused by impurities adsorbed on the carbon film surface. The pattern may fall due to a hem or undercut. For this reason, it is preferable to spin coat the resist underlayer film material of the present invention on the carbon film.

  The resist underlayer film forming method using the resist underlayer film material of the present invention will be described. The resist underlayer film can be formed on the substrate by a spin coat method or the like in the same manner as the ordinary photoresist film forming method. is there. After forming the resist underlayer film by a spin coat method or the like, it is desirable to evaporate the organic solvent and bake to promote the crosslinking reaction in order to prevent mixing with the photoresist film. The baking temperature is preferably in the range of 80 to 300 ° C. and in the range of 10 to 300 seconds. Although the thickness of the resist underlayer film is appropriately selected, it is preferably 10 to 200 nm, particularly preferably 20 to 150 nm. When the resist underlayer film is used as an antireflection film, the film thickness is high in antireflection effect. Can be selected. After the resist underlayer film is thus formed, a photoresist film is formed thereon.

In this case, as the photoresist composition for forming this photoresist film, for example, a base polymer made of a known polymethacrylate as disclosed in JP-A-9-73173 and JP-A-2000-336121 can be used. it can.
The thickness of the photoresist film is not particularly limited, but is preferably 30 to 500 nm, particularly 50 to 400 nm.

  In the case of forming a photoresist film from the photoresist composition, a spin coat method or the like is preferably used as in the case of forming the resist underlayer film. After the photoresist film is formed by spin coating or the like, pre-baking is performed, but it is preferably performed at 80 to 180 ° C. for 10 to 300 seconds.

  Thereafter, in accordance with a conventional method, the pattern circuit region of the resist film is exposed, post-exposure baking (PEB), and development is performed to obtain a resist pattern.

  A resist protective film can also be applied to the upper layer of the resist film (photoresist film). The resist protective film can have an antireflection function, and includes water-soluble and water-insoluble materials. As water-insoluble materials, there are materials that dissolve in alkaline developer and materials that do not dissolve in alkaline developer and can be removed with a fluorine-based solvent. However, the former is a process that can be removed simultaneously with resist development. There is a merit. In the case of immersion exposure, a protective film may be provided for the purpose of preventing elution of an additive such as an acid generator from the resist and for improving the sliding property. As the protective film, those having the property of not dissolving in water but dissolving in alkali are preferable. High molecular compounds having α-trifluoromethylhydroxy group are higher alcohols having 4 or more carbon atoms or ether compounds having 8 to 12 carbon atoms. What was dissolved in is used. As a method for forming the protective film, a liquid for protective film is spin-coated on the resist film after pre-baking, and the protective film is formed by pre-baking. The thickness of the protective film is preferably in the range of 10 to 200 nm.

  When a protective film is used, after dry or immersion exposure, post-exposure baking (PEB) is performed, and development is performed with an alkali developer for 10 to 300 seconds. As the alkali developer, a 2.38 mass% tetramethylammonium hydroxide aqueous solution is generally widely used. When a development-soluble protective film is used, the protective film is peeled off and the resist film is developed simultaneously.

  When immersion exposure is performed, water on the protective film is completely removed before PEB, so spin drying before PEB, purging with dry air or nitrogen on the film surface, or water recovery nozzle on the stage after exposure It is preferable to dry or recover the water on the membrane by optimizing the shape and water recovery process. If the water on the protective film is completely removed before PEB, the water will suck out the acid in the resist into PEB, and there is little possibility that pattern formation cannot be performed.

  For the development, a paddle method using an alkaline aqueous solution, a dip method, or the like is used, and in particular, a paddle method using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is preferably used. Then, the substrate is rinsed with pure water and dried by spin drying or nitrogen blowing.

Next, the resist underlayer film and the substrate are etched by dry etching or the like using the photoresist film on which the resist pattern is formed as a mask. This etching can be performed by a conventional method. In addition to oxygen gas, inert gases such as He and Ar, and CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , and NO ₂ gas can also be added. If the substrate is SiO ₂ or SiN, Etching mainly using CFC-based gas, and etching mainly using chlorine-based or bromine-based gas are performed for polysilicon (p-Si), Al, and W. The resist underlayer film obtained from the resist underlayer film material of the present invention is characterized by a high etching rate when etching these substrates. By this etching, a pattern is formed on the substrate.

