JP2005048152A - Polymer compound, antireflection film material, and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film material having a high selective ratio in etching a resist, namely, having a high speed in etching the resist, to provide a method for forming a pattern, capable of forming an antireflection film layer on a base by using the antireflection film material, and to provide a method for forming the pattern by using the antireflection film as a hard mask for processing the base. <P>SOLUTION: A polymer compound having repeating units expressed by general formula (1) (R<SP>1</SP>is a single bond, a 1-20C straight-chain, branched-chain or cyclic alkylene in which -COO-, -CONH- or -O- may intervene, -COO-, -CONH-, -O- or a siloxane bond) is provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an antireflection film material mainly composed of a polymer compound containing a substituent containing a silicon atom, which is suitable as an antireflection film material used for microfabrication in a manufacturing process of a semiconductor element or the like, and a distant film using the same. Pattern formation method suitable for UV, ArF excimer laser light (193 nm), F ₂ laser light (157 nm), Kr ₂ laser light (146 nm), Ar ₂ laser light (126 nm) exposure (resist pattern formation method and integration on substrate) Circuit pattern forming method).

  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 mercury lamp g-line (436 nm) or i-line (365 nm) as a light source is widely used, and as a means for further miniaturization, A method of shortening the wavelength of exposure light has been considered effective. For this reason, in the mass production process of the 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 (processing dimension is 0.13 μm or less), a light source with a shorter wavelength is required, and in particular, an ArF excimer laser (193 nm) is used. Lithography has been studied.

  In the early stages of KrF lithography, steppers were developed that combine achromatic lenses or reflective optics with broadband light. However, since the accuracy of the achromatic lens or the aspherical reflecting optical system is not sufficient, a combination of a narrow-band laser beam and a refractive optical system lens has become mainstream.

  In general, in single wavelength exposure, it is a long-known phenomenon that incident light and reflected light from a substrate interfere to generate a standing wave. It is also known that a phenomenon called halation occurs due to light being condensed or scattered by the unevenness of the substrate. Both standing waves and halation cause dimensional fluctuations such as the line width of the pattern and shape collapse. The use of coherent monochromatic light further amplifies standing waves and halation with shorter wavelengths.

  For this reason, as a method for suppressing halation and standing waves, a method of putting a light-absorbing agent in a resist and a method of laying an antireflection film on the resist upper surface and substrate surface have been proposed.

  However, the method of adding a light-absorbing agent has a problem that the resist pattern has a tapered shape. With the recent shortening of wavelengths and the progress of miniaturization, the problem that standing waves and halation have on pattern dimension variation has become serious, and it has become impossible to deal with the method of adding a light absorber.

  On the other hand, the upper-layer transmissive antireflection film is effective only in reducing standing waves in principle and is not effective in halation. Further, the refractive index of the upper antireflection film for completely eliminating the standing wave is ideally the square root of the refractive index of the resist, so that the refractive index of the polyhydroxystyrene resist used in KrF is 1 .8, 1.34 is the ideal value. With an alicyclic acrylic resist refractive index of 1.6 used for ArF, the ideal value is 1.27. The material having such a low refractive index is limited to a perfluoro-based material, but the upper antireflection film is a water-soluble material because it is advantageous in terms of process that it can be peeled off during alkali development. is required. When a hydrophilic substituent is introduced to make a highly hydrophobic perfluoro-based material water-soluble, the refractive index is increased to a value of around 1.42 for KrF and around 1.5 for ArF. . For this reason, when patterning of 0.20 μm or less is performed by KrF lithography, it is impossible to suppress the influence of the standing wave only by the combination of the light absorber and the upper antireflection film. For ArF, the effect of the upper antireflection film can hardly be expected due to the above-mentioned reasons. Also in KrF, when line width management becomes stricter due to further reduction of the line width in the future, an antireflection film is formed on the resist base. It has become necessary to lay.

  In the case where the underlying antireflection film of the resist is a highly reflective substrate such as polysilicon or aluminum, the material of optimum refractive index (n value) and extinction coefficient (k value) is set to an appropriate film thickness. As a result, reflection from the substrate can be reduced to 1% or less, and an extremely large effect can be exhibited. For example, at a wavelength of 193 nm, the refractive index of the resist is 1.8, the refractive index of the lower antireflection film (real part of the refractive index) n = 1.5, the extinction coefficient (imaginary part of the refractive index) k = 0.5 When the film thickness is 42 nm, the reflectance is 0.5% or less (see FIG. 1). However, when there is a step on the base, the thickness of the antireflection film varies greatly on the step. Since the antireflection effect of the base uses not only the light absorption but also the interference effect, the first base of 40 to 45 nm where the interference effect is strong also has a high antireflection effect. The rate fluctuates. A material has been proposed in which the molecular weight of the base resin used for the antireflection film material is increased to suppress the film thickness fluctuation on the step and the conformality is improved (Japanese Patent Laid-Open No. 10-69072). If it is high, problems such as pinholes are likely to occur after spin coating, filtration cannot be performed, viscosity changes with time, film thickness changes, and crystals precipitate at the tip of the nozzle. In addition, the conformal property can be exhibited only at a step having a relatively low height.

  Next, there can be considered a method of adopting a film thickness (170 nm or more) of the third base or more in which the reflectance variation due to the film thickness variation is relatively small. In this case, if the k value is between 0.2 and 0.3 and the film thickness is 170 nm or more, the change in reflectance with respect to the change in film thickness is small, and the reflectance can be suppressed to 1.5% or less. it can. When the base of the antireflection film is a transparent film such as an oxide film or a nitride film, and there is a step under the transparent film, the film thickness of the transparent film is not limited even if the surface of the transparent film is flattened by CMP or the like. Fluctuates. In this case, it is possible to make the film thickness of the antireflection film thereon constant, but if the film thickness of the base transparent film of the antireflection film varies, the thickness of the minimum reflection film in FIG. 1 becomes the film thickness of the transparent film. It shifts by a period of λ / 2n (λ: exposure wavelength, n: refractive index of the transparent film at the exposure wavelength). When the film thickness of the antireflection film is set to the minimum reflection film thickness of 55 nm when the base is a reflection film, a portion having a high reflectance appears due to the film thickness fluctuation of the transparent film. In this case, in order to stabilize the reflectance with respect to the change in the film thickness of the base transparent film, it is necessary to make the film thickness of the antireflection film 170 nm or more as described above.

  Antireflection film materials can be broadly classified into inorganic and organic materials. An inorganic system is a SiON film. This is formed by CVD using a mixed gas of silane and ammonia, and has a large etching selection ratio with respect to the resist. Therefore, there is an advantage that the etching load on the resist is small. is there. In addition, since it is a basic substrate containing nitrogen atoms, there is a drawback that it tends to have a footing in a positive resist and an undercut profile in a negative resist.

  On the other hand, organic systems can be spin-coated and do not require special equipment such as CVD or sputtering, can be peeled off simultaneously with the resist, have no tailing, and have a straight shape and good adhesion to the resist. There is an advantage, and antireflection films based on many organic materials have been proposed. For example, a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin and a light-absorbing agent, or a maleic anhydride copolymer described in US Pat. No. 5,294,680 And a reaction product of a diamine type light absorber, a resin binder described in JP-A-6-186863 and a methylolmelamine-based thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656 A resin-based acrylic resin having the same molecular weight, comprising a methylol melamine and a benzophenone light absorber described in JP-A-8-87115, and a low-molecular light absorber added to a polyvinyl alcohol resin described in JP-A-8-179509 And the like. All of these employ a method in which a light absorber is added to the binder polymer or introduced as a substituent into the polymer. However, since many of the light-absorbing agents have aromatic groups or double bonds, the addition of the light-absorbing agent increases the dry etching resistance, and there is a disadvantage that the dry etching selectivity with the resist is not so high. As the miniaturization progresses and the thinning of the resist is accelerated, the next generation ArF exposure uses an acrylic polymer or an alicyclic polymer as a resist material. descend. Further, as described above, there is a problem that the thickness of the antireflection film must be increased. For this reason, etching is a serious problem, and there is a demand for an antireflection film having a high etching selectivity with respect to a resist, that is, a high etching speed.

