JP5579553B2 - Resist underlayer film material, resist underlayer film forming method, pattern forming method - Google Patents

Description

  The present invention relates to a resist underlayer film material, a resist underlayer film forming method effective as an antireflection film material used for microfabrication in a manufacturing process of a semiconductor element and the like, and far ultraviolet rays, KrF excimer laser light (248 nm) using the same, The present invention relates to a pattern forming method suitable for ArF excimer laser light (193 nm), soft X-rays (EUV, 13.5 nm), and electron beams (EB).

  With the high integration and high speed of LSI, pattern rule miniaturization is progressing rapidly. In particular, the expansion of the flash memory market and the increase in storage capacity are leading to miniaturization. For fine lines in miniaturization, mass production of devices of 65 nm node by ArF lithography is being performed, and preparation for mass production of 45 nm node by next generation ArF immersion lithography is in progress. Next generation 32nm node includes immersion lithography with ultra high NA lens combining liquid with higher refractive index than water, high refractive index lens and high refractive index resist film, vacuum ultraviolet light (EUV) with wavelength of 13.5nm Lithography, double exposure of ArF lithography (double patterning lithography), and the like are candidates and are being studied.

  With the progress of miniaturization, the thinning of the photoresist film has progressed, and a multilayer film process for transferring a thin photoresist pattern has been studied.

  As a multilayer film process, a three-layer resist process has been proposed in which a resist intermediate layer film containing silicon is formed under a photoresist film (hereinafter also referred to as a resist upper layer film), and an organic resist underlayer film is further laminated thereunder. Yes. In general, a single-layer resist has better resolution than a silicon-containing resist, and a high-resolution single-layer resist can be used as an exposure imaging layer in a three-layer resist process. A spin-on-glass (SOG) film is used as the resist intermediate layer film.

  Patent Document 1 proposes a silicon-containing layer material imparted with an antireflection effect. In general, a multilayer antireflection film has a higher antireflection effect than a single-layer antireflection film, and is widely used industrially as an antireflection film for optical materials. By imparting an antireflection effect to both the resist intermediate layer film and the resist underlayer film, a high antireflection effect can be obtained.

The NA of the projection lens exceeds 1 by immersion lithography, and the angle of light incident on the photoresist film, the resist intermediate layer film, and the resist lower layer film becomes much shallower. This increases the proportion of reflected light from the substrate.
As the processing dimensions become finer, the photoresist film becomes thinner, and the ratio of reflection from the substrate also increases as the thickness of the silicon-containing intermediate film becomes thinner. It has become difficult to prevent reflection by relying only on the intermediate layer film, and it is becoming necessary to suppress reflection not only by the intermediate layer film but also by optimizing the optical characteristics of the lower layer film.

The resolution that can be reached with the highest NA of water immersion lithography using an NA 1.35 lens is 40 to 38 nm and cannot reach 32 nm. Therefore, development of a high refractive index material for further increasing NA is being carried out. It is the minimum refractive index among the projection lens, liquid, and resist film that determines the limit of the NA of the lens. In the case of water immersion, the refractive index of water is the lowest compared with the projection lens (refractive index of 1.5 for synthetic quartz) and resist film (refractive index of 1.7 for conventional methacrylate system). The lens NA was fixed. Recently, highly transparent liquids having a refractive index of 1.65 have been developed. In this case, it is necessary to develop a projection lens material having the lowest refractive index and a high refractive index of the projection lens made of synthetic quartz. LUAG (Lu ₃ Al ₅ O ₁₂ ) has a refractive index of 2 or more and is the most expected material, but has a problem of large birefringence and absorption. Even if a projection lens material having a refractive index of 1.8 or higher is developed, the NA of the liquid having a refractive index of 1.65 is only 1.55, and 32 nm cannot be resolved. In order to resolve 32 nm, a liquid having a refractive index of 1.8 or more is required. There is a trade-off between absorption and refractive index, and no such material has yet been found. The development of high refractive index lithography has been discontinued because the problems of high refractive index of liquid and high transparency of high refractive index lens cannot be solved.

Recently, a double patterning process in which a pattern is formed by the first exposure and development, and a pattern is formed just between the first pattern by the second exposure has attracted attention recently. Many processes have been proposed as a double patterning method.
For example, the first exposure and development form a photoresist pattern with 1: 3 line and space spacing, the lower hard mask is processed by dry etching, and another hard mask is laid on the first hard mask. There is a method in which a line pattern is formed by exposure and development of a photoresist film in a space portion of the exposure, and a hard mask is processed by dry etching to form a line and space pattern that is half the pitch of the initial pattern.
Further, a photoresist pattern having a space and line spacing of 1: 3 is formed by the first exposure and development, the underlying hard mask is processed by dry etching, and a photoresist film is applied thereon. There is a method in which a second space pattern is exposed to a portion where the hard mask remains, and the hard mask is processed by dry etching. Either method is a method of processing a hard mask by two dry etchings.

In the above-described method, it is necessary to lay a hard mask twice. In the latter method, only one hard mask is required, but it is necessary to form a trench pattern that is difficult to resolve compared to a line pattern. In the latter method, a negative resist material is used for forming the trench pattern. Negative resist materials can use the same high-contrast light that forms lines with positive patterns, but negative resist materials have lower dissolution contrast than positive resist materials. When the line is formed with a positive resist material and the trench pattern with the same dimensions is formed with a negative resist material, the resolution is lower when the negative resist material is used.
The latter method uses a positive resist material to form a wide trench pattern, then heats the substrate to shrink the trench pattern, or coats a water-soluble film on the developed trench pattern. It may be possible to apply the RELACS method in which the trench is shrunk by heating and then crosslinking the resist film surface. .