  In the above description, a photoresist composition is used as the resist film forming material. However, the resist underlayer film material of the present invention can resist resist undercut and undercut even when using electron beam exposure other than photolithography. It can be used to form a resist underlayer film for prevention.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these description.
AG monomers 1-8 (monomers 1-8) used in the following synthesis examples are shown below.

(Synthesis Example 1)
To the flask was added 3.9 g of AG monomer 1, 9.0 g of methacrylic acid 2,3-epoxypropyl ester, 3.1 g of styrene, and 20 g of tetrahydrofuran as a solvent. 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer shown below.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 1: Methacrylic acid 2,3-epoxypropyl ester: Styrene = 0.07: 0.63: 0.30
Molecular weight (Mw) = 9,200
Dispersity (Mw / Mn) = 1.92
This polymer is referred to as polymer 1 (polymer 1).

(Synthesis Example 2)
To the flask, 2.8 g of AG monomer 2, 9.0 g of methacrylic acid 2,3-epoxypropyl ester, 5.3 g of 4-hydroxyphenyl methacrylate, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer shown below.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: 4-hydroxyphenyl methacrylate = 0.07: 0.63: 0.30
Molecular weight (Mw) = 11,500
Dispersity (Mw / Mn) = 1.64
This polymer is referred to as polymer 2 (polymer 2).

(Synthesis Example 3)
To the flask, 4.8 g of AG monomer 3, 9.0 g of methacrylic acid 2,3-epoxypropyl ester, 5.3 g of 4-tbutoxystyrene, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer shown below.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 3: Methacrylic acid 2,3-epoxypropyl ester: 4-t butoxystyrene = 0.07: 0.63: 0.30
Molecular weight (Mw) = 8,800
Dispersity (Mw / Mn) = 1.84
This polymer is referred to as “polymer 3”.

(Synthesis Example 4)
To the flask was added 3.6 g of AG monomer 4, 12.1 g of 3,4-epoxycyclohexylmethyl methacrylate, 4.9 g of 4-acetoxystyrene, and 20 g of tetrahydrofuran as a solvent. 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 4: 3,4-epoxycyclohexylmethyl methacrylate: 4-acetoxystyrene = 0.08: 0.62: 0.30
Molecular weight (Mw) = 9,800
Dispersity (Mw / Mn) = 1.92
This polymer is referred to as polymer 4 (polymer 4).

(Synthesis Example 5)
In a flask, 3.4 g of AG monomer 5, 9.8 g of methacrylic acid (3-ethyl-3-oxetanyl) methyl, 6.3 g of α-hydroxymethylacrylic acid benzyl ester, 3-oxo-2,7-dioxatrimethacrylate Cyclo [4.2.1.0 ^4,8 ] nonan-9-yl (2.2 g) and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 5: Methacrylic acid (3-ethyl-3-oxetanyl) methyl: α-hydroxymethylacrylic acid benzyl ester: Methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl = 0.07: 0.53: 0.30: 0.10
Molecular weight (Mw) = 9,300
Dispersity (Mw / Mn) = 1.79
This polymer is designated as polymer 5 (polymer 5).

(Synthesis Example 6)
To the flask, 3.1 g of AG monomer 6, 9.2 g of methacrylic acid 2,3-epoxypropyl ester, 5.0 g of 3,5-difluorophenyl methacrylate, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 6: Methacrylic acid 2,3-epoxypropyl ester: Methacrylic acid 3,5-difluorophenyl = 0.10: 0.65: 0.25
Molecular weight (Mw) = 8,900
Dispersity (Mw / Mn) = 1.98
This polymer is referred to as polymer 6 (polymer 6).

(Synthesis Example 7)
To the flask, 5.7 g of AG monomer 7, 8.5 g of methacrylic acid 2,3-epoxypropyl ester, 4.9 g of phenyl methacrylate, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 7: Methacrylic acid 2,3-epoxypropyl ester: Phenyl methacrylate = 0.10: 0.60: 0.30
Molecular weight (Mw) = 9,700
Dispersity (Mw / Mn) = 1.79
This polymer is referred to as "polymer 7".

(Synthesis Example 8)
To the flask, 6.3 g of AG monomer 8, 8.5 g of methacrylic acid 2,3-epoxypropyl ester, 4.1 g of phenyl vinyl sulfide, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 8: Methacrylic acid 2,3-epoxypropyl ester: phenyl vinyl sulfide = 0.10: 0.60: 0.30
Molecular weight (Mw) = 10,300
Dispersity (Mw / Mn) = 1.63
This polymer is referred to as a polymer 8 (polymer 8).