  In addition, a light-absorbing agent for giving an optimum extinction coefficient in an antireflection film has been studied. In particular, an anthracene type is proposed for KrF, and a phenyl type is proposed for ArF. However, as mentioned above, these are also substituents having excellent dry etching resistance, and even when the polymer backbone with the die pendant is made into a polymer having low etching resistance such as acrylic polymer, it is practically limited. There is. On the other hand, in general, it is known that a material containing silicon has a high etching rate and a high selectivity with respect to a resist under etching conditions using a fluorocarbon-based gas. It is considered that the etching selectivity can be dramatically increased by using. For example, an antireflection film for KrF exposure having a polysilane having a phenyl group pendant as a skeleton is proposed in Japanese Patent Application Laid-Open No. 11-60735, and a high etching selectivity is achieved.

In recent years, the resist film is becoming thinner with higher resolution. Although there is a demand for improving the etching resistance of resists as the film thickness is reduced, it is not sufficient. A thin mask resist pattern transfer method includes a hard mask method. When the substrate to be processed is p-Si or the like, an SiO ₂ film is considered. When the substrate to be processed is an SiO ₂ film, SiN, W-Si, amorphous Si, or the like is being studied. The hard mask may be left or peeled off. In particular, when the base is an insulating film such as a SiO ₂ film, the W—Si and amorphous Si films are particularly good conducting films, and therefore need to be peeled off. Since the SiN film is an insulating film, it does not need to be peeled off depending on the case. However, since the constituent elements are similar to those of SiO ₂ , there is a drawback that the etching selectivity as an original function as a hard mask is low. Furthermore, a hard mask of a SiON film that also functions as an antireflection film has been proposed (SPIE 2000 Vol. 4226 p93).

  JP-A-57-83563, JP-A-57-131250, JP-A-56-129261, and Japanese Patent No. 3287119 propose a coating liquid for forming a silica-based insulating film. Many pattern forming methods using this technique and using a silicon-containing polymer as a resist underlayer have been proposed. For example, in Japanese Patent No. 3118887 and Japanese Patent Laid-Open No. 2000-356854, an organic film is formed on a substrate, silica glass is spin-coated thereon, the resist pattern thereon is transferred to a silica glass layer, and then oxygen gas A three-layer process has been proposed in which a pattern is transferred to an organic film layer by etching, and finally the substrate is processed. In JP-A-5-27444, JP-A-6-138664, JP-A-2001-53068, JP-A-2001-92122, and JP-A-2001-343752, a silica glass layer also serving as an antireflection film Silsesquioxane polymer materials have been proposed. Further, US6420088B1 proposes a composition based on a silsesquioxane polymer that has both functions of an antireflection film and a hard mask.

Japanese Patent Laid-Open No. 10-69072 Japanese Patent Publication No. 7-69611 US Pat. No. 5,294,680 Japanese Patent Laid-Open No. 6-118631 JP-A-6-118656 JP-A-8-87115 JP-A-8-179509 Japanese Patent Laid-Open No. 11-60735 JP-A-57-83563 JP 57-131250 A JP-A-56-129261 Japanese Patent No. 3287119 Japanese Patent No. 3118887 JP 2000-356854 A Japanese Patent Laid-Open No. 5-27444 JP-A-6-138664 JP 2001-53068 A JP 2001-92122 A JP 2001-343752 A US Pat. No. 6,420,088 SPIE 2000 Vol. 4226 p93

  An object of the present invention is to provide an antireflection film material having a high etching selectivity with respect to a resist, that is, a high etching speed with respect to the resist, and a pattern for forming an antireflection film layer on a substrate using the antireflection film material. Another object of the present invention is to provide a forming method and a pattern forming method using this antireflection film as a hard mask for substrate processing.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. The present invention provides the following polymer compound, antireflection film material and pattern forming method.
Claim 1:
The high molecular compound characterized by having a repeating unit represented by following General formula (1).
(In the formula, R ¹ is a single bond, or an alkylene group that may be mediated by linear, branched, or cyclic -COO-, -CONH-, or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond.)
Claim 2:
An antireflection film material comprising a polymer compound obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (2).
[Wherein, R ¹ is a single bond or an alkylene group which may be mediated by linear, branched or cyclic -COO-, -CONH- or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond, wherein R ^{2 to} R ⁶ are a hydrogen atom, an alkyl group that may be substituted with a linear, branched, or cyclic fluorine atom having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, or the following general formula (3)
(R ^{7 to} R ¹¹ are a hydrogen atom, an alkyl group which may be substituted with a linear, branched or cyclic fluorine atom having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) It is a silicon-containing group shown by these. R ³ and R ⁴ may be bonded to form a polysilane ring together with the silicon atom to which they are bonded. a is 0 or 1; X ¹ , X ² , and X ³ are each a halogen atom, a hydroxy group, or an alkoxy group having 1 to 10 carbon atoms. m is 0 ≦ m ≦ 10. ]
Claim 3:
It contains a polymer compound obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (2) and a silicon compound having a crosslinking group represented by the following general formula (4). Antireflection film material.
[Wherein, R ¹ is a single bond or an alkylene group which may be mediated by linear, branched or cyclic -COO-, -CONH- or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond, wherein R ^{2 to} R ⁶ are a hydrogen atom, an alkyl group that may be substituted with a linear, branched, or cyclic fluorine atom having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, or the following general formula (3)
(R ^{7 to} R ¹¹ are a hydrogen atom, an alkyl group which may be substituted with a linear, branched or cyclic fluorine atom having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) It is a silicon-containing group shown by these. R ³ and R ⁴ may be bonded to form a polysilane ring together with the silicon atom to which they are bonded. a is 0 or 1; X ¹ , X ² , and X ³ are each a halogen atom, a hydroxy group, or an alkoxy group having 1 to 10 carbon atoms. m is 0 ≦ m ≦ 10. ]
(In the formula, R ¹² is a monovalent organic group having a crosslinking group, and X ¹ , X ² , and X ³ are as described above.)
Claim 4:
An antireflection film material comprising a polymer compound having a repeating unit represented by the following general formula (5) and having a molecular weight of 500 or more.
[Wherein, R ¹ is a single bond or an alkylene group which may be mediated by linear, branched or cyclic -COO-, -CONH- or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond, wherein R ^{2 to} R ⁶ are a hydrogen atom, an alkyl group that may be substituted with a linear, branched, or cyclic fluorine atom having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, or the following general formula (3)
(R ^{7 to} R ¹¹ are a hydrogen atom, an alkyl group which may be substituted with a linear, branched or cyclic fluorine atom having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) It is a silicon-containing group shown by these. R ³ and R ⁴ may be bonded to form a polysilane ring together with the silicon atom to which they are bonded. a is 0 or 1; R ¹² is a monovalent organic group having a crosslinking group, and 0 <c <1, 0 <d <1, and 0.5 ≦ c + d ≦ 1. ]
Claim 5:
The antireflection film material according to any one of claims 2 to 4, further comprising (B) an organic solvent, (C) a crosslinking agent, and (D) an acid generator.
Claim 6:
An antireflection film material according to any one of claims 2 to 5 is applied on a substrate to be processed, baked to form an antireflection film layer, a photoresist solution is applied thereon, and prebaked. Form a photoresist film layer, irradiate the pattern circuit area with radiation, develop with a developing solution to form a resist pattern, and process the antireflection film layer and the substrate to be processed using the photoresist layer as a mask with a dry etching device And a pattern forming method.
Claim 7:
An organic film is formed on a substrate to be processed, and the antireflection film material according to any one of claims 2 to 5 is applied thereon, and baked to form an antireflection film layer. Apply a resist solution, pre-bake to form a photoresist film layer, irradiate the pattern circuit area with radiation, develop with a developing solution to form a resist pattern, and reflect using the photoresist layer as a mask with a dry etching device An anti-reflective film material is processed by using the anti-reflective film material of any one of claims 2 to 5 as a hard mask by dry etching using oxygen plasma, and then an organic film is processed by dry etching. A pattern forming method characterized in that a substrate to be processed is processed using a mask as a mask.
Claim 8:
An antireflection film material according to any one of claims 2 to 5 is applied on a substrate to be processed, baked to form an antireflection film layer, a photoresist solution is applied thereon, and prebaked. A photoresist film layer is formed, the pattern circuit area is irradiated with radiation, developed with a developer to form a resist pattern, and the anti-reflection film layer is processed with a dry etching apparatus using the photoresist layer as a mask, and then dried. A pattern forming method comprising processing a substrate to be processed by etching using an antireflection film layer as a hard mask.