  In the former and latter methods, the substrate processing needs to be etched twice, so that there is a problem that the throughput is lowered and the pattern is deformed or displaced due to the two etchings.

  In order to complete the etching once, there is a method in which a negative resist material is used in the first exposure and a positive resist material is used in the second exposure. There is also a method in which a positive resist material is used in the first exposure, and a negative resist material dissolved in a higher alcohol having 4 or more carbon atoms in which the positive resist material is not dissolved in the second exposure. In these cases, since a negative resist material having a low resolution is used, the resolution is deteriorated.

  The most critical problem in double patterning is the alignment accuracy of the first and second patterns. Since the size of the positional deviation is a variation in line dimensions, for example, if it is attempted to form a 32 nm line with an accuracy of 10%, an alignment accuracy within 3.2 nm is required. Since the alignment accuracy of the current scanner is about 8 nm, a significant improvement in accuracy is necessary.

Due to the problem of the alignment accuracy of the scanner and the problem that it is difficult to divide one pattern into two, a method of halving the pitch by one exposure is being studied.
A method has been proposed in which a film is attached to the side walls on both sides of the line pattern, thereby halving the pitch (Non-Patent Document 1). As such a sidewall process, in the 4th immersion symposium (2007), lecture number; PR-01, title; The spacer space method using the hard mask under the photoresist film and the film attached to the sidewall of the photoresist film and the film embedded in the space between the films as an etching pattern, and the film attached to the hard mask sidewall under the photoresist film are etched. A spacer line method used as a pattern has been proposed. In either method, a film attached to the side wall of the hard mask under the resist is used as an etching mask.

  When the resist line deviates from the target dimension, the line CD used as an etching mask in the spacer space method varies, and the spacer line method leads to variations in line position. In either method, it is necessary to improve both the film thickness control of the side wall spacer and the dimension control of the resist pattern after development. With either side wall spacer method, the pitch can be halved with one exposure, but the end point of the line becomes donut-shaped, and the end line may be unnecessary, so this is erased. Exposure is required, and at least two exposures are required. However, in this case, very high-precision alignment is not required for halving the pitch in the second exposure.

In general, polysilicon, a silicon oxide film, a silicon nitride film, a silicon nitride oxide film, a titanium nitride film, an amorphous carbon film, or the like is used as a hard mask. These films are formed by a CVD method or the like. As the sidewall pattern, a material different from the hard mask is used in order to process the hard mask and the underlying substrate.
In the sidewall spacer method, in order to obtain an etching pattern based on a film attached only to the sidewall of the hard mask, the film on the hard mask and the spacer must be removed. In the spacer space method, it is necessary to remove the side wall pattern after filling the space. In the spacer line method, after the space pattern is formed on the side wall of the hard mask, it is necessary to remove only the hard mask. Both are expensive processes with a large number of etching processes and film removal steps, a low throughput.

  A method of reducing the hole pattern diameter by forming a silicon oxide film on a resist pattern by a chemical vapor deposition (CVD) method has been proposed, and studies for directly attaching a silicon oxide film to the resist pattern are in progress. . The ALD (Atomic Layer Deposition) method is a kind of CVD method and is a method of laminating silicon oxide at an atomic level. It is considered that the film is excellent in conformality and film thickness uniformity and suitable for forming a silicon oxide film for a sidewall spacer. Since the ALD method can deposit an oxide film at a low temperature of 100 ° C. or lower, the deformation of the resist pattern due to heat can be suppressed. The disadvantage of the ALD method is that the throughput is low, but the processing capacity per unit time per sheet has been increased by batch processing a large number of wafers. As a result, examination of a process for directly forming an oxide film spacer on the side wall of the resist pattern is accelerated.

  On the resist pattern, apply an alcohol that does not dissolve the resist pattern, or a silicone compound dissolved in water. The etch pattern and chemical mechanical polishing (CMP) are used to crush the head of the resist pattern. An image reversal technique for processing a substrate has been proposed. For example, a dot pattern or an isolated line pattern is formed using a positive resist, and a hole pattern or a trench pattern is formed using the positive / negative reversal technique. The method of forming a hole pattern or trench pattern by image inversion by forming a dot pattern or line pattern that has better optical contrast than using a positive resist to form a hole pattern or trench pattern is from the viewpoint of limit resolution and dimensional uniformity. It is advantageous.

  When a sidewall spacer or an inversion film is formed directly on the resist pattern, a silicon oxide film is used as these films. In this case, a hydrocarbon film is used for the lower layer of the photoresist curtain from the viewpoint of etching. In the case of the three-layer resist process, the reflection can be reduced by the two-layer antireflection film as described above. However, in the case of forming the sidewall spacer directly on the resist pattern or in the case of the inversion film forming process, the photoresist screen is used. Antireflection is performed in one lower layer. Although it is conceivable to carry out antireflection by making the hydrocarbon film into two layers, application of the lower layer film twice is disadvantageous from the viewpoint of throughput. From the viewpoint of improving throughput and reducing cost, it is desirable to obtain an antireflection effect by applying a single resist underlayer film.

