JP4638378B2 - Resist underlayer film material and pattern forming method using the same - Google Patents

Description

The present invention relates to a resist underlayer film material of a multilayer 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 laser light (193 nm), F ₂ laser. The present invention relates to a resist underlayer film material of a multilayer resist film suitable for exposure with light (157 nm), Kr ₂ laser light (146 nm), Ar ₂ laser light (126 nm), soft X-ray, electron beam, ion beam, X-ray or the like. 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.

On the other hand, conventionally, it is known that a multilayer resist process is excellent for forming a high aspect ratio pattern on a stepped substrate such as a damascene process. This multi-layer resist process has been studied in order to overcome the decrease in etching resistance accompanying the progress of thinning of the resist with the rapid progress of miniaturization of pattern rules in recent years.
Such a multilayer resist process includes a two-layer resist process using a resist upper layer film containing silicon atoms on the resist lower layer film, and a resist intermediate containing silicon atoms between the resist upper layer film and the resist lower layer film. A three-layer resist process in which a layer film is applied can be given (for example, see Non-Patent Document 1).

  Of these, the silicon-containing resist intermediate layer film of the three-layer resist process may or may not have a function as an antireflection film, but the substrate reflection cannot be sufficiently suppressed. May further apply a normal organic antireflection film on the silicon-containing resist intermediate film. Therefore, the silicon-containing resist intermediate layer film having an antireflection function is more advantageous in terms of process simplicity because an organic antireflection film is unnecessary.

  In addition, the resist underlayer film of the three-layer resist process is required to have high dry etching resistance during processing of the substrate to be processed, an antireflection film function for suppressing substrate reflection, embedding characteristics in a high aspect substrate, and the like. In particular, materials having a high carbon content are being studied in order to improve dry etching resistance during substrate processing.

By the way, an insulating film having a dielectric constant lower than that of a silicon oxide film has been used since the 90 nm process, and a damascene process for embedding a copper wiring having a high electric conductivity has been applied. The dielectric constant of the insulating film is further lowered, and materials having a relative dielectric constant of 2.5 or less are being studied at 45 nm. Porous silica is promising as a material having a relative dielectric constant of 2.5 or less. Porous silica significantly reduces the relative dielectric constant by forming a hole having a relative dielectric constant of 1.0 in the film. Initially, there was a drawback that the mechanical strength decreased due to the presence of pores in the film, but the mechanical strength decrease was minimized by optimizing the hole structure, size and distribution, or improving the silica. Yes. However, a problem with porous silica is that basic substances are likely to be adsorbed by chemical treatment such as cleaning of the substrate. This basic substance is generated from the porous silica substrate during the lithography process, so that the acid in the resist is deactivated. In the positive resist, so-called poisoning occurs where undissolved or footing occurs where it should be dissolved. There was a problem.
For this reason, it is also important to construct a multilayer resist film in consideration of this poisoning problem.

  Further, the surface of the resist underlayer film after such a porous silica film is processed by dry etching is covered with a Teflon (registered trademark) -like layer that has been altered by a fluorocarbon dry etching gas. In this case, Teflon (registered trademark) is thermally and chemically stable and does not dissolve in the stripping solution, so that it is difficult to strip the resist underlayer film by chemical treatment. Therefore, the resist underlayer film is peeled off by ashing with oxygen gas, ammonia gas, hydrogen gas, etc., but ashing with a high-concentration gas for a long time is preferable because it alters the surface of the porous silica and lowers the dielectric constant. Absent.

  Therefore, in particular, a material having a high ashing speed is required as an embedding resist underlayer film directly on the porous silica.

Further, in the resist pattern after exposure and development on a mask substrate of Cr or the like, there is a problem that the positive photoresist has a trailing shape at the substrate interface. This is considered to be caused by a decrease in acid concentration in the photoresist in the vicinity of the substrate due to diffusion of acid generated in the photoresist by exposure to a mask substrate such as Cr. In order to reduce the tailing, improvements have been made by using a protecting group having a low activation energy for the deprotection reaction by acid, but it has not been sufficient. In order to reduce tailing, it is effective to use an organic film between the photoresist and the Cr substrate. In the case of light exposure, the organic film needs to have an antireflection function. However, since an electron beam (EB) is used for drawing a mask pattern, the antireflection function is not particularly necessary. What is required for the organic film is an excellent acid blocking function that prevents the acid generated in the photoresist from diffusing into the substrate, and a high etching speed.
As described above, when the mask substrate is exposed to an electron beam, a material capable of preventing the bottoming and undercut of the resist pattern is required as a resist underlayer film formed between the photoresist and the substrate.

J. et al. Vac. Sci. Technol. , 16 (6), Nov. / Dec. 1979

The present invention has been made in view of such problems, and is a resist underlayer film material for a multi-layer resist process, which has a high ashing speed after substrate etching. Therefore, the substrate directly under the ashing is altered. An object of the present invention is to provide a resist underlayer film material that can be prevented from being formed, and a method for forming a pattern on a substrate by lithography using the resist underlayer film material.
The present invention also provides a resist underlayer film material capable of preventing the bottoming and undercut of a resist pattern when a pattern is formed on a substrate using electron beam exposure, and a method of forming a pattern on a substrate by lithography using the resist underlayer film material The purpose is to provide.

（上記一般式（１）中、Ｒ¹は水素原子または一価の有機基である。） The present invention has been made to solve the above problems, and is a resist underlayer film material of a multilayer resist film used in lithography, and includes at least a polymer having α-hydroxymethyl acrylate as a repeating unit. A resist underlayer film material is provided . In this case, the repeating unit is preferably represented by the following general formula (1) .

(In the general formula (1), R ¹ is a hydrogen atom or a monovalent organic group.)

As described above, the resist underlayer film material of the present invention contains at least α-hydroxymethyl acrylate, in particular, a polymer having the general formula (1) as a repeating unit as a base resin. The resist underlayer film formed from such a resist underlayer film material has a high ashing speed after the substrate etching. For this reason, the resist underlayer film can be peeled off easily and quickly after the substrate etching. As described above, the resist underlayer film of the present invention requires a short ashing time, and therefore, even when the resist underlayer film is porous silica, it is possible to prevent alteration of the surface and to lower the relative dielectric constant. Can be minimized.
In addition, the resist underlayer film formed from such a resist underlayer film material can prevent skirting and undercut of the resist pattern when forming a pattern on the substrate using electron beam exposure, thus forming a highly accurate pattern. can do.

Moreover, the resist underlayer film material of the present invention may further contain one or more of water and organic solvents .

  Water or an organic solvent can be used for the resist underlayer film material of the present invention, and the polymer having the repeating unit is dissolved in these.

The resist underlayer film material of the present invention preferably further contains one or more of an acid generator and a crosslinking agent .

  As described above, the resist underlayer film material of the present invention contains one or more of a crosslinking agent and an acid generator, thereby promoting a crosslinking reaction in the resist underlayer film by baking after being applied to the substrate. You can do that. Therefore, the resist underlayer film formed from such a material is less likely to be intermixed with the resist upper layer film or the resist intermediate layer film, and the low molecular component is less diffused into the resist upper layer film.