(Synthesis Example 9)
2.8 g of AG monomer 2 in the flask, 9.0 g of methacrylic acid 2,3-epoxypropyl ester, methacrylic acid 4- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene-1 -9.8 g of yl and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: Methacrylic acid 4- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene-1-yl = 0.07 : 0.63: 0.30
Molecular weight (Mw) = 8,700
Dispersity (Mw / Mn) = 1.79
This polymer is referred to as "polymer 9".

(Synthesis Example 10)
To the flask, 2.8 g of AG monomer 2, 9.0 g of methacrylic acid 2,3-epoxypropyl ester, 5.1 g of phenyl vinyl sulfone, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer shown below.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: phenyl vinyl sulfone = 0.07: 0.63: 0.30
Molecular weight (Mw) = 9,500
Dispersity (Mw / Mn) = 1.89
This polymer is designated as polymer 10 (polymer 10).

(Synthesis Example 11)
To the flask, 2.8 g of AG monomer 2, 9.0 g of methacrylic acid 2,3-epoxypropyl ester, 4.6 g of phenyl vinyl sulfoxide, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: phenyl vinyl sulfoxide = 0.07: 0.63: 0.30
Molecular weight (Mw) = 8,600
Dispersity (Mw / Mn) = 1.96
This polymer is referred to as "polymer 11".

(Synthesis Example 12)
AG monomer 2 (4.0 g), methacrylic acid 2,3-epoxypropyl ester (12.8 g), and 20 g of tetrahydrofuran as a solvent were added to the flask. 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester = 0.1: 0.9
Molecular weight (Mw) = 9,600
Dispersity (Mw / Mn) = 1.69
This polymer is referred to as a polymer 12 (polymer 12).

(Synthesis Example 13)
8.8 g of AG monomer 2 in the flask, 7.1 g of methacrylic acid 2,3-epoxypropyl ester, methacrylic acid 1,1,1-trifluoro-2-hydroxy-6-methyl-2- (trifluoromethyl) heptane 6.7 g of -4-yl, 4.2 g of 2,4-difluorobenzyl methacrylate, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: 1,1,1-trifluoro-2-hydroxy-6-methyl-2- (trifluoromethyl) heptan-4-yl methacrylate: methacryl Acid 2,4-difluorobenzyl = 0.10: 0.50: 0.20: 0.20
Molecular weight (Mw) = 9,600
Dispersity (Mw / Mn) = 1.69
This polymer is referred to as a polymer 13 (polymer 13).

(Synthesis Example 14)
8.8 g of AG monomer 2 in the flask, 7.1 g of methacrylic acid 2,3-epoxypropyl ester, 8.7 g of methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5-yl, tetrahydrofuran as a solvent 20 g of was 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: Methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5-yl = 0.10: 0.50: 0.40
Molecular weight (Mw) = 9,900
Dispersity (Mw / Mn) = 1.95
This polymer is referred to as polymer 14 (polymer 14).

(Synthesis Example 15)
8.8 g of AG monomer 2 in the flask, 7.1 g of methacrylic acid 2,3-epoxypropyl ester, 9.9 g of methacrylic acid (2-oxo-2,3-dihydrobenzoxazol-5-yl), and tetrahydrofuran as a solvent 20 g was 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: Methacrylic acid (2-oxo-2,3-dihydrobenzoxazol-5-yl) = 0.10: 0.50: 0.40
Molecular weight (Mw) = 9,600
Dispersity (Mw / Mn) = 1.96
This polymer is referred to as a polymer 15 (polymer 15).

(Synthesis Example 16)
In a flask, 8.8 g of AG monomer 2, 7.1 g of methacrylic acid 2,3-epoxypropyl ester, 2-vinyl-6- (2,2,2-trifluoroethylcarbonyloxy) naphthalene 11.2 g, as a solvent 20 g of tetrahydrofuran was 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: 2-vinyl-6- (2,2,2-trifluoroethylcarbonyloxy) naphthalene = 0.10: 0.50: 0.40
Molecular weight (Mw) = 9,100
Dispersity (Mw / Mn) = 1.93
This polymer is referred to as a polymer 16 (polymer 16).