Patent Document 2 discloses a lower layer film material containing a copolymer of hydroxystyrene and acenaphthylene, and Patent Document 3 shows a lower layer film material containing a copolymer of hydroxystyrene and nortricyclene.
These materials have excellent etching resistance, but the n value is low, the k value is high, and there is a sufficient antireflection effect for light at a shallow incident angle in immersion lithography using NA of 1.3 or more. I can't say that.

US Pat. No. 6,506,497 JP-A-2005-250434 JP 2004-205658 A

J. et al. Vac. Sci. Technol. B 17 (6), Nov / Dec 1999 4th Immersion Symposium (2007) Lecture number; PR-01, Title; Implementation of immersion lithography to NAND / CMOS lithography to NAND / CMOS device manufacturing

  The present invention has been made in view of the above circumstances, and a resist underlayer film of a multilayer resist film used in lithography, in particular, a resist underlayer film of a multilayer resist film having three layers, and a silicon oxide film directly on the sidewall of the resist pattern. A resist underlayer film used for forming a silicon oxide film on a resist pattern and performing positive / negative reversal, and a resist underlayer film material for forming a resist underlayer film that can reduce reflectivity and has high etching resistance Another object of the present invention is to provide a resist underlayer film forming method and a pattern forming method using the resist underlayer film forming method.

  In order to solve the above problems, according to the present invention, a resist underlayer film material for forming a resist underlayer film of a multilayer resist film used in lithography, wherein a styrene derivative unit having at least fluorine atoms is a repeating unit. A resist underlayer film material characterized by comprising a polymer contained as

  Such a resist underlayer film material functions as an excellent antireflection film particularly for exposure at a short wavelength, and has a high n value (refractive index) and k value (extinction coefficient) equivalent to those of a photoresist, Furthermore, a resist underlayer film having excellent etching resistance in substrate processing can be formed. The resist underlayer film obtained by using such a resist underlayer film material can be a resist underlayer film of a multilayer resist film having three layers, or a silicon oxide film can be directly formed on the side wall of the resist pattern, or a silicon oxide film can be formed on the resist pattern. This is particularly useful as a resist underlayer film directly under a resist pattern when a film is formed and a positive / negative reversal process is performed.

（上記一般式（１）中、Ｒ^１は水素原子又はメチル基である。Ｒ^２は水素原子、ヒドロキシ基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、炭素数１〜１０のアルキル基、アルコキシ基、炭素数１〜１１のアルコキシメチル基、アシロキシ基、アルコキシカルボニル基、炭素数１〜１２のアルコキシエチル基、及び、グリシジルエーテル基のいずれかであり、ヒドロキシ基及びカルボキシル基の水素は酸不安定基、フッ素で置換されたアルキル基、及びフッ素で置換されたアシル基のいずれかで置換されていても良い。ｍは１〜５の整数、ｎは０〜３の整数である。ａは０＜ａ≦１．０の範囲である。） In this case, the polymer preferably contains a styrene derivative unit having at least a fluorine atom represented by the following general formula (1).

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrogen atom, a hydroxy group, a carboxyl group, a hydroxymethyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group. Group, an alkoxymethyl group having 1 to 11 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an alkoxyethyl group having 1 to 12 carbon atoms, and a glycidyl ether group. It may be substituted with any of a stabilizing group, an alkyl group substituted with fluorine, and an acyl group substituted with fluorine, m is an integer of 1 to 5, n is an integer of 0 to 3. a is 0 <a ≦ 1.0.)

  Thus, examples of the polymer include those containing a repeating unit represented by the above general formula (1), that is, those containing a styrene derivative unit in which a fluorine atom is introduced into a benzene ring.

  In this case, the polymer is preferably a copolymer of a styrene derivative having at least a fluorine atom and acenaphthylene (derivative) and / or norbornadiene (derivative).

  Thus, in addition to a styrene derivative having at least a fluorine atom, acenaphthylene (derivative), that is, acenaphthylene and its derivative, and / or norbornadiene (derivative), that is, a polymer obtained by copolymerizing norbornadiene and its derivative. For example, it is possible to easily adjust to an ideal optical constant and improve etching resistance.

（上記一般式（２）中、Ｒ^１は水素原子又はメチル基である。Ｒ^２は水素原子、ヒドロキシ基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、炭素数１〜１０のアルキル基、アルコキシ基、炭素数１〜１１のアルコキシメチル基、アシロキシ基、アルコキシカルボニル基、炭素数１〜１２のアルコキシエチル基、及び、グリシジルエーテル基のいずれかであり、ヒドロキシ基及びカルボキシル基の水素は酸不安定基、フッ素で置換されたアルキル基、及びフッ素で置換されたアシル基のいずれかで置換されていても良い。Ｒ^３、Ｒ^４は水素原子、フッ素原子、ヒドロキシ基、カルボキシル基、ヒドロキシメチル基、炭素数１〜６のアルキル基、アシロキシ基、アルコキシカルボニル基、アセトキシメチル基、及びアルコキシメチル基のいずれかであり、カルボキシル基の水素は、フッ素原子又は酸素原子を含んでも良いアルキル基で置換されていても良い。ｍは１〜５の整数、ｎは０〜３の整数である。ａ、ｂ１、ｂ２はそれぞれ０＜ａ＜１．０、０≦ｂ１＜１．０、０≦ｂ２＜１．０、０＜ｂ１＋ｂ２＜１．０の範囲である。） At this time, examples of the polymer include those represented by the following general formula (2).