  According to the present invention, an antireflection film having a high etching selectivity with respect to the resist, that is, a high etching speed is obtained, and this antireflection film has an extinction coefficient sufficient to exhibit a sufficient antireflection effect, and The resist shape after patterning is also good.

  That is, Kashiyama et al. In Japanese Patent Application Laid-Open No. 2002-107938 show that a compound having a silicon-silicon σ bond has strong absorption from the far ultraviolet region to the vacuum ultraviolet region, particularly in the vicinity of the ArF wavelength region, that is, ArF (193 nm). In order to obtain a sufficient antireflection effect by a methacrylic polymer in which a silane such as disilane, trisilane, tetrasilane, or pentasilane is pendant, even if the main chain is not silicon-silicon as in polysilane. It was reported that absorption can be obtained, and as a result of using this as an antireflection film material, an antireflection film having a high etching selectivity can be obtained. Conventionally, a compound having a benzene ring or a polymer body has been used as a 193 nm light absorber, but by using a polymer body having a silicon-silicon pendant, the etching rate can be increased, and an antireflection film. It has become possible to increase the film thickness.

  In contrast, the present invention proposes an antireflection film in which the main chain is silsesquioxane and the silicon-silicon σ bond is pendant. In US6420088B1, silsesquioxane using an aromatic group as a light absorber is used, but the silsesquioxane of the present invention has a very high silicon content, and the etching speed for the upper resist can be increased. The etching rate with respect to the oxide film can be reduced, and the etching resistance effect as a hard mask can be enhanced. Also, a normal resist is formed in the upper layer, a film having silicon in the intermediate layer, and an organic film is formed in the lower layer. After development of the upper layer resist, the silicon-containing intermediate layer is etched using the resist pattern as a mask, and the silicon-containing film is used as a mask. In a three-layer process in which an organic film is processed by oxygen gas etching, the silsesquioxane of the present invention is characterized by high resistance to oxygen gas etching because of its high silicon content.

  The polymer compound of the present invention has far higher reproducibility of the synthesis result than the synthesis of polysilane, that is, controllability of molecular weight, dispersity, and transmittance, and is overwhelmingly advantageous in terms of cost. In this case, a silicone polymer, in particular, a silsesquioxane polymer obtained by condensing a trifunctional alkoxysilane or halogen silane is used as a polymer for pendating silanes.

  According to the present invention, an antireflection film having a high etching selectivity with respect to the resist, that is, a high etching speed is obtained, and this antireflection film has an extinction coefficient sufficient to exhibit a sufficient antireflection effect, and The resist shape after patterning is also good.

Hereinafter, the present invention will be described in more detail.
The novel polymer compound of the present invention has a repeating unit represented by the following general formula (1).
(In the formula, R ¹ is a single bond, or linear, branched or cyclic —COO—, —CONH— or —O— having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms. Is an alkylene group, —COO—, —CONH—, —O—, or a siloxane bond which may be interposed.
In this case, examples of the alkylene group for R ¹ include an ethylene group and a propylene group.

In order to obtain the polymer material represented by the general formula (1) of the present invention, a silicon-containing compound represented by the following general formula (6) is used.

Here, R ¹ is as described above, and X ¹ , X ² and X ³ are each a halogen atom, a hydroxy group, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. It is.

In the above general formula (6), an example of a method for producing an organosilicon compound in which X ¹ , X ² , and X ³ are methoxy groups is as follows.

  The present invention provides a polymer of the above general formula (1) obtained by hydrolysis / condensation of a silicon compound represented by the following general formula (2) which can also include the organosilicon compound of the above formula (6). It is obtained by hydrolyzing and condensing a polymer compound that can also include a compound, or a silicon compound represented by the following general formula (2) and a silicon compound having a crosslinking group represented by the following general formula (4). An antireflective film material containing the obtained polymer compound is provided.

[Wherein, R ¹ is as described above. R ^{2 to} R ⁶ are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 alkyl groups which may be substituted with linear, branched or cyclic fluorine atoms, and carbon atoms. An aryl group having a number of 6 to 20, preferably 6 to 12, more preferably 6 to 10, or the following general formula (3)
(R ^{7 to} R ¹¹ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 and more preferably 1 to 4 which may be substituted with a linear, branched or cyclic fluorine atom, Or an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms). R ³ and R ⁴ may be bonded to form a polysilane ring together with the silicon atom to which they are bonded. a is 0 or 1; X ¹ , X ² and X ³ are as defined above. m is 0 ≦ m ≦ 10. ]
(In the formula, R ¹² is a monovalent organic group having a crosslinking group, and X ¹ , X ² , and X ³ are as described above.)

Here, examples of the alkylene group that may be interposed by —COO—, —CONH—, or —O— of R ¹ include the following.

Moreover, the following are mentioned as a siloxane bond of R < ¹ >.
(However, R < ⁷ >, R < ⁸ > is as above-mentioned, n is an integer of 1-10, especially 1-6.)

Examples of the alkyl group represented by R ^{2 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, a hexyl group, and a cyclohexyl group. The fluorine-substituted alkyl group includes these alkyl groups. Examples thereof include a trifluoromethyl group and a 3,3,3-trifluoropropyl group in which part or all of the hydrogen atoms in the group are substituted with fluorine atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
Examples of the polysilane ring formed by combining R ³ and R ⁴ include those represented by the following formula.
(B is 2 to 7, and R ⁷ , R ⁸ and R ¹⁰ are as described above.)

  Examples of the compound represented by the general formula (2) include the following, but are not limited thereto.