(Synthesis Example 17)
To the flask, 8.8 g of AG monomer 2, 7.1 g of methacrylic acid 2,3-epoxypropyl ester, 6.9 g of acenaphthylene, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: Methacrylic acid 2,3-epoxypropyl ester: acenaphthylene = 0.10: 0.50: 0.40
Molecular weight (Mw) = 6,100
Dispersity (Mw / Mn) = 1.79
This polymer is designated as polymer 17 (polymer 17).

(Synthesis Example 18)
To the flask, 8.8 g of AG monomer 2, 3.5 g of t-butoxystyrene, 11.9 g of acenaphthylene, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: t-butoxystyrene: acenaphthylene = 0.10: 0.20: 0.70
Molecular weight (Mw) = 6,900
Dispersity (Mw / Mn) = 1.73
This polymer is designated as polymer 18.

(Synthesis Example 19)
To the flask, 8.8 g of AG monomer 2, 9.5 g of 6-t-butoxy-2-vinylnaphthalene, 8.2 g of acenaphthylene, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio AG monomer 2: 6-t-butoxy-2-vinylnaphthalene: acenaphthylene = 0.10: 0.40: 0.50
Molecular weight (Mw) = 7,300
Dispersity (Mw / Mn) = 1.79
This polymer is referred to as a polymer 19 (polymer 19).

(Comparative Synthesis Example 1)
To a 100 mL flask was added 9.9 g of methacrylic acid 2,3-epoxypropyl ester, 3.1 g of styrene, and 20 g of tetrahydrofuran as a solvent. 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio Methacrylic acid 2,3-epoxypropyl ester: styrene = 0.7: 0.3
Molecular weight (Mw) = 9,800
Dispersity (Mw / Mn) = 1.81
This polymer is referred to as comparative polymer 1 (comparative polymer 1).

(Comparative Synthesis Example 2)
In a 100 mL flask, 11.3 g of methacrylic acid 6- [3,3,3-trifluoro-2-hydroxy-2-trifluoroethylpropyl] bicyclo [2,2,1] hept-2-yl, methacrylic acid 2 , 3-epoxypropyl ester 5.7 g, styrene 3.1 g, and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio 6- [3,3,3-trifluoro-2-hydroxy-2-trifluoroethylpropyl methacrylate] bicyclo [2,2,1] hept-2-yl: 2,3-epoxypropyl methacrylate Ester: styrene = 0.3: 0.4: 0.3
Molecular weight (Mw) = 9,600
Dispersity (Mw / Mn) = 1.73
This polymer is referred to as comparative polymer 2 (comparative polymer 2).

(Comparative Synthesis Example 3)
To a 100 mL flask were added 7.5 g of methacrylic acid 2,3-epoxypropyl ester, 8.1 g of 4-hydroxyphenyl methacrylate, and 20 g of tetrahydrofuran as a solvent. 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization composition ratio 2,3-epoxypropyl methacrylate: 4-hydroxyphenyl methacrylate = 0.50: 0.50
Molecular weight (Mw) = 9,800
Dispersity (Mw / Mn) = 1.81
This polymer is referred to as comparative polymer 3 (comparative polymer 3).

(Comparative Synthesis Example 4)
To a 100 mL flask, 7.5 g of methacrylic acid 2,3-epoxypropyl ester and 20 g of tetrahydrofuran 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, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Polymerization ratio Methacrylic acid 2,3-epoxypropyl ester = 1.0
Molecular weight (Mw) = 12,300
Dispersity (Mw / Mn) = 2.10
This polymer is referred to as comparative polymer 4 (comparative polymer 4).

(Preparation of resist underlayer film material)
The polymer shown by said polymers 1-19, the polymer shown by comparative polymers 1-4, the acid generator shown by the following TAG1, TAG2, and PAG1, the crosslinking agent shown by following CR1, CR2 are FC-4430 ( Resist underlayer film material (UDL-1) by dissolving in an organic solvent containing 0.1% by mass in a proportion shown in Tables 1 and 2 and filtering through a 0.1 μm fluororesin filter. -19 and comparative UDLs 1-7) were prepared respectively.

The resist underlayer film material (UDL 1-19, comparative UDL-1-7) prepared above was applied on a silicon substrate, baked at 210 ° C. for 60 seconds, UDL-1-16, 18, 19 and comparison UDL-1 to 6 formed a resist underlayer film (antireflection film) having a thickness of 80 nm, UDL-17 and comparative UDL-7 having a thickness of 10 nm.
After formation of the resist underlayer film, J.P. A. The refractive index (n, k) at a wavelength of 193 nm was determined with a spectroscopic ellipsometer (VASE) with variable incident angle from Woollam, and the results are shown in Tables 1 and 2 below.