(In the general formula (2), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrogen atom, a hydroxy group, a carboxyl group, a hydroxymethyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group. Group, an alkoxymethyl group having 1 to 11 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an alkoxyethyl group having 1 to 12 carbon atoms, and a glycidyl ether group. R ³ and R ⁴ may be substituted with any of a stable group, an alkyl group substituted with fluorine, and an acyl group substituted with fluorine, wherein R ³ and R ⁴ are a hydrogen atom, a fluorine atom, a hydroxy group, a carboxyl group, and hydroxymethyl. Group, an alkyl group having 1 to 6 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an acetoxymethyl group, and an alkoxy group. It is any of a methyl group, and the hydrogen of the carboxyl group may be substituted with an alkyl group which may contain a fluorine atom or an oxygen atom, m is an integer of 1 to 5, and n is an integer of 0 to 3. A, b1, and b2 are ranges of 0 <a <1.0, 0 ≦ b1 <1.0, 0 ≦ b2 <1.0, and 0 <b1 + b2 <1.0, respectively.

  As shown in the general formula (2), the polymer contained in the resist underlayer film material of the present invention further includes an acenaphthylene (derivative) unit b1 and / or a norbornadiene (derivative) unit b2 in addition to the repeating unit a. A polymer is mentioned.

（上記一般式（３）中、Ｒ^１、Ｒ^３、Ｒ^４、ｍ、ｎ、ａ、ｂ１、ｂ２は前述の通りであり、Ｒは水素原子、炭素数１〜１０のアルキル基、アシル基、フッ素で置換されたアシル基、及び酸不安定基のいずれかである。） At this time, the polymer is preferably one represented by the following general formula (3).

(In the general formula (3), R ¹ , R ³ , R ⁴ , m, n, a, b1, b2 are as described above, and R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an acyl group , An acyl group substituted with fluorine, and an acid labile group.)

  If a polymer containing a fluorinated styrene repeating unit having a substituted or unsubstituted hydroxy group represented by the repeating unit a in the general formula (3) is included, the crosslinking density is increased, and etching resistance is improved. Further improvement can be achieved.

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

  Thus, if the resist underlayer film material further contains any one or more of an organic solvent, an acid generator, and a crosslinking agent, the applicability of the material to a substrate or the like can be improved. The crosslinking reaction in the resist underlayer film can be promoted by baking or the like after application to the substrate. Therefore, the resist underlayer film obtained from such a resist underlayer film material has good film thickness uniformity, less risk of intermixing with the resist upper layer film, and low diffusion of low molecular components into the resist upper layer film. It becomes.

  The present invention also provides a method for forming a resist underlayer film of a multilayer resist film used in lithography, wherein a resist underlayer film is formed by coating the resist underlayer film material of the present invention on a substrate by a spin coating method. A resist underlayer film forming method is provided.

  Thus, by coating the resist underlayer film material of the present invention on the substrate by spin coating, a resist underlayer film having excellent antireflection effect and etching resistance and having good film thickness uniformity can be obtained. It is preferable because

  Further, in the present invention, a method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film is formed on the substrate using the resist underlayer film material, and silicon atoms are contained on the resist underlayer film. Forming a resist intermediate layer film using the resist intermediate layer film material, forming a resist upper layer film on the resist intermediate layer film using a resist upper layer film material made of a photoresist composition, The pattern circuit region is exposed, and then developed with a developer to form a resist pattern on the resist upper layer film, and the resist intermediate layer film is etched using the obtained resist pattern as an etching mask. The resist underlayer film is etched using the layer film pattern as an etching mask, and the obtained resist underlayer film pattern is In the Tchingumasuku provide a pattern forming method comprising forming a pattern on a substrate by etching the substrate.

  The present invention also provides a method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film is formed on the substrate using the resist underlayer film material, and a photoresist composition is formed on the resist underlayer film. The resist upper layer film was formed using the resist upper layer film material, the pattern circuit region of the resist upper layer film was exposed, and then developed with a developer to form a resist pattern on the resist upper layer film. There is provided a pattern forming method comprising: etching a resist underlayer film using a resist pattern as an etching mask; and etching the substrate using the obtained resist underlayer film pattern as an etching mask to form a pattern on the substrate.

  The resist underlayer film material of the present invention is for obtaining a resist underlayer film of a three-layer resist process or a resist underlayer film of a two-layer resist process having such a resist intermediate layer film (silicon-containing intermediate layer) containing silicon atoms. It is particularly useful as a material.

  The present invention also provides a method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film is formed on the substrate using the resist underlayer film material, and a photoresist composition is formed on the resist underlayer film. The resist upper layer film was formed using the resist upper layer film material, the pattern circuit region of the resist upper layer film was exposed, and then developed with a developer to form a resist pattern on the resist upper layer film. A silicon oxide film is formed on the resist pattern by spin coating or CVD, and at least the silicon oxide film at the top of the resist pattern and the space is removed by etching while leaving the silicon oxide film on the side wall of the resist pattern, and the resist pattern is etched. The resist underlayer film is processed using the silicon oxide film on the sidewall as a mask, Strike underlayer film pattern as an etching mask to provide a pattern forming method comprising forming a pattern on a substrate.