The present invention is also 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 of the present invention, and a photoresist is formed on the underlayer film. A resist upper layer film of the composition is formed to form a two-layer resist film, the pattern circuit region of the two-layer resist film is exposed, and then developed with a developer to form a resist pattern on the resist upper layer film. The resist underlayer film is etched using the resist upper layer film formed as a mask, and the substrate is etched using at least the resist underlayer film formed as a mask to form a pattern on the substrate. Further, the resist underlayer film is formed by ashing. There is provided a pattern forming method characterized by peeling a film .

  The resist underlayer film material of the present invention can thus be used as a material for forming a resist underlayer film in a two-layer resist process. As described above, since the resist underlayer film of the present invention has a high ashing speed after etching the substrate, the ashing time can be short. For this reason, even when the resist underlayer film is porous silica, it is possible to prevent the surface of the porous silica from being altered by the gas used in ashing, and to minimize the decrease in the dielectric constant. it can.

The present invention is also a method of forming a pattern on a substrate by lithography, wherein at least a first resist underlayer film is formed on the substrate using the resist underlayer film material of the present invention, and the first resist A second resist underlayer film is formed on the lower layer film, a resist upper layer film of a photoresist composition is formed on the second resist underlayer film to form a two-layer resist film, and the two-layer resist film After the pattern circuit area is exposed, the resist pattern is formed on the resist upper film by developing with a developing solution, and the first and second resist lower films are etched using the resist upper film on which the pattern is formed as a mask. The substrate is etched using at least the first and second resist underlayer films on which the pattern is formed as a mask to form a pattern on the substrate, and the pattern is further formed by ashing. A pattern forming method and performing peeling strike underlayer film.

  Although the above method is also a two-layer resist process, the resist underlayer film is formed of the first and second layers. This is a particularly effective method when it is desired to further improve the etching resistance of the resist underlayer film in the dry etching of the substrate to be processed.

The present invention is also 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 of the present invention, and silicon atoms are formed on the underlayer film. A resist intermediate layer film containing a photoresist composition, forming a resist upper layer film of a photoresist composition on the intermediate layer film to form a three-layer resist film, and exposing a pattern circuit region of the resist three-layer film Thereafter, development is performed with a developer to form a resist pattern on the resist upper layer film, and the resist intermediate layer film is etched using the resist upper layer film on which the pattern is formed as a mask, so that at least the resist intermediate layer film on which the pattern is formed is formed. The resist underlayer film is etched using the mask, and the substrate is etched using at least the patterned resist underlayer film as a mask. Down to form further provides a pattern forming method, which comprises carrying out the peeling of the resist underlayer film by ashing.

  Thus, the resist underlayer film material of the present invention can also be used as a material for forming a resist underlayer film in a three-layer resist process. In the three-layer resist process, it is also possible to use a single-layer resist with high resolution as the resist upper layer film. For this reason, it is possible to form a pattern on the resist upper layer film and consequently the substrate with higher accuracy.

Furthermore, the present invention is a method for forming a pattern on a substrate by lithography, wherein at least a first resist underlayer film is formed on the substrate using the resist underlayer film material of the present invention, and the first resist underlayer film is formed. A second resist underlayer film is formed on the film, a resist intermediate layer film containing silicon atoms is formed on the second underlayer film, and a resist upper layer of a photoresist composition is formed on the intermediate layer film A film is formed to form a three-layer resist film, the pattern circuit region of the resist three-layer film is exposed, developed with a developer to form a resist pattern on the resist upper layer film, and the resist on which the pattern is formed The resist intermediate layer film is etched using the upper layer film as a mask, and the first and second resist lower layer films are etched using at least the resist intermediate layer film on which the pattern is formed as a mask. The pattern is formed by etching the substrate using the first and second resist underlayer films on which the pattern is formed as a mask to form a pattern on the substrate, and further removing the resist underlayer film by ashing Provide a method .

  Although the above method is also a three-layer resist process, the resist underlayer film is formed of the first and second layers. This is a particularly effective method when it is desired to further improve the etching resistance of the resist underlayer film in the dry etching of the substrate to be processed.

In the pattern forming method, the pattern circuit area can be exposed using an electron beam .
The resist underlayer film formed from the resist underlayer film material of the present invention can prevent the bottoming and undercut of the resist pattern when the pattern is formed on the substrate using electron beam exposure, so that a highly accurate pattern can be formed. Can do.

As described above, the resist underlayer film material of the present invention includes at least α-hydroxymethyl acrylate, that is, a polymer having the above general formula (1) as a repeating unit as a base resin. The speed is fast. For this reason, since the resist underlayer film can be peeled off in a short time by ashing after the substrate processing, there is little fear that the substrate surface is altered or the relative dielectric constant is lowered by the ashing for a long time.
In addition, if the resist underlayer film formed from the resist underlayer film material of the present invention is used when a pattern is formed on the substrate using electron beam exposure, the acid generated in the photoresist due to the exposure is diffused to the substrate. Since the resist pattern can be prevented from skirting or undercutting, a highly accurate pattern can be formed.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these.
The present inventors have intensively studied to develop a resist underlayer film material having a high ashing speed after substrate etching.
As described above, conventionally, a resist underlayer film having high resistance to dry etching during substrate processing has been studied. In order to increase dry etching resistance during substrate processing, a material having a high carbon ratio has been preferred. However, the resist underlayer film having improved dry etching resistance by increasing the carbon ratio has a disadvantage that the ashing speed is slow.
As a result of the study, the present inventors have found that a material having a low carbon ratio and a high oxygen or nitrogen ratio is suitable for increasing the ashing rate.

Examples of the material having a low carbon ratio and a high oxygen or nitrogen ratio include water-soluble polymers.
The atomic composition ratios of monomers constituting the repeating units of various water-soluble polymers are shown below. Of these, it can be seen that the α-hydroxymethyl acrylate has a lower carbon ratio than acrylic acid, methacrylic acid, and vinyl alcohol.

  In view of the above, the present inventors have described that if the resist underlayer film material contains at least a polymer having α-hydroxymethylacrylic acid or α-hydroxymethyl acrylate having a low proportion of carbon as a repeating unit, the resist underlayer film material The resist underlayer film formed from the film material has a high ashing speed, and in particular, it can be easily and quickly peeled off from the porous silica, thus completing the present invention.

  Moreover, the present inventors provide a resist underlayer film formed from the resist underlayer film material between the substrate and the photoresist, so that the acid generated in the photoresist by the exposure of the resist underlayer film diffuses into the substrate. When the resist underlayer film material is used to form a pattern on a substrate using electron beam exposure, because the resist pattern can be prevented from being skirted or undercut caused by lowering the acid concentration in the photoresist. As a result, the present invention was completed.

（上記一般式（１）中、Ｒ¹は水素原子または一価の有機基である。） That is, the resist underlayer film material of the present invention is a resist underlayer film material of a multilayer resist film used in lithography, and contains at least a polymer having α-hydroxymethyl acrylate as a repeating unit. Moreover, as this repeating unit, what is shown by following General formula (1) can be mentioned.

(In the general formula (1), R ¹ is a hydrogen atom or a monovalent organic group.)

When a hole having a high aspect ratio is formed on the substrate to be processed, it must be sufficiently filled up to the bottom of the hole when coating the lower layer film. In order to improve the embedding property, it is necessary to lower the glass transition point (Tg) of the polymer. In order to lower the glass transition point (Tg), it is effective to replace the hydrogen atom of R ^{1 in} the general formula (1) with a monovalent organic group. Especially when substituted with an acid labile group, the embedding property is high at the time of spin coating, and the deprotection of the acid labile group proceeds simultaneously with the crosslinking of the polymer by acid or heat after spin coating, the carbon ratio decreases, There is an advantage that the ashing speed is improved.