Each composition in Tables 1 and 2 is as follows.
Polymers 1 to 19: From Synthesis Examples 1 to 19 Comparative Polymers 1 to 4: From Comparative Synthesis Examples 1 to 4 Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
CyH (cyclohexanone)

Cross-linking agent: CR1, CR2 (see structural formula below)

Acid generator: TAG1, TAG2, PAG1 (see the following structural formula)

  As shown in Table 1, in UDLs 1 to 16, 18, and 19, the n value of the refractive index of the resist underlayer film is in the range of 1.5 to 1.8, and the k value is in the range of 0.2 to 0.45. In particular, it can be seen that the film has an optimum refractive index (n) and extinction coefficient (k) sufficient to exhibit a sufficient antireflection effect at a film thickness of 30 nm or more.

Preparation of ArF resist 1 for evaluation of ArF patterning, carbon film material / carbon film polymer-containing lower layer film material Organic containing FC-4430 (manufactured by Sumitomo 3M) at 0.1% by mass of ArF resist polymer 1 in the proportions shown in Table 3 below. ArF resist 1 was prepared by dissolving in a solvent and filtering through a 0.1 μm fluororesin filter.

ArF resist polymer 1 (see the structural formula below)
Molecular weight (Mw) = 7,300
Dispersity (Mw / Mn) = 1.67

Acid generator: PAG2 (see structural formula below)

Basic compound: Quencher 1 (see the structural formula below)

Water repellent polymer (see structural formula below)
Molecular weight (Mw) = 8,800
Dispersity (Mw / Mn) = 1.75

Carbon membranes were prepared by dissolving each carbon membrane polymer in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co.) at a ratio shown in Table 4 and filtering with a 0.1 μm fluororesin filter. Materials 1 and 2 and carbon film polymer-containing lower layer film materials 1 and 2 were prepared.

The carbon film polymers 1 to 3 in Table 4 are shown below.
Carbon film polymer 1
Molecular weight (Mw) = 4,300
Dispersity (Mw / Mn) = 5.80
Carbon film polymer 2
Molecular weight (Mw) = 7,300
Dispersity (Mw / Mn) = 1.80
Carbon film polymer 3
Molecular weight (Mw) = 980
Dispersity (Mw / Mn) = 3.30

ArF patterning evaluation 1 (Examples 1-1 to 14, Comparative Examples 1-1 to 6)
The resist underlayer film material (UDL1-14, comparative UDL-1-6) prepared above is applied on a Si substrate and baked at 210 ° C. for 60 seconds to form a resist underlayer film (antireflection film) having a thickness of 90 nm. Formed. An ArF resist 1 was applied thereon and prebaked at 100 ° C. for 60 seconds to form a 90 nm-thick photoresist film. Using an ArF excimer laser scanner (manufactured by Nikon Corporation, NSR-S610C, NA1.30, σ0.98 / 0.78, 35 degree dipole illumination, azimuthally polarized illumination, 6% halftone phase shift mask) A pattern with a direction of 40 nm line and 80 nm pitch is exposed. After exposure, the pattern is immediately baked at 95 ° C. for 60 seconds, developed with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 30 seconds. Got a space pattern. The cross-sectional shape of the 40 nm line and space pattern of the obtained pattern was observed with an electron microscope (SEM). The results are shown in Table 5.

ArF patterning evaluation 2 (Examples 2-1 to 10, Comparative Examples 2-1 to 9)
Carbon film material 1 was applied on a Si substrate and baked at 180 ° C. for 60 seconds and then at 350 ° C. for 60 seconds to form carbon film 1 having a film thickness of 100 nm (Examples 2-1 to 4 and Comparative Example 2- 1-7).
The carbon film material 2 was applied on a Si substrate and baked at 100 ° C. for 60 seconds and then at 220 ° C. for 60 seconds to form a carbon film 2 having a thickness of 100 nm (Examples 2-5, 7, 8 and Comparative Examples). 2-8).
An amorphous carbon film having a thickness of 100 nm was formed by CVD (Example 2-6, Comparative Example 2-9).

  In Examples 2-1 to 8 and Comparative Examples 2-1 to 6, the resist underlayer film materials (UDL1, 2, 15, 16, 18, 19, comparative UDL-1 to 6) was applied and baked at 210 ° C. for 60 seconds to form a resist underlayer film (antireflection film) having a thickness of 70 nm. In Comparative Examples 2-7, 2-8, and 2-9, no resist underlayer film was formed.