Examples of the monovalent organic group having the R ¹² cross-linking group include linear, branched or cyclic alkenyl groups having 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms (vinyl group, allyl group, butenyl group, Hexenyl group, cyclohexenyl group, etc.); aryl groups such as phenyl groups having 6 to 12 carbon atoms having the alkenyl group; cyclic ether groups such as epoxy, oxetane, tetrahydrofuran, etc., and ether groups other than these cyclic ether groups ( -O-) may be present in an epoxy group-containing monovalent hydrocarbon group having 3 to 20 carbon atoms, particularly 3 to 12 carbon atoms, particularly an alkyl group; hydroxyl group, chlorine atom, 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms. Ether group (-O-), imine containing one or two or more of alkoxy group, acetoxy group, (meth) acryl group, isocyanate group, mercapto group, amino group, etc. Group _{(-NH -, - NCH 3 -} , - NC 2 H 5 -, - NC 6 H 5 - , etc.), a ketone group (-CO-), carbon atoms, which may ester group (-COO-) or the like is interposed Examples thereof include monovalent hydrocarbon groups of 1 to 20, particularly 1 to 12, particularly alkyl groups, alkenyl groups, aryl groups, aralkyl groups; silicon atom-bonded hydrogen atoms (SiH groups) and the like.

  Examples of the silicon compound having a crosslinking group represented by the general formula (4) include those exemplified below.

  The antireflection film of the present invention has a repeating unit represented by the following formula (5) obtained by hydrolyzing and condensing a light-absorbing component represented by the general formula (2) and a crosslinking component represented by the general formula (4). Although it is preferable to use a high molecular compound as a base polymer, one or more of the light-absorbing components (A) shown below can be further hydrolyzed and condensed.

  Furthermore, in order to increase the molecular weight, the silane compound (B) shown below can be cohydrolyzed and condensed.

  Here, X is the same or different halogen atom, hydroxy group, or alkoxy group having 1 to 10 carbon atoms.

  In addition, although the component shown by General formula (2) and (4) and the said component (A) and (B) may be one each, two or more types can each be hydrolyzed and condensed.

  The antireflection film material of the present invention has a weight average molecular weight of 500 or more, preferably 500 to 1,000,000, more preferably 800 to 500,000, still more preferably having a repeating unit represented by the following general formula (5). It contains 1,000 to 300,000 polymer compounds. In addition, a weight average molecular weight is a measured value by polystyrene conversion using gel permeation chromatography (GPC).

Here, as described above, R ^{1 to} R ⁸ and R ¹² are 0 <c <1, 0 <d <1, and 0.5 ≦ c + d ≦ 1. Preferably, 0.1 ≦ c ≦ 0.9, 0.1 ≦ d ≦ 0.9, 0.6 ≦ c + d ≦ 1, and more preferably 0.2 ≦ c ≦ 0.8, 0.2. ≦ d ≦ 0.8 and 0.7 ≦ c + d ≦ 1.
Here, for example, c + d = 1 indicates that in the polymer compound containing the repeating units c and d, the total amount of the repeating units c and d is 100 mol% with respect to the total amount of all the repeating units. , C + d <1 indicates that the total amount of the repeating units c and d is less than 100 mol% with respect to the total amount of all the repeating units and has other repeating units in addition to c and d.

In this case, when c + d is less than 1, the remaining units are units derived from the component (A) and / or the component (B). In addition,
The unit derived from is a Q unit represented by SiO _4/2 ,

The unit derived from is a T unit represented by -SiO _3/2 ,
The units derived from - (CH ₃₎ a D unit represented by SiO _2/2.

  As a method for synthesizing the polymer compound, the monomers represented by the general formulas (2) and (4) and, if necessary, the monomers (A) and (B) are added and co-condensation by hydrolysis is performed. The amount of water in the hydrolysis reaction is preferably 0.2 to 10 moles per mole of monomer. At this time, a catalyst can also be used. Examples of the catalyst include acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, oxalic acid. Acid, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, etc., ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, trimethylamine, triethylamine, triethanol Amine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0]- Amine compounds such as 5-nonene (DBN) Group, tetraalkoxy titanium, trialkoxy mono (acetyl acetonate) titanium, tetraalkoxy zirconium, may be mentioned metal chelate compounds such as trialkoxy mono (acetylacetonato) zirconium.

  As the reaction operation, the monomer is dissolved in an organic solvent, and water is added to start the hydrolysis reaction. The catalyst may be added to water or may be added to an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 40 to 80 ° C. for aging is preferable. As the organic solvent, those hardly soluble or insoluble in water are preferable, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, 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, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate -Butyl, tert-butyl propionate, propylene glycol mono tert- Chill ether acetate, and γ- butyrolactone are preferred.

Thereafter, the catalyst is neutralized, and the organic solvent layer is separated and dehydrated. It is necessary to sufficiently perform the remaining of water in order to advance the condensation reaction of the remaining silanol. Preferable examples include an adsorption method using a salt such as magnesium sulfate and molecular sieve, and an azeotropic dehydration method while removing the solvent.
Those containing an epoxy group in the cross-linking group may be ring-opened during the condensation reaction with an acid catalyst to form an alcohol form.

The antireflection film material of the present invention is
(A) In addition to the above polymer compound,
(B) an organic solvent,
(C) a crosslinking agent,
(D) It is preferable to contain an acid generator.

  Here, as one of the performances required for the antireflection film, there is no intermixing with a resist, and there is no diffusion of low molecular components into the resist layer [Proc. SPIE Vol. 2195, 225-229 (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, when a crosslinking agent is added as a component of the antireflection film material, a method of introducing a crosslinkable substituent into the polymer may be used.

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

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

When the crosslinking group of the compound of the general formula (4) contains an epoxy group, it is effective to add a compound containing a hydroxy group. Particularly preferred are compounds containing two or more hydroxy groups in the molecule. For example, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] -decane, pentaerythritol, 1,2,6-hexanetriol, 4,4 ′, 4 ″ -methylidene Triscyclohexanol, 4,4 ′-[1- [4- [1- (4-hydroxycyclohexyl) -1-methylethyl] phenyl] ethylidene] biscyclohexanol, [1,1′-bicyclohexyl] -4, Alcohol group-containing compounds such as 4′-diol, methylenebiscyclohexanol, decahydronaphthalene-2,6-diol, [1,1′-bicyclohexyl] -3,3 ′, 4,4′-tetrahydroxy, 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′-cyclohexylidenebisphenol, 4,4 ′-(1,3-dimethylbutylidene) bisphenol, 4,4 '-(1-methylethylidene) bis [2,6-dimethylphenol], 4,4'-oxybisphenol, 4,4'-methylenebisphenol, bis (4-hydroxyphenyl) methanone, 4,4'-methylenebis [2-Methylphenol], 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 4,4 ′-(1,2-ethanediyl) bisphenol, 4,4 ′-(diethylsilylene) ) Bisphenol, 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol, 4,4 ′, 4 ″ -methylide Trisphenol, 4,4 ′-[1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4- Methylphenol, 4,4 ′, 4 ″ -ethylidenetris [2-methylphenol], 4,4 ′, 4 ″ -ethylidenetrisphenol, 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-me Tilcalix [4] allene, 2,2′-methylenebis [6-[(2,5 / 3,6-dimethyl-4 / 2-hydroxyphenyl) methyl] -4-methylphenol, 2,2′-methylenebis [ 6-[(3,5-dimethyl-4-hydroxyphenyl) methyl] -4-methylphenol, 4,4 ′, 4 ″, 4 ′ ″-tetrakis [(1-methylethylidene) bis (1,4 -Cyclohexylidene)] phenol, 6,6'-methylenebis [4- (4-hydroxyphenylmethyl) -1,2,3-benzenetriol, 3,3 ', 5,5'-tetrakis [(5-methyl And phenolic low nuclei such as 2-hydroxyphenyl) methyl]-[(1,1′-biphenyl) -4,4′-diol].