  The resist underlayer film material of the present invention exhibits an excellent antireflection effect even when there is no silicon-containing intermediate layer film. Therefore, even when the sidewall spacer is directly formed on such a photoresist pattern, the antireflection effect is obtained by one layer of the resist underlayer film, and the shape of the photoresist pattern directly formed on the resist underlayer film becomes good. Furthermore, since throughput improvement and cost reduction can be achieved, it can be suitably used. Moreover, since it has the etching tolerance outstanding with respect to the board | substrate, a favorable pattern can be formed in a board | substrate.

  The present invention also provides a method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film is formed on the substrate using the resist underlayer film material, and a photoresist composition is formed on the resist underlayer film. The resist upper layer film was formed using the resist upper layer film material, the pattern circuit region of the resist upper layer film was exposed, and then developed with a developer to form a resist pattern on the resist upper layer film. A silicon oxide film is formed on the resist pattern, and at least the silicon oxide film above the resist pattern is removed by etching while leaving the silicon oxide film between the resist patterns, and the resist is masked by using the silicon oxide film between the remaining resist patterns as a mask. Process the underlayer film, and pattern the pattern on the substrate using the resulting resist underlayer film pattern as an etching mask. Forming a pattern forming method characterized by.

The resist underlayer film material of the present invention exhibits an excellent antireflection effect even when there is no silicon-containing intermediate layer film. Therefore, even when a negative oxide inversion is performed by spin-coating a silicon oxide (SiO ₂ film) material on the photoresist pattern, the anti-reflective effect is obtained by the resist underlayer film, and it is formed directly on the resist underlayer film. The formed photoresist pattern shape is improved, and further, throughput can be improved and cost reduction can be achieved. Moreover, since it has the etching tolerance outstanding with respect to the board | substrate, a favorable pattern can be formed in a board | substrate.

  According to the present invention, for example, a resist underlayer film material for a multi-layer resist process in which the upper layer film contains silicon, particularly a three-layer resist process, a silicon oxide film is formed directly on the side wall of the resist pattern, A resist underlayer film material used when positive / negative reversal is performed by forming a silicon oxide film on a pattern, and functions as an excellent antireflection film especially for exposure at a short wavelength, that is, polyhydroxystyrene, cresol novolak To obtain a resist underlayer film material having higher n value (refractive index) and k value (quenching coefficient), higher transparency than naphthol novolak, etc., and excellent etching resistance in substrate processing Can do.

In the three-layer resist process, the n value of the intermediate layer film (SiUL) is 1.7, the k value is 0.1, the film thickness is 40 nm, the n value of the lower layer film (CUL) is 1.6, and the k value is 0 to 1. It is a graph which shows the relationship of a board | substrate reflectance when changing 0 and a film thickness in the range of 0-200 nm. In the three-layer resist process, the n value of the intermediate layer film (SiUL) is 1.7, the k value is 0.1, the film thickness is 40 nm, the k value of the lower layer film (CUL) is 0.4, and the n value is 1.0 to 2.0 is a graph showing the relationship of the substrate reflectivity when the film thickness is changed in the range of 0 to 200 nm. In the three-layer resist process, the n value of the intermediate layer film (SiUL) is 1.7, the k value is 0.1, the film thickness is 20 nm, the n value of the lower layer film (CUL) is 1.6, and the k value is 0 to 1. It is a graph which shows the relationship of a board | substrate reflectance when changing 0 and a film thickness in the range of 0-200 nm. In the three-layer resist process, the n value of the intermediate layer film (SiUL) is 1.7, the k value is 0.1, the film thickness is 20 nm, the k value of the lower layer film (CUL) is 0.4, and the n value is 1.0 to 2.0 is a graph showing the relationship of the substrate reflectivity when the film thickness is changed in the range of 0 to 200 nm. A graph showing the relationship of substrate reflectivity when the n value of the lower layer film (CUL) in the two-layer resist process is 1.3, the k value is 0 to 1.2, and the film thickness is changed in the range of 0 to 150 nm. is there. A graph showing the relationship between the substrate reflectivity when the n value of the lower layer film (CUL) in the two-layer resist process is 1.4, the k value is 0 to 1.2, and the film thickness is changed in the range of 0 to 150 nm. is there. The graph which shows the relationship of a substrate reflectance when the n value of the lower layer film (CUL) in a two layer resist process is 1.5, k value is changed in the range of 0-1.2, and film thickness is changed in the range of 0-150 nm. is there. A graph showing the relationship between the substrate reflectivity when the n value of the lower layer film (CUL) in the two-layer resist process is 1.6, the k value is 0 to 1.2, and the film thickness is changed in the range of 0 to 150 nm. is there. The graph which shows the relationship of the substrate reflectivity when changing the n value of the lower layer film (CUL) in the two-layer resist process to 1.7, the k value from 0 to 1.2, and the film thickness from 0 to 150 nm. is there. In the two-layer resist process, the n-value of the lower layer film (CUL) is 1.8, the k value is 0 to 1.2, and the graph shows the relationship of the substrate reflectivity when the film thickness is changed in the range of 0 to 150 nm. is there. In the two-layer resist process, the n-value of the lower layer film (CUL) is 1.9, the k value is 0 to 1.2, and the graph shows the relationship of the substrate reflectivity when the film thickness is changed in the range of 0 to 150 nm. is there. It is a graph which shows the relationship of a substrate reflectance when n value of the lower layer film (CUL) in a two-layer resist process is 2.0, k value is changed in the range of 0 to 1.2, and film thickness is changed in the range of 0 to 150 nm. is there. It is explanatory drawing of a two-layer resist process. It is explanatory drawing of the side wall spacer method which attaches a silicon oxide film directly to the side wall of a resist pattern. It is explanatory drawing of the image reversal method which attaches a silicon oxide film between resist patterns and performs positive / negative inversion. It is explanatory drawing of a 3 layer resist process.

Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.
As a result of intensive studies to achieve the above object, the present inventors have found that a polymer containing a repeating unit of styrenes substituted with fluorine (a styrene derivative unit having at least a fluorine atom) has a wavelength of, for example, 193 nm. In the exposure of short wavelengths such as the above, it has a high n-value and optimum k-value equivalent to those of a photoresist, and also has excellent etching resistance. It has been found that this is a promising material as a resist underlayer film for a positive / negative reversal process by forming a silicon oxide film or forming a silicon oxide film on a resist pattern, and has made the present invention.

Here, FIG. 1 shows a silicon-containing intermediate layer film (SiUL) having an n value of 1.7, a k value of 0.1 and a film thickness of 40 nm below the photoresist film 100 nm, and a resist underlayer film having an n value of 1.6 below it. The reflectivity when the k value of (CUL) and the film thickness are changed is shown. The optical conditions are ArF immersion lithography with NA of 1.35, and 44 nm LS pattern of dipole s-polarized illumination. It can be seen that there is a region with a reflectance of 1% or less (refractiveity of 0.01 or less) in a wide range of k value of 0.1 to 0.4.
FIG. 2 shows the reflectance when the k value of the resist underlayer film is 0.4 and the refractive index n and the film thickness are changed. There is a region where the reflection is 1% or less in a wide range of n from 1.5 to 1.9. Other conditions are the same as in FIG.

  FIG. 3 shows the case where the film thickness of the silicon-containing intermediate layer film of FIG. 1 is 20 nm in terms of n and k values. Similarly, the case where the film thickness of the silicon-containing intermediate layer film of FIG. As shown in FIG. As the pattern size is reduced, the resist film has been made thinner, and the silicon-containing intermediate layer for processing the thinned resist pattern has been made thinner. At present, the silicon-containing intermediate layer film is used with a film thickness of about 40 nm. However, in the comparison between FIG. 1 and FIG. 3 and the comparison between FIG. 2 and FIG. In addition, it is shown that the optimum n and k value ranges of the lower layer film for suppressing reflection are narrowing, and in particular, the optimum n value range is narrowing.

  In the sidewall spacer method in which the silicon oxide film pattern on the sidewall of the resist pattern is formed and the resolution is doubled, or in the image reversal method in which a silicon oxide film is formed on the pattern and the positive / negative reversal is performed, the lower layer directly on the resist is the hydrocarbon film. Become. Although the antireflection effect can be improved by making the hydrocarbon film multi-layered, it is preferable from the viewpoint of cost reduction and throughput improvement that the hydrocarbon film is formed by one coating of one material.

  FIGS. 5 to 12 are substrate reflections when an underlayer film of one layer is assumed and the projection lens NA is 1.35 ArF immersion lithography and dipole s-polarized illumination is 40 nm LS. The film thickness of the lower layer (CUL) when the refractive index of the lower layer film is changed in the range of 1.3 to 2.0 and the reflectance from the lower layer film when the k value is changed are shown. In the case of the three-layer resist process shown in FIGS. 1 and 2, there is a relatively wide range in which the reflectance is 1% or less. However, in the case of a single-layer antireflection film, the optimum n and k values and film thicknesses are present. The range of is narrow. For example, in the lower layer film of the three-layer resist film in FIG. 1, when the n value is 1.6, the reflectance is 1% or less. The region where 1 is 1% or less is narrow and almost close to one point. In the case of a single lower layer film, the reflection cannot be made 1% when n is 1.5 or less, and n of 1.7 or more is required.

  The lower layer film needs to have a thickness of 100 nm or more because it needs not only the antireflection function but also resistance when etching a substrate to be processed using a mask. A refractive index as high as 1.9 or 2.0 is not preferable because the film thickness when the reflection is 1% or less becomes less than 100 nm. Therefore, the optimum n value is in the range of 1.7 to 1.8. The optimum k value at this time is in the range of 0.15 to 0.25.

  A condensed polycyclic hydrocarbon in which aromatic groups are bonded to each other improves etching resistance, but lowers the n value. For example, n value of polyvinyl naphthalene is 1.2 and fullerene is 1.3. On the other hand, the n value of alicyclic compounds is relatively high, and the n value of polynorbornene or hydrogenated metathesis ring-opening norbornene is about 1.7. However, these compounds have a problem of low etching resistance. is there.