Examples of the monovalent organic group for R ¹ include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and hydroxy groups. Examples thereof include an adhesive group having a group, an ester, an ether, and a lactone, and an acid labile group.

（上記式中、Ｍｅはメチル基を示す。） Examples of the adhesive group include the following.

(In the above formula, Me represents a methyl group.)

Examples of the acid labile group include groups represented by the following formulas (AL10) and (AL11), tertiary alkyl groups having 4 to 40 carbon atoms represented by the following formula (AL12), and those having 1 to 6 carbon atoms. A trialkylsilyl group, an oxoalkyl group having 4 to 20 carbon atoms, and the like are preferable.

In the above formulas (AL10) and (AL11), R ⁶ and R ⁹ are linear, branched, and cyclic alkyl groups, aryl groups, and aralkyl groups having 1 to 20 carbon atoms, such as oxygen, sulfur, nitrogen, and fluorine. Of heteroatoms. a is an integer of 0-10. R ⁷ and R ⁸ are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may include heteroatoms such as oxygen, sulfur, nitrogen, and fluorine. R ⁷ and R ⁸ , R ⁷ and R ⁹ , R ⁸ and R ⁹ may be bonded to form a ring.
In the above formula (AL12), R ¹⁰ , R ¹¹ and R ¹² are each a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Indicates a group. R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹⁰ and R ¹² may be bonded to each other to form a ring.

  Specific examples of the compound represented by the formula (AL10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl. Groups, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, and substituents represented by the following general formulas (AL10) -1 to (AL10) -9.

（上記式中、Ｒ^２０は同一又は非同一の炭素数１〜８の直鎖状、分岐鎖状または環状のアルキル基、炭素数６〜２０のアリール基、アラルキル基を示す。Ｒ^２１は存在しないかあるいは炭素数１〜２０の直鎖状、分岐鎖状または環状のアルキル基を示す。Ｒ^２２は炭素数６〜２０のアリール基、アラルキル基を示す。）

(In the above formula, R ²⁰ represents the same or non-identical linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms, and aralkyl group. R ²¹ is present. Or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ²² represents an aryl group or aralkyl group having 6 to 20 carbon atoms.)

Examples of the compound represented by the above formula (AL11) include the following (AL11) -1 to (AL11) -23.

（上記式中、Ｒ^２０は同一又は非同一の炭素数１〜８の直鎖状、分岐鎖状または環状のアルキル基、炭素数６〜２０のアリール基、アラルキル基を示す。Ｒ^２１、Ｒ^２３は存在しないかあるいは炭素数１〜２０の直鎖状、分岐鎖状または環状のアルキル基を示す。Ｒ^２２は炭素数６〜２０のアリール基、アラルキル基を示す。） As the tertiary alkyl group represented by the above formula (AL12), for example, a tert-butyl group, a triethylcarbyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, 2- (2 -Methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group, etc. or the following general formulas (AL12) -1 to (AL12) -18 can be mentioned.

(In the above formula, R ²⁰ represents the same or non-identical linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group. R ²¹ , R ²³ is not present or represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ²² represents an aryl group or aralkyl group having 6 to 20 carbon atoms.

R ²⁰ , R ²¹ , R ²² , and R ²³ may have heteroatoms such as oxygen, nitrogen, and sulfur. Specific examples thereof include the following (13) -1 to (13) -7. Can be mentioned.

  Examples of the trialkylsilyl group having 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group and the like.

The resist underlayer film material of the present invention contains at least a polymer having α-hydroxymethyl acrylate as a repeating unit as a base resin, but other olefin compounds, specifically (meth) acrylic acid derivatives, hydroxystyrene derivatives, It may be copolymerized with vinyl ether derivatives, styrene derivatives, vinyl naphthalene, vinyl anthracene, vinyl carbazole, maleic anhydride, maleimide derivatives, itaconic acid derivatives, itaconic anhydride, indene, acenaphthylene and the like.
In this case, the proportion of the other olefin compound is preferably 0 to 90 mol%, more preferably 0 to 80 mol%.

In addition, the resist underlayer film material of the present invention contains at least a polymer having α-hydroxymethyl acrylate as a repeating unit. In addition, for example, cresol novolacs, acrylic derivatives, vinyl alcohol, vinyl ethers, allyl ethers, Styrene derivatives, allylbenzene derivatives, olefins such as ethylene, propylene and butadiene, and polymers by metathesis ring-opening polymerization can also be blended.
In this case, the blend ratio is 10 to 1000 parts by mass with respect to 100 parts by mass of the polymer according to the present invention.

  As in the present invention, a resist underlayer film material containing a polymer having α-hydroxymethyl acrylate as a repeating unit as a base resin has a feature that the peeling speed is high in peeling by ashing after substrate processing. In particular, ashing peeling on a low dielectric constant film material such as porous silica is easy and quick.

  The resist underlayer film of the present invention is used as a resist underlayer film for a multilayer resist process, in particular, a high energy ray having a wavelength of 300 nm or less, specifically, an excimer laser of 248 nm, 193 nm, 157 nm, or a soft X-ray of 3-20 nm. It can be suitably used for lithography using electron beam and X-ray.

  Here, there are cases where it is desired to further improve the etching resistance of the resist underlayer film in the dry etching of the substrate to be processed. In this case, it is preferable to form a second resist underlayer film having higher etching resistance on the resist underlayer film of the present invention.

  Such a second resist underlayer film can be formed of a material containing a carbon-containing compound having a carbon content of 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more as a base. . Examples of the carbon-containing compound used for the second resist underlayer film include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, and 3,4-dimethyl. Phenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-t-butylphenol, 3-t -Butylphenol, 4-t-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol , Resorcinol, 2-methyl resorci 4-methylresorcinol, 5-methylresorcinol, catechol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropyl Phenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4 '-(9H-fluorene-9- Ylidene) bisphenol, 2,2′dimethyl-4,4 ′-(9H-fluorene-9-ylidene) bisphenol, 2,2′diallyl-4,4 ′-(9H-fluorene-9-ylidene) bisphenol, 2, 2′difluoro-4,4 ′-(9H Fluorene-9-ylidene) bisphenol, 2,2′diphenyl-4,4 ′-(9H-fluorene-9-ylidene) bisphenol, 2,2′dimethoxy-4,4 ′-(9H-fluorene-9-ylidene) Bisphenol, 2,3,2 ′, 3′-tetrahydro- (1,1 ′)-spirobiindene-6,6′-diol, 3,3,3 ′, 3′-tetramethyl-2,3,2 ', 3'-tetrahydro- (1,1')-spirobiindene-6,6'-diol, 3,3,3 ', 3', 4,4'-hexamethyl-2,3,2 ', 3 '-Tetrahydro- (1,1')-spirobiindene-6,6'-diol, 2,3,2 ', 3'-tetrahydro- (1,1')-spirobiindene-5,5'- Diol, 5,5′-dimethyl-3,3,3 ′, 3′-te Tramethyl-2,3,2 ′, 3′-tetrahydro- (1,1 ′)-spirobiindene-6,6′-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4- Dihydroxynaphthalene such as methoxy-1-naphthol, 7-methoxy-2-naphthol and 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, methyl 3-hydroxy-naphthalene-2-carboxylate , Indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, Re Novolak resins such as monene, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly (meth) Examples thereof include acrylates and copolymers thereof.