  In Examples 2-9 and 2-10, the carbon film polymer-containing lower layer film material 1 and the carbon film polymer-containing lower layer film material 2 were applied on the Si substrate, then at 100 ° C. for 60 seconds, and then at 220 ° C. for 60 seconds. Baking was performed to form carbon underlayer-containing resist underlayer films 1 and 2 having a thickness of 100 nm. The surface of the carbon film polymer-containing resist underlayer film 1 is covered with a polymer 13 containing fluorine after coating. In the case of the carbon film polymer-containing resist underlayer film 2, the surface is covered with a polymer 16 after coating.

  An ArF resist was applied thereon and prebaked at 100 ° C. for 60 seconds to form a resist film having a thickness of 90 nm. Using an ArF excimer laser scanner (manufactured by Nikon Corporation, NSR-S610C, NA1.30, σ0.98 / 0.78, 35 ° dipole illumination, azimuthally polarized illumination, 6% halftone phase shift mask) A pattern with a direction of 40 nm line and 80 nm pitch is exposed. After exposure, the pattern is immediately baked at 95 ° C. for 60 seconds, developed with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 30 seconds. Got a space pattern. The cross-sectional shape of the 40 nm line and space pattern of the obtained pattern was observed with SEM. The results are shown in Table 6.

ArF patterning evaluation 3 (Examples 3-1, 2 and Comparative Examples 3-1-7)
The carbon film material 1 was applied on a Si substrate and baked at 180 ° C. for 60 seconds and then at 350 ° C. for 60 seconds to form a carbon film 1 having a thickness of 100 nm. A 35 nm SiON film was formed thereon by CVD. A resist underlayer film material (UDL-1, 2, comparative UDL-1 to 6) was applied on the SiON film and baked at 210 ° C. for 60 seconds to form a resist underlayer film (antireflection film) having a thickness of 70 nm. . In Comparative Example 3-7, no lower layer film was applied.
An ArF resist was applied thereon and prebaked at 100 ° C. for 60 seconds to form a resist film having a thickness of 90 nm. Using an ArF excimer laser scanner (manufactured by Nikon Corporation, NSR-S610C, NA1.30, σ0.98 / 0.78, 35 degree dipole illumination, azimuthally polarized illumination, 6% halftone phase shift mask) A pattern with a direction of 40 nm line and 80 nm pitch is exposed. After exposure, the pattern is immediately baked at 95 ° C. for 60 seconds, developed with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 30 seconds. Got a space pattern. The cross-sectional shape of the 40 nm line and space pattern of the obtained pattern was observed with SEM. The results are shown in Table 7.

Sidewall spacer formation (Examples 4-1 to 10, Comparative Examples 4-1 to 9)
A silicon oxide film having a thickness of 30 nm was formed on the photoresist pattern shown in Table 6 using a batch type ALD apparatus ALDINNA (registered trademark) manufactured by Hitachi Kokusai Electric, and the cross section of the formed pattern was observed by SEM. The results are shown in Table 8. Even after the formation of the silicon oxide film, the shape of the photoresist pattern after development was reflected as it was.

Preparation of EB Resist 1 for Electron Beam Patterning Evaluation EB resist polymer 1 was dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M) at the ratio shown in Table 9 below, and 0.1 μm fluorine EB resist 1 was prepared by filtering with a resin filter.

EB resist polymer 1
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.96

An electron beam patterning evaluation underlayer film material (UDL17, comparative UDL-7) was applied on a Si substrate and baked at 210 ° C. for 60 seconds to form a resist underlayer film having a thickness of 10 nm. An EB resist was spin-coated thereon and pre-baked on a hot plate at 110 ° C. for 60 seconds to produce a 100 nm resist film. To this, drawing in a vacuum chamber was performed at an HV voltage of 50 keV using HL-800D manufactured by Hitachi, Ltd.
Immediately after drawing, post-exposure baking (PEB) was performed on a hot plate for 95 seconds for 60 seconds, and paddle development was performed for 30 seconds with a 2.38 mass% TMAH aqueous solution to obtain a positive pattern. The cross-sectional shape of the 90 nm line and space pattern of the obtained pattern was observed. The results are shown in Table 10.