  The benzene ring has a maximum absorption value at a wavelength of 193 nm, that is, a maximum k value. The maximum value of the refractive index n value of 4-polyhydroxystyrene exists at a wavelength of 205 nm, the value of n decreases at shorter wavelengths, and is about 1.6 at a wavelength of 193 nm. The k value is approximately 1.0 due to high absorption. As described above, the polycycloolefin has an n value of 1.7 and a k value close to 0. Examples of the polycycloolefin include metathesis ring-opening polymerization (ROMP) such as polynorbornene and norbornene, norbornene and maleic anhydride, norbornene and maleimide, and the like. Tricyclodecene or tetracyclododecene having one more norbornene ring can also be used. It is possible to adjust the n value within the range of 1.6 to 1.7 and the k value within the range of 0.15 to 0.25 by copolymerizing or blending polycycloolefin and polystyrene. However, since the n value is 1.7 or less, the target value is not reached. In the past, introduction of sulfur atoms has been considered effective for increasing the refractive index, and introduction of sulfur atoms has been attempted as a base polymer for high refractive index immersion lithography resists. However, even if sulfur atoms are introduced, the refractive index increases only slightly.

  Here, the n value at the maximum peak of 4-polyhydroxystyrene at a wavelength of 205 nm is 2.1 or more. The inventors of the present invention believe that if this peak is shifted by a short wavelength, the refractive index at a wavelength of 193 nm can be improved efficiently. In order to shift the wavelength by a short wavelength, the introduction of fluorine atoms, particularly the benzene ring, is considered. It has been found that polystyrenes into which fluorine atoms are introduced are effective.

  That is, the resist underlayer film material of the present invention is a resist underlayer film material for forming a resist underlayer film of a multilayer resist film used in lithography, and contains at least a styrene derivative unit having a fluorine atom as a repeating unit. A resist underlayer film material characterized by comprising a polymer.

（上記一般式（１）中、Ｒ^１は水素原子又はメチル基である。Ｒ^２は水素原子、ヒドロキシ基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、炭素数１〜１０のアルキル基、アルコキシ基、炭素数１〜１１のアルコキシメチル基、アシロキシ基、アルコキシカルボニル基、炭素数１〜１２のアルコキシエチル基、及び、グリシジルエーテル基のいずれかであり、ヒドロキシ基及びカルボキシル基の水素は酸不安定基、フッ素で置換されたアルキル基、及びフッ素で置換されたアシル基のいずれかで置換されていても良い。ｍは１〜５の整数、ｎは０〜３の整数である。ａは０＜ａ≦１．０の範囲である。） In particular, the polymer preferably contains a styrene derivative unit having at least a fluorine atom represented by the following general formula (1).

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrogen atom, a hydroxy group, a carboxyl group, a hydroxymethyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group. Group, an alkoxymethyl group having 1 to 11 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an alkoxyethyl group having 1 to 12 carbon atoms, and a glycidyl ether group. It may be substituted with any of a stabilizing group, an alkyl group substituted with fluorine, and an acyl group substituted with fluorine, m is an integer of 1 to 5, n is an integer of 0 to 3. a is 0 <a ≦ 1.0.)

  From such a resist underlayer film material of the present invention comprising a polymer containing, as a repeating unit, a styrene derivative unit having at least a fluorine atom, that is, a unit in which a benzene ring of substituted or unsubstituted styrene is substituted with fluorine. The formed resist underlayer film is a multi-layer resist process such as a three-layer resist process having a silicon-containing intermediate layer film, or a silicon oxide film is formed directly on the sidewall of the resist pattern, or the resist pattern is filled with a silicon oxide film to perform positive / negative reversal. It is a novel resist underlayer film that is particularly effective for the process to be performed. In particular, it exhibits an excellent antireflection effect in exposure at a short wavelength such as 193 nm, and has excellent etching resistance under substrate etching conditions.

（上記一般式（２）中、Ｒ^１は水素原子又はメチル基である。Ｒ^２は水素原子、ヒドロキシ基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、炭素数１〜１０のアルキル基、アルコキシ基、炭素数１〜１１のアルコキシメチル基、アシロキシ基、アルコキシカルボニル基、炭素数１〜１２のアルコキシエチル基、及び、グリシジルエーテル基のいずれかであり、ヒドロキシ基及びカルボキシル基の水素は酸不安定基、フッ素で置換されたアルキル基、及びフッ素で置換されたアシル基のいずれかで置換されていても良い。Ｒ^３、Ｒ^４は水素原子、フッ素原子、ヒドロキシ基、カルボキシル基、ヒドロキシメチル基、炭素数１〜６のアルキル基、アシロキシ基、アルコキシカルボニル基、アセトキシメチル基、及びアルコキシメチル基のいずれかであり、カルボキシル基の水素は、フッ素原子又は酸素原子を含んでも良いアルキル基で置換されていても良い。ｍは１〜５の整数、ｎは０〜３の整数である。ａ、ｂ１、ｂ２はそれぞれ０＜ａ＜１．０、０≦ｂ１＜１．０、０≦ｂ２＜１．０、０＜ｂ１＋ｂ２＜１．０の範囲である。） The styrene derivative having at least a fluorine atom which is a monomer of a styrene derivative unit having at least a fluorine atom is preferably copolymerized with acenaphthylene (derivative) and / or norbornadiene (derivative). That is, the polymer contains an acenaphthylene (derivative) unit b1 and / or a nortricyclene (derivative) unit b2 in addition to a styrene derivative unit a having at least a fluorine atom as shown in the following general formula (2). It is possible to adjust to an ideal optical constant and further improve etching resistance.