  Moreover, you may add water, an organic solvent, an acid generator, a crosslinking agent, etc. to the resist underlayer film material of this invention so that it may demonstrate below.

  One of the performances required for the lower layer film including the antireflection film is that there is no intermixing with the upper layer film and that no low molecular component diffuses into the upper layer film [Proc. SPIE Vol. 2195, p225-229 (1994)]. In order to prevent these problems, a method is generally employed in which thermal crosslinking is performed by baking after spin coating of the antireflection film. Therefore, it is preferable to add a crosslinking agent as a component of the antireflection film material. In this case, in addition to the method of using it as an additive as it is, a method of introducing a crosslinkable substituent into the polymer may be used.

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

Examples of the epoxy compound among the various compounds include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether and the like. 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, and 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, and a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, tetramethylolguanamine 1 Examples include compounds in which 4 methylol groups are acyloxymethylated and mixtures thereof. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 of the methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, tetramethylolglycoluril Or a mixture thereof in which 1 to 4 of the methylol groups are acyloxymethylated. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or 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.

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, decahydronaphthalene- 2,6-diol, [1,1′-bicyclohexyl] -3,3 ′, 4,4′-teto Alcohol group-containing compounds such as hydroxy, bisphenol, methylene bisphenol, 2,2′-methylene bis [4-methylphenol], 4,4′-methylidene-bis [2,6-dimethylphenol], 4,4 ′-(1 -Methyl-ethylidene) bis [2-methylphenol], 4,4'-cyclohexylidene bisphenol, 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-ethane Yl) 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 ′ ″-(1, 2 Ethanediylidene) tetrakisphenol, 4,4 ′, 4 ″, 4 ′ ″-ethanediylidene) tetrakis [2-methylphenol], 2,2′-methylenebis [6-[(2-hydroxy-5-methylphenyl) methyl ] -4-methylphenol], 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidyne) tetrakisphenol, 2,4,6-tris (4-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 [(5 −Me Adding a cross-linking agent in which the hydroxy group of a phenolic low nucleus such as (l-2-hydroxyphenyl) methyl]-[(1,1′-biphenyl) -4,4′-diol] is substituted with glycidyl ether You can also.

  The blending amount of the crosslinking agent in 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 risk of mixing with the upper layer film, and if it is 50 parts or less, there is little risk of cracking in the film after crosslinking.

In addition, when the repeating unit of the polymer contained in the resist underlayer film material is α-hydroxymethylacrylic acid, in the presence of an acid, intermolecular crosslinking or intramolecular reaction may occur due to the condensation reaction shown below. Therefore, the cross-linking agent is not always necessary.

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

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

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

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, part or all of hydrogen atoms of these groups may be substituted by an alkoxy group, etc. R ^101b and R ^{101c May} form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, K ⁻ represents a non-nucleophilic counter ion, R ^101d , R ^101e , R ^101f , and R ^101g are represented by adding a hydrogen atom to R ^101a , R ^101b , and R ^101c , R ^101d and R ^101e , and R ^101d , R ^101e, and R ^101f may form a ring. In the case of forming a ring, R ^101d and R ^101e and R ^101d and R ^{10 1e} and R ^101f represent an alkylene group having 3 to 10 carbon atoms.)

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f and R ^101g may be the same as or different from each other. Specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl Group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. Arylsulfonates such as 4-fluorobenzenesulfonate, 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.

上記一般式（Ｋ−１）中、Ｒ^１０２は水素原子、炭素数１〜２０の直鎖状、分岐状、環状のアルキル基、アシル基、炭素数２〜２０のアルケニル基、炭素数６〜２０のアリール基、アリーロキシ基である。上記一般式（Ｋ−２）中、Ｒ^１０３は水素原子、炭素数１〜２０の直鎖状、分岐状、環状のアルキル基、炭素数２〜２０のアルケニル基、炭素数６〜２０のアリール基である。

In the general formula (K-1), R ¹⁰² 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, or 6 to 6 carbon atoms. 20 aryl groups and aryloxy groups. In general formula (K-2), R ¹⁰³ represents 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, or an aryl having 6 to 20 carbon atoms. It is a group.

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

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

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

Specific examples of 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, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is the formula (P1a-1), can be exemplified the same ones as described in (P1a-2) and (P1a-3).

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

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

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

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を示す。Ｒ^１０５は、Ｐ２式のものと同様である。）

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

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

（式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

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

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

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

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

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

  Specifically, examples of the onium salt include tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, p- Tetramethylammonium toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) Phenyl iodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert- Toxiphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfone Acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid Triphenylsulfonium, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, p-toluenesulfone Trimethylsulfonium, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, trifluoro Dicyclohexylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [methyl (2-oxo Cyclopentyl) sulfonium trifluoromethanesulfo Nate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, triethylammonium nonaflate, tributylammonium nonaflate, tetraethylammonium nonaflate, tetrabutylammonium nonaflate, triethylammonium bis (trifluoromethylsulfonyl) imide, Examples include onium salts such as triethylammonium tris (perfluoroethylsulfonyl) methide.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, and 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-amino) Sulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane And diazomethane derivatives.

  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 include glyoxime derivatives such as bis -O- (camphorsulfonyl)-.alpha.-dimethylglyoxime.

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

Examples of the β-ketosulfone derivative 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.

Among them, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p -Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonic acid Arm, 1,2'-naphthyl carbonyl methyl tetrahydrothiophenium triflate onium salts such as,
Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis ( diazomethane derivatives such as n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane,
Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime,
Bissulfone derivatives such as bisnaphthylsulfonylmethane,
N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid A sulfonic acid ester derivative of an N-hydroxyimide compound such as an ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, or N-hydroxynaphthalimide benzenesulfonic acid ester is preferably used.

  In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types.

  The addition amount of the acid generator is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts with respect to 100 parts of the base resin. If the amount is 0.1 part or more, the amount of acid generated is sufficient and the crosslinking reaction is unlikely to be insufficient. If the amount is 50 parts or less, there is little possibility of mixing due to the acid moving to the upper resist.

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

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

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

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

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

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

  The compounding amount of the basic compound is suitably 0.001 to 2 parts, particularly 0.01 to 1 part, based on 100 parts of the total base resin. If the blending amount is 0.001 part or more, a sufficient blending effect is obtained, and if it is 2 parts or less, there is little possibility that all the acid generated by heat will be trapped and not crosslinked.

Examples of the solution that can be used in the resist underlayer film forming material of the present invention include water and organic solvents.
The organic solvent is not particularly limited as long as the polymer containing the α-hydroxymethyl acrylate as a repeating unit, an acid generator, a crosslinking agent, and other additives can be dissolved. 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. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and a mixed solvent thereof are preferably used.

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

In addition to the above, an alcohol-based organic solvent can also be added to the resist underlayer film material of the present invention. Specifically, a monovalent alcohol having 1 to 7 carbon atoms is preferably used. Specifically, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-heptyl alcohol, allyl alcohol, crotyl alcohol, cyclohexyl Although alcohol and benzyl alcohol are mentioned, isopropyl alcohol is particularly preferred.
The addition amount of the alcohol organic solvent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of water.