  The blending amount of the crosslinking agent (C) in the present invention is preferably 5 to 50 parts, particularly 10 to 40 parts, relative to 100 parts (parts by mass, the same applies hereinafter) of the base resin (the polymer compound of the component (A)). Is preferred. If it is less than 5 parts, it may cause mixing with the resist. If it exceeds 50 parts, the antireflection effect may be reduced, or cracks may occur in the crosslinked film.

  In the present invention, an acid generator can be added as the component (D) for further promoting the crosslinking reaction by heat. 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 the acid generator (D) used in 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.

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 each a hydrogen atom, 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 group having 6 to 20 carbon atoms. Or carbon An aralkyl group or an aryl oxoalkyl group having 7 to 12, some or all of the hydrogen atoms of these groups may be replaced by alkoxy or other groups. Also, R ^101d, R ^101e, R ^101d, R ^101e And R ^101f may form a ring. In the case of forming a ring, R ^101d and R ^101e are each an alkylene group having 1 to 6 carbon atoms, and R ^101d , R ^101e and R ^101f are each 4 to 6 carbon atoms. 10 represents an alkylene group or a heteroaromatic ring having a nitrogen atom in the formula in the ring.)

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f and R ^101g may be the same as or different from each other. Specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl Group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the 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. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate. The heteroaromatic ring in which R ^101d , R ^101e , R ^101f and R ^101g have a nitrogen atom in the formula is an imidazole derivative (for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole). Etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.), imidazoline derivatives, imidazolidine Derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridy 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 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 (for example, Quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pro Examples include a teridine derivative, a carbazole derivative, a phenanthridine derivative, an acridine derivative, a phenazine derivative, a 1,10-phenanthroline derivative, an adenine derivative, an adenosine derivative, a guanine derivative, a guanosine derivative, a uracil derivative, and a uridine derivative.
(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.

(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).

(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.

(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. A linear or branched alkylene group.)

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.

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

(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, 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, for example, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, triethylammonium nonafluorobutanesulfonate, pyridinium nonafluorobutanesulfonate, triethylammonium camphorsulfonate, pyridinium camphorsulfonate, nona Tetra n-butylammonium fluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, p-Toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid ( -Tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, trifluoromethane Tris (p-tert-butoxyphenyl) sulfonium sulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxy) p-toluenesulfonate Phenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobuta Triphenylsulfonium sulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate ( 2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, trifluoro Lomethanesulfone Cyclohexylmethyl (2-oxocyclohexyl) sulfonium acid, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2 ' -Onium salts such as naphthylcarbonylmethyltetrahydrothiophenium triflate.

  Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) ) Diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, B hexylsulfonyl-1-(tert-butylsulfonyl) diazomethane, 1-cyclohexyl sulfonyl-1-(tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1-(tert-butylsulfonyl) diazomethane derivatives such as diazomethane.

  Bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime Bis-O- (p-toluenesulfonyl) -2,3-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- (n-butanesulfonyl) -2- Til-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, Scan -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

Bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane.
Β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.
Sulfonic acid ester derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene .

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 -Chloroethane sulfonic acid ester, N-hydroxysuccinimide benzene sulfonic acid ester, N- Droxysuccinimide-2,4,6-trimethylbenzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide methanesulfonate N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimide ethanesulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonic acid ester, N-hydroxyglutarimide methanesulfonic acid ester, N-hydroxyglutarimide benzenesulfonic acid Esters, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimidebenzenesulfonate, N-hydroxyphthalate Imidotrifluoromethanesulfonic 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-dicarboximide p-toluenesulfonate Sulfonic acid ester derivatives of N-hydroxyimide compounds such as triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxy), and the like. Phenyl) 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) sulfonium Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonate L) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propyl) Diazomethane derivatives such as sulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) ) -Α-dimethylglyoxime and other glyoxime derivatives; bissulfone derivatives such as bisnaphthylsulfonylmethane; N-hydroxysuccinimide methanesulfonate; Cinimide trifluoromethanesulfonate ester, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide p-toluenesulfonate A sulfonic acid ester derivative of an N-hydroxyimide compound such as an 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 (D) 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 less than 0.1 part, the amount of acid generated is small and the crosslinking reaction may be insufficient. If the amount exceeds 50 parts, a mixing phenomenon may occur due to the acid moving to the upper resist.

  As the organic solvent (B) that can be used in the antireflection film material of the present invention, the above-mentioned polysilsesquioxane containing a substituent containing a silicon atom, an acid generator, a crosslinking agent, a crosslinking promoting additive, and other additives If an agent etc. melt | dissolve, there will be no restriction | limiting in particular. 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. Is not to be done. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, ethyl lactate, propylene glycol monomethyl ether acetate and mixed solvents thereof are preferably used.

  The blending amount of the solvent is preferably 500 to 10,000 parts, particularly preferably 1,000 to 5,000 parts, relative to 100 parts of the base resin.

  In the first pattern formation method of the present invention, the antireflection film material is applied on a substrate to be processed, and baked to form an antireflection film layer, and a photoresist solution is applied thereon, prebaked, and photo-processed. Form a resist film layer, irradiate the pattern circuit area with radiation, develop with a developing solution to form a resist pattern, and process the antireflection film layer and the substrate to be processed using the photoresist layer as a mask with a dry etching apparatus Is.

  In the second pattern forming method, an organic film is formed on a substrate to be processed, the antireflection film material is applied thereon, baked to form an antireflection film layer, and a photoresist solution is formed thereon. Apply and pre-bake to form a photoresist film layer, irradiate the pattern circuit area with radiation, develop with a developing solution to form a resist pattern, and then use a dry etching apparatus to mask the photoresist layer as an antireflection film The layer and the substrate to be processed are processed, and then the lower organic film is processed by dry etching using oxygen plasma using the antireflection film material as a hard mask, and the substrate is processed by dry etching using the organic film as a mask.

  2 to 5 illustrate this. As shown in FIG. 2, a film to be processed (substrate to be processed) 2 is formed on the substrate 1, an organic film 3 is formed thereon, and then An antireflection film 4 is formed using the antireflection film material according to the present invention, a resist film 5 is further formed thereon, and patterned according to a conventional method. Next, as shown in FIG. 3, the antireflection film 4 is dry-etched according to this resist pattern. Further, as shown in FIG. 4, the resist film 5 is removed, and the antireflection film 4 is used as a hard mask to remove oxygen. Gas dry etching is performed to process the organic film 3. Thereafter, as shown in FIG. 5, the film 2 is processed by dry etching using the organic film 3 as a mask.

  Although the etching apparatus for obtaining the etching shown in FIGS. 2, 3 or 3 and 4 may be the same or different, the productivity is improved by continuously etching with the same apparatus. Alternatively, all of the etching in FIGS. 2 to 4 can be continuously performed using the same etching apparatus.

  In the third pattern forming method, an antireflection film material is applied on a substrate to be processed, and baked to form an antireflection film layer. A photoresist solution is applied thereon, and prebaked to form a photoresist film layer. Forming, irradiating the pattern circuit area with radiation, developing with a developing solution to form a resist pattern, processing the antireflection film layer using the photoresist layer as a mask with a dry etching apparatus, and then anti-reflection film by dry etching The substrate to be processed is processed using the layer as a hard mask.