  As shown in Tables 5, 6, 7, 8, and 10, the resist film on the resist underlayer film (antireflection film) formed using the resist underlayer film material of the present invention has a rectangular shape and no tailing. It was confirmed that a good resist pattern was formed.

  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.

Claims (10)

A resist underlayer film material comprising a polymer compound having a repeating unit represented by the following general formula (1) and generating sulfonic acid by light and / or heat.

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, such as an ester group, an ether group, a lactone ring, a fluorine atom, It may have any of a cyano group, an aromatic group, a double bond, and a triple bond, R is a hydrogen atom or a fluorine atom, 0 <a ≦ 1.0, and M ⁺ is a sulfonium. , Iodonium, or ammonium.) The resist underlayer film material according to claim 1, wherein the sulfonic acid generated by light and / or heat is a sulfonic acid having a repeating unit represented by the following general formula (2).

(In the formula, R ¹ , R ² , R, and a are as described above.) M ⁺ in the general formula (1) is one or more selected from the following general formulas (M-1), (M-2), and (M-3). The resist underlayer film material according to claim 1 or 2.

(In the formula, 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 having 6 to 20 carbon atoms. An aryl group, and an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, and a part or all of hydrogen atoms of these groups are a fluorine atom, a trifluoromethyl group, an alkyl group, and an alkoxy group In addition, R ^101b and R ^101c may form a ring, and in the case of forming a ring, R ^101b and R ^101c are each an alkylene having 1 to 6 carbon atoms. ^.R 101d of the ^{proximal, R 101e, R 101f, 101g} R are each a hydrogen atom, the number 1 to 12 linear, branched or cyclic An alkyl group, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and a hydrogen atom of these groups R ^101d and R ^101e , R ^101d , R ^101e and R ^101f form a ring, part or all of which may be substituted by any of a fluorine atom, a trifluoromethyl group, an alkyl group and an alkoxy group. In the case of forming a ring, R ^101d and R ^101e , R ^101d , R ^101e and R ^{101f each} have an alkylene group having 3 to 10 carbon atoms or a nitrogen atom in the formula in the ring Represents a heteroaromatic ring.)   The resist underlayer film material according to any one of claims 1 to 3, wherein the resist underlayer film material has an antireflection film function.   The resist underlayer film material according to any one of claims 1 to 4, wherein the polymer compound further contains a repeating unit having an epoxy group and / or a hydroxyl group.   The resist underlayer film material according to any one of claims 1 to 5, wherein the polymer compound further contains a repeating unit having a light-absorbing group containing an aromatic ring.   The resist underlayer film material further contains at least one of an organic solvent, an acid generator, a basic compound, and a cross-linking agent. The resist underlayer film material described.   A method of forming a pattern on a substrate by lithography, wherein a resist underlayer film is formed on the substrate using at least the resist underlayer film material according to any one of claims 1 to 7, and the resist underlayer A photoresist film made of a photoresist composition is formed on the film, the pattern circuit region of the photoresist film is exposed, developed with a developer to form a resist pattern on the photoresist film, and the obtained resist Etching the resist underlayer film and the substrate using a pattern as a mask to form a pattern on the substrate.   A method for forming a pattern on a substrate by lithography, wherein at least an organic film is formed on the substrate, a silicon-containing film is formed on the organic film, and the silicon-containing film is formed on the silicon-containing film. A resist underlayer film is formed using the resist underlayer film material described in any one of 7 above, a photoresist film made of a photoresist composition is formed on the resist underlayer film, and a pattern circuit of the photoresist film is formed. After exposing the region, the resist film is developed with a developing solution to form a resist pattern, and the resist underlayer film and the silicon-containing film are etched using the resist pattern as a mask. The organic film is etched using the containing film as a mask, and the substrate is etched using the organic film on which the pattern is formed as a mask to form a pattern on the substrate. Pattern forming method and forming. A method of forming a pattern on a substrate by lithography, wherein at least a carbon film is formed on the substrate, and the resist underlayer film material according to any one of claims 1 to 7 is formed on the carbon film. A resist underlayer film is formed, a photoresist film is formed on the resist underlayer film, a pattern circuit region of the photoresist film is exposed, developed with a developer, and a resist pattern is formed on the photoresist film. Forming a silicon-containing film on a sidewall of the resist pattern, etching the resist underlayer film and the carbon film using the silicon-containing film as a mask, and forming a substrate using the carbon film on which the pattern is formed as a mask. A pattern forming method comprising forming a pattern on a substrate by etching.