  The alcohol-based organic solvent has an effect of reducing microbubbles in the aqueous solution as shown in JP-A-9-34115. Microbubbles in the solution of the water-soluble material cause pattern defects. For example, Japanese Patent Application Laid-Open No. 9-6007 introduces the addition of acetylene alcohol to prevent microbubbles.

  The acetylene alcohol shown here can be represented by the following general formulas AA-1 and AA-2.

（上記式中、Ｒ^１１〜Ｒ^１４、Ｒ^１７、Ｒ^１８は互いに同一又は異種の炭素数１〜２０のアルキル基を示し、Ｒ^１５、Ｒ^１６、Ｒ^１９は互いに同一又は炭素数１〜１０のアルキレン基を示し、ａ及びｂはそれぞれａ＋ｂ＝０〜６０となる整数、ｃは０〜３０の整数である。）

(In the above formula, R ^{11 to} R ¹⁴ , R ¹⁷ and R ¹⁸ represent the same or different alkyl group having 1 to 20 carbon atoms, and R ¹⁵ , R ¹⁶ and R ¹⁹ are the same or have 1 to 10 carbon atoms. And a and b are each an integer such that a + b = 0 to 60, and c is an integer of 0 to 30.)

A surfactant can also be added to the resist underlayer film material of the present invention. The acetylene alcohols described in the organic solvent are also effective as a surfactant, but other surfactants can be added. Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monovalmitate, sorbitan monostearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monovalmitate, polyoxyethylene sorbitan monostearate Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tochem Products), MegaFuck F171, F172, F173 ( Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431, FC4430 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10 , Fluorosurfactants such as KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP-341, X-70-092, X-70-0 3 (Shin-Etsu Chemical), acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (Kyoeisha Oil Chemical Co., Ltd.). Further, surfactants having a perfluoroalkyl ether group described in JP-A-9-43838 and JP-A-2001-125259 can be mentioned.
These can be used alone or in combination of two or more. The addition amount of the surfactant is preferably in the range of 0.0001 to 5% of water or the organic solvent.

  The present invention is also 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 of the present invention, and silicon atoms are formed on the underlayer film. A resist intermediate layer film containing a photoresist composition, forming a resist upper layer film of a photoresist composition on the intermediate layer film to form a three-layer resist film, and exposing a pattern circuit region of the resist three-layer film Thereafter, development is performed with a developer to form a resist pattern on the resist upper layer film, and the resist intermediate layer film is etched using the resist upper layer film on which the pattern is formed as a mask, so that at least the resist intermediate layer film on which the pattern is formed is formed. The resist underlayer film is etched using the mask, and the substrate is etched using at least the patterned resist underlayer film as a mask. Down to form further provides a pattern forming method, which comprises carrying out the peeling of the resist underlayer film by ashing.

  Furthermore, the present invention is a method of forming a pattern on a substrate by lithography, wherein at least a first resist underlayer film is formed on the substrate using the resist underlayer film material of the present invention, and the first resist A second resist lower layer film is formed on the lower layer film, a resist intermediate layer film containing silicon atoms is formed on the second lower layer film, and a photoresist composition resist is formed on the intermediate layer film. An upper layer film was formed to form a three-layer resist film, the pattern circuit region of the resist three-layer film was exposed, and developed with a developing solution to form a resist pattern on the resist upper layer film, whereby the pattern was formed The resist intermediate layer film is etched using the resist upper layer film as a mask, and the first and second resist lower layer films are etched using at least the resist intermediate layer film on which the pattern is formed as a mask. The pattern is formed on the substrate by etching the substrate using the first and second resist underlayer films having at least a pattern as a mask, and the resist underlayer film is peeled off by ashing. A forming method is also provided.

These three-layer resist processes will be described more specifically with reference to FIGS.
First, as shown in FIGS. 1A and 2A, on a substrate 10, a (first) resist underlayer film 11, a (second resist underlayer film 15), a resist intermediate layer film 12, and a resist are formed. An upper layer film 13 is formed.
The resist underlayer film 11 of the present invention can be formed on the substrate to be processed 10 by a spin coat method or the like, similarly to the photoresist. After spin coating, it is desirable to evaporate the solvent and perform baking to promote the crosslinking reaction in order to prevent mixing with the resist intermediate layer film 12. 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 11 is appropriately selected, it is preferably 30 to 20,000 nm, particularly 50 to 15,000 nm.

After this resist underlayer film 11 is formed, a second resist underlayer film 15 having higher etching resistance may be formed thereon as shown in FIG. 2, or silicon as shown in FIG. A resist intermediate layer film 12 containing may be formed.
Although the resist underlayer film 11 of the present invention has a feature of a high ashing speed, there are cases where it is desired to further improve the resistance of the substrate 10 to be processed in dry etching. In that case, as shown in FIG. 2, a second resist underlayer film 15 having high etching resistance is formed on the first resist underlayer film 11 of the present invention, and a resist intermediate layer film is further formed thereon. The method of forming 12 is preferably taken.
A resist upper layer film 13 of a photoresist composition is formed on the silicon-containing resist intermediate layer film 12, and an organic antireflection film is formed below the resist upper layer film 13 (on the silicon-containing resist intermediate layer film 12). A film may be formed.

  When the resist upper layer film 13 is formed from a photoresist composition, the spin coating method is preferably used as in the case of forming the resist lower layer film 11. Then, after the resist upper layer film 13 is formed by a spin coating method or the like, pre-baking is performed. The thickness of the resist upper layer film 13 is not particularly limited, but is preferably 30 to 500 nm, particularly 50 to 400 nm.

Here, as the material for forming the (first) resist underlayer film 11, as described above, the resist underlayer film material of the present invention containing at least a polymer having α-hydroxymethyl acrylate as a repeating unit is used. .
Furthermore, as a material for forming the second resist underlayer film 15, as described above, a material having a high etching resistance with a carbon content of 50% by mass or more is preferably used.

Further, as the silicon-containing resist intermediate layer film 12 for the three-layer resist process, a silsesquioxane-based resist intermediate layer film is preferably used.
By making the resist intermediate layer film effective as an antireflection film, reflection can be further suppressed. In particular, for exposure at 193 nm, when the resist underlayer film containing α-hydroxymethyl acrylate as a repeating unit has no absorbing group, substrate reflection can be reduced to 0.5% or less by suppressing reflection with the resist intermediate layer film. As the resist intermediate layer film having an antireflection effect, an anthracene is preferably used for exposure at 248 nm and 157 nm, and a silsesquioxane having a phenyl group or a silicon-silicon bond and being crosslinked with acid or heat is preferably used for exposure at 193 nm. It is done.

Further, as the resist intermediate layer film, a resist intermediate layer film formed by a chemical vapor deposition (CVD) method can also be used. As a silicon-containing resist intermediate layer film formed by CVD, an SiON film is known as an antireflection film.
However, the formation of the resist intermediate film by the spin coating method has an advantage that there is no cost for introducing the CVD apparatus than the CVD method.

Further, as the photoresist composition for forming the resist upper layer film 13, a known composition can be used.
The resist upper layer film 13 in the three-layer resist process may be either a positive type or a negative type, and the same one as a commonly used single layer resist can be used.