  FIGS. 6 and 7 illustrate this. As shown in FIG. 6, a processed film (processed substrate) 2 is formed on the substrate 1, and the antireflection film material according to the present invention is formed thereon. An antireflection film 4 is formed using the resist film 5 and a resist film 5 is further formed thereon, followed by patterning according to a conventional method. Next, as shown in FIG. 7, the antireflection film 4 and further the film to be processed 2 are dry-etched according to this resist pattern.

  In order to obtain the pattern shown in FIG. 7, the dry etching of the antireflection film of the present invention and the dry etching of the film to be processed below may be performed using the same etching apparatus or different ones. The productivity is improved by continuously etching with a material.

After the pattern formation in FIG. 4, the antireflection film of the present invention can be peeled off simultaneously with the etching of the substrate by dry etching with a fluorocarbon gas if the substrate to be processed is SiO ₂ , SiN, or SiON in FIG. is there. Further, even if the antireflection film cannot be sufficiently peeled off, it can be peeled off simultaneously with the organic film by wet treatment with sulfuric acid hydrogen peroxide solution or the like.
After the pattern formation in FIG.

  The hard mask film made of an inorganic material was difficult to selectively peel off while leaving the substrate to be processed, but the hard mask antireflection film of the present invention can be selectively peeled without affecting the substrate to be processed. .

Here, the substrate is not particularly limited, and is a material different from the film to be processed (substrate to be processed) such as Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al or the like. Is used. Various low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and their stopper films are used as the work film. Usually, it can be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. The organic film is generated by heating a cresol novolak, naphthol novolak, cresol dicyclopentadiene novolak, amorphous carbon, polyhydroxystyrene, (meth) acrylate, polyimide, polysulfone, etc. mixed with a crosslinking agent and an acid generator. The acid-crosslinked material is preferably used, and can usually be formed to a thickness of 50 to 2,000 nm, particularly 100 to 1,500 nm.

  The antireflection film of the present invention can be produced on a substrate by a spin coat method or the like, similar to a photoresist. After spin coating, it is desirable to evaporate the solvent and bake to accelerate the crosslinking reaction in order to prevent mixing with the upper layer resist. The baking temperature is preferably in the range of 80 to 300 ° C. and in the range of 10 to 300 seconds. After the antireflection film layer is produced, a resist layer is produced thereon, and the spin coat method is preferably used as in the antireflection film layer. Pre-baking is performed after spin-coating the resist, and a range of 10 to 300 seconds at 80 to 180 ° C. is preferable. Thereafter, exposure is performed, post-exposure baking (PEB), and development is performed to obtain a resist pattern.

Etching of the antireflection film is performed using chlorofluorocarbon gas, nitrogen gas, carbon dioxide gas or the like. The antireflection film of the present invention is characterized in that the etching rate with respect to the gas is high and the film loss of the upper resist film is small. The next base film is etched mainly using a chlorofluorocarbon gas for SiO ₂ and SiN, and etching mainly using a chlorine and bromine gas for p-Si, Al, and W. The antireflection film of the present invention is excellent in etching resistance to chlorine and bromine, and can be applied as a hard mask particularly when the base is p-Si, Al, W or the like. Even when the underlayer is a SiO ₂ or SiN film, the antireflection film of the present invention has an etching rate faster than that of the photoresist but is slower than that of the underlayer and can function as a hard mask.

The antireflection film of the present invention can also be applied as an intermediate layer in a three-layer resist process. In this process, an organic layer is first formed on a substrate to be processed by a spin coating method or the like. Since this organic layer functions as a mask when etching the substrate to be processed, it is desirable that the organic layer has high etching resistance, and it is required not to mix with the upper silicon-containing antireflection film. It is desirable to crosslink by. An antireflection film layer and a photoresist layer of the present invention are produced thereon by the above method, and a resist pattern is obtained by exposure and development. Next, the antireflection film is etched, the resist pattern is transferred to the antireflection film, the pattern of the antireflection film is transferred to the organic layer by oxygen plasma etching, and the substrate to be processed is etched.
The oxygen plasma etching gas is mainly oxygen gas, but can be mixed with SO ₂ , CO ₂ , CO, N ₂ , NH ₃ , NO, NO ₂ gas.

  The photoresist material used here may be a positive type or a negative type, but a chemical amplification type containing a base resin having an acid labile group and an acid generator is particularly preferable. A positive type is preferable. Known resist materials can be used.

  The antireflection film of the present invention exhibits an effect at a wavelength of 200 nm or less, and in particular, exposure with an ArF excimer laser with a wavelength of 193 nm is preferably used. As a resist material used in this respect, a base resin having a structure not containing aromatics is preferably used. In particular, the base resin is poly (meth) acrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride. Three or more quaternary copolymer with alternating polymer and poly (meth) acrylic acid or its derivative, three or quaternary or more with cycloolefin derivative-maleimide alternating polymer and poly (meth) acrylic acid or its derivative And one or more polymer polymers selected from two or more of these, or polynorbornene and metathesis ring-opening polymers, are preferred. 8) Weight average molecular weight having a repeating unit represented by 1,000 to 500,000, preferably 5,000 to 100,000 Those based resin a polymer compound are preferable.

Here, R ⁰⁰¹ represents a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or CH ₂ CO ₂ R ⁰⁰³ . R ⁰⁰² represents a hydrogen atom, a methyl group or CO ₂ R ^003. R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert -Butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group, butyladamantyl group Examples include groups. R ⁰⁰⁴ represents a hydrogen atom, a C 1-15 carboxy group or a monovalent hydrocarbon group containing a hydroxyl group (preferably a linear, branched or cyclic alkyl group), specifically carboxyethyl, Examples thereof include carboxybutyl, carboxycyclopentyl, carboxycyclohexyl, carboxynorbornyl, carboxyadamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl and the like. At least one of R ^{005 to} R ^{008 is} a C 1-15 carboxy group or a monovalent hydrocarbon group containing a hydroxyl group (preferably a linear, branched or cyclic alkyl group), or fluorine at the β-position A hydroxy group having an atom or a fluorinated alkyl group, and the rest each independently represents a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms or a fluorinated alkyl Indicates a group. Specific examples of the monovalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group include carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, and 2-carboxyethoxy. Carbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxy Carbonyl, hydroxynorbornyloxycarbonyl, hydroxyadamantyloxycarbonyl There can be exemplified. Examples of the straight, the branched or cyclic alkyl group, specifically exemplified the same ones as exemplified for R ^003. R ^{005 to} R ⁰⁰⁸ may form a ring with each other, and in that case, at least one of R ^{005 to} R ⁰⁰⁸ is a divalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group ( Preferably a linear or branched alkylene group), and the rest each independently represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. Specific examples of the divalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group include one hydrogen atom from those exemplified for the monovalent hydrocarbon group containing a carboxy group or a hydroxyl group. Excluded are examples. Specific examples of the linear, branched or cyclic alkylene group having 1 to 15 carbon atoms include those obtained by removing one hydrogen atom from those exemplified for ^R003 . R ⁰⁰⁹ represents a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 3 to 15 carbon atoms, specifically 2-oxooxolan-3-yl, 4,4-dimethyl-2-oxo. Examples include oxolan-3-yl, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolan-5-yl and the like. . At least one of R ^{010 to} R ⁰¹³ represents a —CO ₂ — partial structure having 2 to 15 carbon atoms or a monovalent hydrocarbon group containing sulfone or sulfonamide, and the rest each independently represents a hydrogen atom or 1 carbon atom. -15 linear, branched or cyclic alkyl groups are shown. Specific examples of the monovalent hydrocarbon group containing a —CO ₂ — partial structure having 2 to 15 carbon atoms include 2-oxooxolan-3-yloxycarbonyl and 4,4-dimethyl-2-oxooxo. Lan-3-yloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolane-5 -Ilyloxycarbonyl and the like can be exemplified. Examples of the straight, the branched or cyclic alkyl group, specifically exemplified the same ones as exemplified for R ^003. R ^{010 to} R ⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the rest each independently represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. Specific examples of the divalent hydrocarbon group containing a —CO ₂ — partial structure having 1 to 15 carbon atoms include 1-oxo-2-oxapropane-1,3-diyl and 1,3-dioxo-2. - oxa-1,3-diyl, 1-oxo-2-Okisabutan-1,4-diyl, other like 1,3-dioxo-2-Okisabutan-1,4-diyl, the -CO ₂ - partial structure The thing etc. which remove | excluded one hydrogen atom from what was illustrated with the monovalent | monohydric hydrocarbon group containing this can be illustrated. Specific examples of the linear, branched or cyclic alkylene group having 1 to 15 carbon atoms include those obtained by removing one hydrogen atom from those exemplified for ^R003 . R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specifically, norbornyl, bicyclo [3.3.1] nonyl, tricyclo [5. 2.1.0 ^2,6 ] decyl, adamantyl, ethyladamantyl, butyladamantyl, norbornylmethyl, adamantylmethyl and the like. R ⁰¹⁵ represents an acid labile group. R ⁰¹⁶ represents a methylene or oxygen atom. R ⁰¹⁷ does not exist or is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and may contain a substituent containing a heteroatom such as hydroxy, alkoxy group or acetyl group. R ⁰¹⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. k is 0 or 1. a1, a2, a3, b1, b2, b3, c1, c2, c3, d1, d2, d3, e are numbers from 0 to less than 1.