Next, as shown in FIGS. 1B and 1C and FIGS. 2B and 2C, exposure and development are performed.
After the resist upper layer film 13 is formed as described above, exposure 14 is performed according to a conventional method (see FIGS. 1B and 2B), post-exposure baking (PEB), development is performed, and a resist pattern is formed. (See FIG. 1 (c), FIG. 2 (c)).

Next, as shown in FIGS. 1D and 2D, the silicon-containing resist intermediate film 12 is etched using the obtained resist pattern as a mask.
At this time, it is preferable to use a fluorocarbon gas. Examples of the fluorocarbon gas include CF ₄ , CHF ₃ , C ₂ F ₆ , C ₂ F ₄ , C ₃ F ₁₀ , C ₃ F ₈ , C ₄ F ₁₀ , and C ₄ F ₈ .

Next, as shown in FIG. 1E and FIG. 2E, the (first) resist underlayer film 11 (and the second resist underlayer film 15) is formed using the silicon-containing resist intermediate layer film 12 as a mask. Etching is performed.
The gas used at this time is oxygen, hydrogen, ammonia gas, or the like. In addition to oxygen gas or the like, it is also possible to add an inert gas such as He or Ar, or CO, CO ₂ , SO ₂ , N ₂ , or NO ₂ gas. In particular, the latter gas is used for side wall protection for preventing undercut of the pattern side wall.

Next, as shown in FIGS. 1F and 2F, the substrate 10 is etched.
Etching of the substrate 10 can also be performed by a conventional method. For example, if the substrate 10 is a SiO ₂ , SiN, or silica-based low dielectric constant film, etching is mainly performed using a fluorocarbon gas, and p-Si, Al, or W is performed using mainly a chlorine-based or bromine-based gas. . When the substrate processing is etched with chlorofluorocarbon gas, the silicon-containing resist intermediate film 12 is peeled off simultaneously with the processing of the substrate 10 to be processed.

Next, as shown in FIGS. 1G and 2G, ashing is performed to remove the resist underlayer film 11 and the like.
Ashing for removing the resist underlayer film 11 and the like can be performed using oxygen, hydrogen gas, or the like.
The resist underlayer film 11 formed from the resist underlayer film material of the present invention has a very high ashing speed.

As shown in FIGS. 1 and 2, the substrate 10 may be composed of a base layer 10b and a layer to be processed 10a. The base layer 10b of the substrate 10 is not particularly limited, and is a layer to be processed (substrate to be processed) 10a made of Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, or the like. Different materials are used. The layer to be processed _{10a, Si, SiO 2, SiON} , SiN, p-Si, α-Si, W, W-Si, Al, Cu, various low dielectric Al-Si, etc. (Low-k) film and A stopper film is used, and can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.
Since the resist underlayer film of the present invention has a high ashing speed and a short ashing time, it is particularly effective for processing a low-K film such as porous silica.

  The present invention is also 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 of the present invention, and a photoresist is formed on the underlayer film. A resist upper layer film of the composition is formed to form a two-layer resist film, the pattern circuit region of the two-layer resist film is exposed, and then developed with a developer to form a resist pattern on the resist upper layer film. The resist underlayer film is etched using the resist upper layer film formed as a mask, and the substrate is etched using at least the resist underlayer film formed as a mask to form a pattern on the substrate. Further, the resist underlayer film is formed by ashing. There is also provided a pattern forming method characterized in that the film is peeled off.

  The present invention is also a method of forming a pattern on a substrate by lithography, wherein at least a first resist underlayer film is formed on the substrate using the resist underlayer film material of the present invention, and the first resist A second resist underlayer film is formed on the lower layer film, a resist upper layer film of a photoresist composition is formed on the second resist underlayer film to form a two-layer resist film, and the two-layer resist film After the pattern circuit area is exposed, the resist pattern is formed on the resist upper film by developing with a developing solution, and the first and second resist lower films are etched using the resist upper film on which the pattern is formed as a mask. The substrate is etched using at least the first and second resist underlayer films on which the pattern is formed as a mask to form a pattern on the substrate, and the pattern is further formed by ashing. A pattern forming method and performing peeling strike underlayer film.

Thus, the resist underlayer film material of the present invention can also be used as a material for forming a resist underlayer film in a two-layer resist process.
The two-layer resist process will be described more specifically with reference to FIGS.
First, as shown in FIGS. 3A and 4A, the (first) resist underlayer film 11, (second resist underlayer film 15), and resist upper layer film 13 of the present invention are formed on a substrate 10. Form.
In the two-layer resist process, the resist intermediate layer film 12 as described in the three-layer resist process of FIGS. 1 and 2 is not provided, and the resist upper layer film 13 and the resist lower layer film 11 (, 15) are formed.
As the resist upper layer film 13, a polymer containing silicon is used. Examples of the silicon-containing polymer include silsesquioxane, a vinyl silane derivative, and a siloxane pendant acrylic.
The resist underlayer films 11 and 15 are the same as described in the three-layer resist process.

Next, as shown in FIGS. 3B, 3C, 4B, and 4C, exposure 14 and development are performed to obtain a resist pattern.
Next, as shown in FIGS. 3D and 4D, etching of the (first) resist underlayer film 11 (and the second resist underlayer film 15) is performed using the silicon-containing resist upper layer film 13 as a mask. I do.
Next, as shown in FIGS. 3E and 4E, the substrate 10 is etched using the patterned resist underlayer film 11 (15) as a mask.
Finally, as shown in FIGS. 3 (f) and 4 (f), ashing is performed to peel off the resist underlayer film 11 (, 15).
3 and 4, the substrate 10 may be composed of a base layer 10b and a layer to be processed 10a. Examples of the layer to be processed 10a and the base layer 10b include those described in FIGS. It is done.
The exposure can be performed using an electron beam. In this case, the resist underlayer film produced from the resist underlayer film material of the present invention has an excellent acid blocking function that prevents acid generated in the photoresist (resist upper layer film) during exposure from diffusing into the substrate. Therefore, the acid concentration in the photoresist can be prevented from being lowered, and the resist pattern can be prevented from being skirted or undercut.

  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.

[Synthesis Example 1]
15.8 g of α-hydroxymethyl acrylate and 20 g of tetrahydrofuran as a solvent were added to a 100 mL 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, 0.2 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
α-hydroxymethyl acrylate t-butyl = a1 (molar ratio) = 1.0
Molecular weight (Mw) = 9000
Dispersity (Mw / Mn) = 1.60
This polymer is referred to as polymer 1.

[Synthesis Example 2]
In a 100 mL flask, 14.3 g of α-hydroxymethyl acrylate, 1.2 g of 4-hydroxystyrene, 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethyl acrylate t-butyl: 4-hydroxystyrene = a1: b1 (molar ratio) = 0.9: 0.1
Molecular weight (Mw) = 8,800
Dispersity (Mw / Mn) = 1.77
This polymer is designated as Polymer 2.

[Synthesis Example 3]
To a 100 mL flask, 14.3 g of α-hydroxymethyl acrylate, 0.7 g of acrylic acid, 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethyl acrylate t-butyl: acrylic acid = a1: c1 (molar ratio) = 0.9: 0.1
Molecular weight (Mw) = 8,300
Dispersity (Mw / Mn) = 1.62
This polymer is designated as Polymer 3.