Specific examples of the acid labile group for ^R015 include groups represented by the following general formulas (L1) to (L5), a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, and each alkyl group. Examples thereof include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

In the formula, R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, an ethyl group or a propyl group. Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may form a ring, and in the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each have 1 to 18 carbon atoms, Preferably 1-10 linear or branched alkylene groups are shown.

R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula ( And a tertiary alkyl group specifically includes a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, 1 -Ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, etc. Specifically, a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like can be given as an oxoalkyl group. Specific examples include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-5-oxooxolan-4-yl group. a is an integer of 0-6.

R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, as a linear, branched or cyclic alkyl group. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, A cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, etc. can be exemplified. Specific examples of the aryl group which may be substituted include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl. Group, pyrenyl group and the like. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

R ^L06 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, and specific examples thereof are the same as those of R ^L05. it can. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, Linear, branched or cyclic alkyl groups such as cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, alkoxy groups Carbonyl group, oxo group, amino group, alkylamino group, cyano group, mercapto group, Kiruchio group, can be exemplified those sulfo group. R ^{L07 to} R ^L16 may form a ring with each other (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 And R ^L14 ), in which case a divalent hydrocarbon group which may contain a heteroatom having 1 to 15 carbon atoms is shown, and one hydrogen atom is removed from those exemplified above for the monovalent hydrocarbon group The thing etc. can be illustrated. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

  Of the acid labile groups represented by the formula (L1), specific examples of the linear or branched ones include the following groups.

  Among the acid labile groups represented by the above formula (L1), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated.

  Specific examples of the acid labile group of the above formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec- Butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl, 3 -Ethyl-1-cyclohexen-3-yl and the like can be exemplified.
Specific examples of the acid labile group of the above formula (L4) include the following groups.

In addition, examples of the tertiary alkyl group, trialkylsilyl group, and oxoalkyl group of the acid labile group represented by ^R015 include those exemplified above.
Specific examples of the acid labile group of the above formula (L5) include the following groups.

  As the acid generator used for the chemically amplified resist material, the same acid generator as that described for the antireflection film material can be used.

  EXAMPLES Hereinafter, although a synthesis example and an Example are shown and this invention is demonstrated concretely, this invention is not limited by these description.

[Synthesis Example 1]
31.6 g of tris (trimethylsilyl) silylethyltrimethoxysilane and 28.3 g of 3-glycidoxypropyltriethoxysilane were dissolved in 200 g of tetrahydrofuran (THF) and 100 g of pure water. 21 g was added dropwise over 1 hour, and then the temperature was raised to 64 ° C. to conduct silanol condensation reaction, epoxy group ring-opening reaction, and hydrochloric acid addition reaction.

  200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 60 ° C. Under reduced pressure, THF and diethyl ether water were removed to obtain polymer 1 shown below.

The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by C ¹³ -NMR as follows.

[Synthesis Example 2]
Dissolve 31.6 g of tris (trimethylsilyl) silylethyltrimethoxysilane and 28.3 g of 3-glycidoxypropyltriethoxysilane in 200 g of tetrahydrofuran and 100 g of pure water, bring the liquid temperature to 35 ° C., and add 9.6 g of 70% nitric acid. The solution was added dropwise over 1 hour, and then the temperature was raised to 64 ° C. to conduct a silanol condensation reaction and an epoxy group ring-opening reaction.

200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 60 ° C. Under reduced pressure, THF and diethyl ether water were removed to obtain polymer 2 shown below.
The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by C ¹³ -NMR as follows.

[Synthesis Example 3]
In 200 g of tetrahydrofuran and 100 g of pure water, 15.9 g of tris (trimethylsilyl) silylethyltrimethoxysilane, 28.3 g of 3-glycidoxypropyltriethoxysilane and 13.9 g of 1-naphthyltriethoxysilane were dissolved, and the liquid temperature was 35. Then, 9.6 g of 70% nitric acid was added dropwise over 1 hour, and then the temperature was raised to 64 ° C. to conduct a silanol condensation reaction and an epoxy group ring-opening reaction.

200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 60 ° C. Under reduced pressure, THF and diethyl ether water were removed to obtain polymer 3 shown below.
The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by C ¹³ -NMR as follows.

[Synthesis Example 4]
In 200 g of tetrahydrofuran and 100 g of pure water, 31.6 g of tris (trimethylsilyl) silylethyltrimethoxysilane and 28.3 g of 3-glycidoxypropyltriethoxysilane were dissolved, the liquid temperature was adjusted to 35 ° C., tetramethylammonium hydroxide 5 water 5 g of the Japanese product was added dropwise over 1 hour, and then the temperature was raised to 60 ° C. to conduct a silanol condensation reaction.
200 g of diethyl ether was added to the reaction liquid, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 60 ° C. Under reduced pressure, THF and diethyl ether water were removed to obtain a polymer 4 shown below.
The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by C ¹³ -NMR as follows.

[Example]
The silicone polymer represented by the above polymers 1 to 4, the acid generator represented by AG1 and 2, and the crosslinking agent represented by CR1 and 2 are represented in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M). Antireflective film solutions were prepared by dissolving at a ratio shown in 1 and filtering through a 0.1 μm fluororesin filter.

  Next, the antireflection film solution was applied onto a silicon substrate and baked at 200 ° C. for 120 seconds to form an antireflection film having a thickness of 193 nm (hereinafter abbreviated as BARC 1 to 6). J. et al. A. Table 1 shows the results of obtaining the refractive indices (n, k) of BARC 1 to 6 at a wavelength of 193 nm using a spectroscopic ellipsometer (VASE) with variable incident angle from Woollam.