[Synthesis Example 4]
To a 100 mL flask, 14.3 g of α-hydroxymethyl acrylate, 1.8 g of phenyl α-hydroxymethyl acrylate, 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethyl acrylate t-butyl: α-hydroxymethyl acrylate phenyl = a1: a2 (molar ratio) = 0.9: 0.1
Molecular weight (Mw) = 9,200
Dispersity (Mw / Mn) = 1.64
This polymer is designated as polymer 4.

[Synthesis Example 5]
In a 100 mL flask, α-hydroxymethyl acrylate 1-ethylcyclopentyl 14.3 g, α-hydroxymethyl acrylate-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2- Propyl) cyclohexyl 5.2 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethyl acrylate 1-ethylcyclopentyl: α-hydroxymethyl acrylate-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = a3: a4 (Molar ratio) = 0.9: 0.1
Molecular weight (Mw) = 8,400
Dispersity (Mw / Mn) = 1.70
This polymer is designated as polymer 5.

[Synthesis Example 6]
To a 100 mL flask, 14.3 g of 1-ethylcyclopentyl α-hydroxymethyl acrylate, 1.2 g of maleic anhydride, and 10 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethyl acrylate 1-ethylcyclopentyl: maleic anhydride = a3: d1 (molar ratio) = 0.9: 0.1
Molecular weight (Mw) = 7,300
Dispersity (Mw / Mn) = 1.78
This polymer is designated as polymer 6.

[Synthesis Example 7]
Α-hydroxymethyl acrylate 1-ethylcyclopentyl 14.3 g, N-phenylmaleimide 1.2 g, and 10 g of tetrahydrofuran as a solvent were added to a 100 mL 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethyl acrylate 1-ethylcyclopentyl: N-phenylmaleimide = a3: e1 (molar ratio) = 0.9: 0.1
Molecular weight (Mw) = 6,400
Dispersity (Mw / Mn) = 1.55
This polymer is designated as polymer 7.

[Synthesis Example 8]
Α-hydroxymethyl acrylate 1-ethylcyclopentyl 14.3 g, α-hydroxymethyl acrylate-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl 2 in a 100 mL flask 0.4 g and 10 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethyl acrylate 1-ethylcyclopentyl: α-hydroxymethyl acrylate-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl = a3: a5 (molar ratio) = 0.9: 0.1
Molecular weight (Mw) = 5,800
Dispersity (Mw / Mn) = 1.59
This polymer is designated as polymer 8.

[Synthesis Example 9]
To a 100 mL flask, 17.6 g of α-hydroxymethyl acrylate-1-adamantyl, 2.4 g of 4-hydroxystyrene, 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethylacrylic acid-1-adamantyl: 4-hydroxystyrene = a6: b1 (molar ratio) = 0.8: 0.2
Molecular weight (Mw) = 9,800
Dispersity (Mw / Mn) = 1.78
This polymer is designated as polymer 9.

[Synthesis Example 10]
To a 100 mL flask, 16.5 g of α-hydroxymethylacrylic acid-8-tricyclodecanyl, 2.4 g of 4-hydroxystyrene, 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, 0.2 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.
Copolymer composition ratio
α-hydroxymethylacrylic acid-8-tricyclodecanyl: 4-hydroxystyrene = a7: b1 (molar ratio) = 0.8: 0.2
Molecular weight (Mw) = 9,400
Dispersity (Mw / Mn) = 1.82
This polymer is designated as polymer 10.

  Further, m-cresol novolak and poly-p-hydroxystyrene were prepared as conventionally used polymers.

[Preparation of resist underlayer film material]
The polymer, the cross-linking agent represented by CR1, and the acid generator represented by AG1 and AG2 were dissolved in an organic solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M) at a ratio shown in Table 1. The solutions of the resist underlayer film materials (Examples 1 to 12 and Comparative Examples 1 and 2) were prepared by filtering through a 0.1 μm fluororesin filter.

酸発生剤： ＡＧ１、ＡＧ２（下記構造式参照）

有機溶剤：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート） The composition of each resist underlayer film material in Table 1 is as follows.
Polymers 1 to 10: From Synthesis Examples 1 to 10 Crosslinking agent: CR1 (see the following structural formula)

Acid generator: AG1, AG2 (see structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

[Preparation of silicon-containing resist interlayer film material]
Next, in the organic solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M), the following polymer (ArF silicon-containing intermediate layer polymer 1) and acid generator represented by AG1 are listed in Table 1. A solution of the resist intermediate layer film material (SOG1) was prepared by dissolving at the indicated ratio and filtering through a 0.1 μm fluororesin filter.

（o=0.20, p=0.8, Mw=3,400）
酸発生剤： ＡＧ１（前記参照）
有機溶剤： ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート） The composition of the resist intermediate layer material in Table 1 is as follows.
Polymer: ArF silicon-containing intermediate layer polymer 1 (see structural formula below)

(O = 0.20, p = 0.8, Mw = 3,400)
Acid generator: AG1 (see above)
Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

[Preparation of resist upper layer film material]
Next, an organic containing 0.1% by mass of the following polymer (ArF single layer resist polymer 1), an acid generator represented by PAG1, and a basic compound represented by TMMEA (manufactured by Sumitomo 3M) A solution of the resist upper layer film material (ArF SL resist) was prepared by dissolving in a solvent at a ratio shown in Table 2 and filtering through a 0.1 μm fluororesin filter.

（u=0.40,v=0.30,w=0.30 Mw7,800）
酸発生剤： ＰＡＧ１（下記構造式参照）

塩基性化合物： ＴＭＭＥＡ（下記構造式参照）

有機溶剤： ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート） The composition of the resist upper layer film material in Table 2 is as follows.
Polymer: ArF single layer resist polymer 1 (see structural formula below)

(U = 0.40, v = 0.30, w = 0.30 Mw7,800)
Acid generator: PAG1 (see structural formula below)

Basic compound: TMMEA (see structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

[Ashing test]
Next, a solution of the resist underlayer film material prepared above (Examples 1 to 12, Comparative Examples 1 and 2) was applied on a Si (silicon) substrate, and baked at 200 ° C. for 60 seconds to form a resist having a thickness of 300 nm. A lower layer film was formed.

The ashing speed was tested. This test was performed by ashing the formed resist underlayer film under the following conditions (O ₂ -based gas) using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Limited.

(Ashing test with O ₂ gas)
The ashing conditions are as shown below.
Chamber pressure 40.0Pa
RF power 600W
Gap 9mm
O ₂ gas flow rate 5ml / min
N ₂ gas flow rate 500ml / min
Time 15sec

  And the film thickness difference of the resist underlayer film before and after ashing was measured. The results are shown in Table 3.

  In this test, it was confirmed that the resist underlayer film formed using the materials of Examples 1 to 12 had a very high ashing speed.

[Observation of resist pattern shape after development]
Next, the resist pattern shape was tested.
First, a solution of a resist underlayer film material (Examples 1 to 12, Comparative Examples 1 and 2) was applied on a Si substrate and baked at 200 ° C. for 60 seconds to form a first resist underlayer film.
Similarly, a second resist underlayer film and a silicon-containing resist intermediate layer film were sequentially formed.
Further, a resist upper layer film material (SL resist for ArF) solution shown in Table 2 was applied thereon and baked at 120 ° C. for 60 seconds to form a resist upper layer film having a thickness of 180 nm.
In this way, a laminated structure in which the first and second resist lower layer films, the resist intermediate layer film, and the resist upper layer film were laminated on the substrate was formed.