PGMEA; propylene glycol monomethyl ether acetate

  Next, resist solutions 1 to 3 for ArF comprising ArF resist polymers 1 to 3, an acid generator PAG1, a base additive, and a solvent having the composition shown in Table 2 were prepared. This resist solution was applied on the silicon substrate on which the antireflection films BARC1 to BARC1-6 were formed, and baked at 120 ° C. for 60 seconds to form a resist film layer having a thickness of 250 nm. Next, the film was exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 ring illumination, Cr mask), baked at 110 ° C. for 90 seconds (PEB), and 2.38% by mass. Development was performed with an aqueous tetramethylammonium hydroxide (TMAH) solution to obtain a positive pattern. The pattern shape of 0.11 μmL / S of the obtained pattern was observed, and it was confirmed that no bottoming, undercut, or intermixing phenomenon occurred in the vicinity of the substrate, and a rectangular pattern was obtained.

  Next, a dry etching resistance test was performed. First, the same antireflection film (BARC 1 to 6) used for the refractive index measurement was prepared, and a resist solution was prepared with the composition shown in Table 2 in the same manner as described above.

(1) Etching test of the above antireflection film and resist film with CHF ₃ / CF ₄ gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the difference in film thickness between the antireflection film and the resist before and after etching is measured. The results are shown in Table 3.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,300W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
Time 10sec

₍₂₎ Cl ₂ / BCl ₃ system using an etching test Nichiden Anelva Co., Ltd. dry etching apparatus L-507D-L Gas was calculated the difference between the film thickness of before and after etching of the polymer film.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30ml / min
BCl ₃ gas flow rate 30ml / min
CHF ₃ gas flow rate 100ml / min
O ₂ gas flow rate 2ml / min
60 sec

As shown in Table 1, each BARC has a refractive index k value of 0.15 or more, and is an extinction coefficient sufficient to exhibit a sufficient antireflection effect. As shown in Table 3, the CF ₄ / CHF ₃ gas The dry etching rate is sufficiently faster than that of the resist, sufficiently slower than the SiO ₂ film, and has a sufficient function as a hard mask in the SiO ₂ film etching. On the other hand, as shown in Table 4, Cl ₂ / BCl ₃ etching for etching the substrate p-Si is sufficiently slower than p-Si and satisfies the performance as a hard mask. Moreover, it was recognized that the resist shape after patterning is also good.

It is a graph which shows the relationship between the film thickness of an antireflection film, and a reflectance. It is sectional drawing of the state in which the example of the pattern formation method of this invention was shown and the resist pattern was formed. In the example, it is sectional drawing of the state which etched the antireflection film. In the same example, it is sectional drawing of the state which etched the organic film. In the same example, it is sectional drawing of the state which etched the to-be-processed film. It is sectional drawing of the state in which the other example of the pattern formation method of this invention was shown and the resist pattern was formed. In the example, it is sectional drawing of the state which etched the antireflection film and the to-be-processed film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Film to be processed 3 Organic film 4 Antireflection film 5 Resist film

Claims (8)

The high molecular compound characterized by having a repeating unit represented by following General formula (1).
(In the formula, R ¹ is a single bond, or an alkylene group that may be mediated by linear, branched, or cyclic -COO-, -CONH-, or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond.) An antireflection film material comprising a polymer compound obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (2).
[Wherein, R ¹ is a single bond or an alkylene group which may be mediated by linear, branched or cyclic -COO-, -CONH- or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond, wherein R ^{2 to} R ⁶ are a hydrogen atom, an alkyl group that may be substituted with a linear, branched, or cyclic fluorine atom having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, or the following general formula (3)
(R ^{7 to} R ¹¹ are a hydrogen atom, an alkyl group which may be substituted with a linear, branched or cyclic fluorine atom having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) It is a silicon-containing group shown by these. R ³ and R ⁴ may be bonded to form a polysilane ring together with the silicon atom to which they are bonded. a is 0 or 1; X ¹ , X ² , and X ³ are each a halogen atom, a hydroxy group, or an alkoxy group having 1 to 10 carbon atoms. m is 0 ≦ m ≦ 10. ] It contains a polymer compound obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (2) and a silicon compound having a crosslinking group represented by the following general formula (4). Antireflection film material.
[Wherein, R ¹ is a single bond or an alkylene group which may be mediated by linear, branched or cyclic -COO-, -CONH- or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond, wherein R ^{2 to} R ⁶ are a hydrogen atom, an alkyl group that may be substituted with a linear, branched, or cyclic fluorine atom having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, or the following general formula (3)
(R ^{7 to} R ¹¹ are a hydrogen atom, an alkyl group which may be substituted with a linear, branched or cyclic fluorine atom having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) It is a silicon-containing group shown by these. R ³ and R ⁴ may be bonded to form a polysilane ring together with the silicon atom to which they are bonded. a is 0 or 1; X ¹ , X ² , and X ³ are each a halogen atom, a hydroxy group, or an alkoxy group having 1 to 10 carbon atoms. m is 0 ≦ m ≦ 10. ]
(In the formula, R ¹² is a monovalent organic group having a crosslinking group, and X ¹ , X ² , and X ³ are as described above.) An antireflection film material comprising a polymer compound having a repeating unit represented by the following general formula (5) and having a molecular weight of 500 or more.
[Wherein, R ¹ is a single bond or an alkylene group which may be mediated by linear, branched or cyclic -COO-, -CONH- or -O- having 1 to 20 carbon atoms, -COO-, -CONH-, -O-, or a siloxane bond, wherein R ^{2 to} R ⁶ are a hydrogen atom, an alkyl group that may be substituted with a linear, branched, or cyclic fluorine atom having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, or the following general formula (3)
(R ^{7 to} R ¹¹ are a hydrogen atom, an alkyl group which may be substituted with a linear, branched or cyclic fluorine atom having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) It is a silicon-containing group shown by these. R ³ and R ⁴ may be bonded to form a polysilane ring together with the silicon atom to which they are bonded. a is 0 or 1; R ¹² is a monovalent organic group having a crosslinking group, and 0 <c <1, 0 <d <1, and 0.5 ≦ c + d ≦ 1. ]   The antireflection film material according to any one of claims 2 to 4, further comprising (B) an organic solvent, (C) a crosslinking agent, and (D) an acid generator.   An antireflection film material according to any one of claims 2 to 5 is applied on a substrate to be processed, baked to form an antireflection film layer, a photoresist solution is applied thereon, and prebaked. Form a photoresist film layer, irradiate the pattern circuit area with radiation, develop with a developing solution to form a resist pattern, and process the antireflection film layer and the substrate to be processed using the photoresist layer as a mask with a dry etching device And a pattern forming method.   An organic film is formed on a substrate to be processed, and the antireflection film material according to any one of claims 2 to 5 is applied thereon, and baked to form an antireflection film layer. Apply a resist solution, pre-bake to form a photoresist film layer, irradiate the pattern circuit area with radiation, develop with a developing solution to form a resist pattern, and reflect using the photoresist layer as a mask with a dry etching device An anti-reflective film material is processed by using the antireflection film material according to any one of claims 2 to 5 as a hard mask by dry etching using oxygen plasma, and then an organic film is processed by dry etching. A pattern forming method characterized in that a substrate to be processed is processed using a mask as a mask. An antireflection film material according to any one of claims 2 to 5 is applied on a substrate to be processed, baked to form an antireflection film layer, a photoresist solution is applied thereon, and prebaked. A photoresist film layer is formed, the pattern circuit area is irradiated with radiation, developed with a developer to form a resist pattern, and the anti-reflection film layer is processed with a dry etching apparatus using the photoresist layer as a mask, and then dried. A pattern forming method comprising processing a substrate to be processed by etching using an antireflection film layer as a hard mask.