Next, the formed resist upper layer film was exposed with an ArF exposure apparatus (manufactured by Nikon Corporation; S307E, NA 0.85, σ 0.93, 4/5 ring illumination, 6% transmittance halftone phase shift mask), The resist was baked (PEB) at 110 ° C. for 60 seconds and developed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds to obtain a positive resist pattern. And the pattern shape of 0.08 microml / S of the obtained pattern was observed.
At this time, the cross section of the pattern was observed with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared. The results are summarized in Table 4.

  Even when the resist underlayer film materials of Examples 1 to 12 were used, it was confirmed that the resist pattern shape after patterning was good as in the conventional resist underlayer film for a three-layer resist process.

(Example 13, Comparative Example 3)
[EB exposure patterning evaluation]
As a resist underlayer film material for EB exposure, the polymer 1, the cross-linking agent represented by CR1, and the acid generator represented by AG1 are dissolved in an organic solvent at a ratio shown in Table 5 to prepare a resist underlayer film material solution. Prepared.

The composition of the resist underlayer film material in Table 5 is as follows.
Polymer 1: From Synthesis Example 1 Crosslinking agent: CR1 (see above)
Acid generator: AG1 (see above)
Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

  Next, a polymer shown below (EB resist polymer 1), an acid generator represented by PAG2, and a basic compound represented by TMMEA were dissolved in an organic solvent at a ratio shown in Table 6 to obtain a 0.2 μm size filter. The solution of positive resist upper layer film material (SL resist for EB) was prepared.

酸発生剤： ＰＡＧ２（下記構造式参照）

塩基性化合物： ＴＭＭＥＡ（前記参照）
有機溶剤： ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート） The composition of the resist upper layer film material in Table 6 is as follows.
Polymer: EB resist polymer 1 (see the following structural formula)

Acid generator: PAG2 (see structural formula below)

Basic compound: TMMEA (see above)
Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

  A 6025 quartz substrate in which a Cr film was formed to a thickness of 100 nm by sputtering was prepared. A solution of the resist underlayer film material prepared above (Example 13) was applied thereon, and baked at 200 ° C. for 60 seconds to form a resist underlayer film having a thickness of 20 nm.

  The resist upper layer material prepared above was spin-coated on this resist lower layer film, and prebaked at 110 ° C. for 90 seconds on a hot plate to prepare a resist upper layer film having a thickness of 150 nm. 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, PEB was carried out on a hot plate at 90 ° C. for 90 seconds, and paddle development was carried out with a 2.38 mass% TMAH aqueous solution for 30 seconds to obtain a positive pattern.
The obtained resist pattern was evaluated as follows, and the results are shown in Table 7 as Example 13 below.
The substrate was cleaved, and the cross-sectional shape of a 0.12 μm line and space was observed with an SEM.

  Further, as Comparative Example 3, except that the resist upper layer film was formed directly on the Cr substrate without forming the resist lower layer film, drawing, developing and evaluation of the obtained resist pattern were performed under the same conditions as in Example 13, The results are shown in Table 7 below.

  From the results of Table 7 above, when a resist pattern is formed by electron beam exposure, a resist underlayer film using the resist underlayer film material of the present invention is provided between the substrate and the resist overlayer film, thereby skirting the resist pattern. It was confirmed that good patterns could be formed by preventing undercuts.

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

It is explanatory drawing which shows an example of the pattern formation method of this invention by a 3 layer resist process. It is explanatory drawing which shows another example of the pattern formation method of this invention by a three-layer resist process. It is explanatory drawing which shows an example of the pattern formation method of this invention by a two-layer resist process. It is explanatory drawing which shows another example of the pattern formation method of this invention by a two-layer resist process.

Explanation of symbols

10 ... Substrate, 10a ... Work layer, 10b ... Base layer,
11 ... (first) resist underlayer film, 12 ... resist intermediate layer film,
13 ... Resist upper layer film, 14 ... Exposure, 15 ... Second resist lower layer film.

Claims (8)

A resist underlayer film material for a multilayer resist film used in lithography, comprising at least a polymer having a repeating unit represented by the following general formula (1) as a repeating unit .

(In the general formula (1), R ¹ is a hydrogen atom or a monovalent organic group.) The resist underlayer film material according to claim 1, further comprising at least one of water and an organic solvent. The resist underlayer film material according to claim 1 or 2, further comprising at least one of an acid generator and a crosslinking agent. 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 3 , and the underlayer film A resist upper layer film of a photoresist composition is formed on the substrate to form a two-layer resist film, the pattern circuit region of the two-layer resist film is exposed, and then developed with a developer to form a resist pattern on the resist upper layer film. Forming a pattern on the substrate by etching the substrate using at least the resist underlayer film on which the pattern is formed as a mask, and etching the substrate using the resist upper layer film on which the pattern is formed as a mask; A pattern forming method, wherein the resist underlayer film is removed by ashing. A method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film material according to any one of claims 1 to 3 is used to form a first resist underlayer film on the substrate, Forming a second resist underlayer film on the first resist underlayer film, forming a resist upper layer film of a photoresist composition on the second resist underlayer film to form a two-layer resist film; After exposing the pattern circuit region of the two-layer resist film, development is performed with a developer to form a resist pattern on the resist upper layer film, and the first and second resists are formed using the resist upper layer film on which the pattern is formed as a mask. Etching the lower layer film, etching the substrate using at least the first and second resist lower layer films on which the pattern is formed as a mask to form a pattern on the substrate, and further ashing Thus the pattern forming method, which comprises carrying out the peeling of the resist underlayer film. 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 3 , and the underlayer film A resist intermediate layer film containing silicon atoms is formed on the substrate, a resist upper layer film of a photoresist composition is formed on the intermediate layer film to form a three-layer resist film, and a pattern of the resist three-layer film After the circuit area was exposed, the resist was developed with a developer to form a resist pattern on the resist upper layer film, and the resist intermediate layer film was etched using the resist upper layer film on which the pattern was formed as a mask to form at least a pattern. Etch the resist underlayer using the resist intermediate layer as a mask, and etch the substrate using at least the patterned resist underlayer as a mask Forming a pattern on a substrate Te, further, a pattern forming method, which comprises carrying out the peeling of the resist underlayer film by ashing. A method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film material according to any one of claims 1 to 3 is used to form a first resist underlayer film on the substrate, A second resist underlayer film is formed on the first resist underlayer film, a resist intermediate layer film containing silicon atoms is formed on the second underlayer film, and a photo film is formed on the intermediate layer film. Forming a resist upper layer film of the resist composition to form a three-layer resist film, exposing the pattern circuit region of the resist three-layer film, developing with a developer to form a resist pattern on the resist upper layer film, The resist intermediate layer film is etched using the resist upper layer film on which the pattern is formed as a mask, and the first and second resist lower layer films are etched using at least the resist intermediate layer film on which the pattern is formed as a mask. Forming a pattern on the substrate by etching the substrate using at least the first and second resist underlayer films on which the pattern is formed as a mask, and further removing the resist underlayer film by ashing. Pattern forming method. The pattern forming method according to any one of claims 4 to 7 the exposure of the pattern circuit region, and performing using an electron beam.

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