(In the general formula (2), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrogen atom, a hydroxy group, a carboxyl group, a hydroxymethyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group. Group, an alkoxymethyl group having 1 to 11 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an alkoxyethyl group having 1 to 12 carbon atoms, and a glycidyl ether group. R ³ and R ⁴ may be substituted with any of a stable group, an alkyl group substituted with fluorine, and an acyl group substituted with fluorine, wherein R ³ and R ⁴ are a hydrogen atom, a fluorine atom, a hydroxy group, a carboxyl group, and hydroxymethyl. Group, an alkyl group having 1 to 6 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an acetoxymethyl group, and an alkoxy group. It is any of a methyl group, and the hydrogen of the carboxyl group may be substituted with an alkyl group which may contain a fluorine atom or an oxygen atom, m is an integer of 1 to 5, and n is an integer of 0 to 3. A, b1, and b2 are ranges of 0 <a <1.0, 0 ≦ b1 <1.0, 0 ≦ b2 <1.0, and 0 <b1 + b2 <1.0, respectively.

（上記一般式（３）中、Ｒ^１、Ｒ^３、Ｒ^４、ｍ、ｎ、ａ、ｂ１、ｂ２は前述の通りであり、Ｒは水素原子、炭素数１〜１０のアルキル基、アシル基、フッ素で置換されたアシル基、及び酸不安定基のいずれかである。） Moreover, it is preferable that the polymer contained in the resist underlayer film material of this invention is what is shown by following General formula (3). By including the polymer containing the repeating unit a having such a substituted or unsubstituted hydroxy group, the crosslinking density is increased, and the etching resistance can be improved.

(In the general formula (3), R ¹ , R ³ , R ⁴ , m, n, a, b1, b2 are as described above, and R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an acyl group , An acyl group substituted with fluorine, and an acid labile group.)

Examples of the monomer used for the polymerization of the repeating unit a in the general formula (1) include those represented by the following formula. Here, a method for synthesizing substituted or unsubstituted fluorinated hydroxystyrene is described in Japanese Patent No. 3804756.

In the above formula, R ⁵ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, which may have a fluorine atom or an acid labile group. Or a glycidyl group. R ⁶ and R ⁷ are each a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and may have a fluorine atom or an acid labile group.

When R ² in the above general formula (1) is an alkyl group having 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, t- Examples thereof include a butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group.
When R ² is an acyloxy group, a formyloxy group, an acetoxy group, a propinoyloxy group, a pivaloyloxy group, a cyclopentylcarbonyloxy group, and a cyclohexylcarbonyloxy group are exemplified.
When R ² is an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a t-butoxycarbonyl group, a t-amyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, an ethylcyclopentyloxycarbonyl group, Examples thereof include a methylcyclopentyloxycarbonyl group and a methylcyclohexyloxycarbonyl group.

R ² is a hydroxy group and a carboxyl group, and these hydrogens may be substituted with an acid labile group. As the acid labile group in this case, those described in paragraphs (0058) to (0084) of JP-A No. 2010-13627 can be used.
An alkoxy group substituted with fluorine (when the hydrogen of the hydroxy group is substituted with an alkyl group substituted with fluorine) includes a trifluoromethoxy group, a trifluoroethoxy group, a pentafluoroisopropoxy group, and a fluorine-substituted group. Examples of the acyloxy group (when the hydrogen of the hydroxy group is substituted with an acyl group substituted with fluorine) include a trifluoroacetoxy group, a trifluoroethylcarbonyloxy group, a pentafluoroisopropylcarbonyloxy group, and the like. .

  Among these, fluorostyrenes having a substituted or unsubstituted hydroxy group or carboxyl group are preferably used. Since the hydroxy group and the carboxyl group serve as a starting point for the crosslinking reaction, the cross-linking after baking increases the rigidity of the film and improves the etching resistance. The hydroxy group or carboxyl group may be unsubstituted or substituted. This is because the crosslinking reaction proceeds when the substituent is eliminated by baking at 250 ° C. or higher.

  In the above general formulas (1) to (3), the position of fluorine substitution on the benzene ring is not particularly limited, but the number of substitutions is preferably 2 rather than 1, since the n value increases and the k value decreases. Used.

The ratio (molar ratio) of the repeating unit a is preferably in the range of 0.05 ≦ a ≦ 0.8, more preferably 0.1 ≦ a ≦ 0.7. When acenaphthylene (derivative) is copolymerized as in general formula (2) or general formula (3), the ratio (molar ratio) of repeating unit b1 is preferably 0.1 ≦ b1 ≦ 0.9. Preferably 0.2 ≦ b1 ≦ 0.85. When norbornadiene (derivative) is copolymerized, the ratio (molar ratio) of the repeating unit b2 is preferably 0.1 ≦ b2 ≦ 0.9, more preferably 0.2 ≦ b2 ≦ 0.85.
Further, n in the general formulas (1) to (3) is preferably 1.

（Ｒ^８、Ｒ^１２は水素原子、Ｒ^９〜Ｒ^１１、Ｒ^１３〜Ｒ^１４は水素原子又は炭素数１〜５のアルキル基を示す。） The monomers for obtaining the repeating units b1 and b2 in the general formulas (2) and (3) can be exemplified below. In order to obtain the nortricyclene derivative unit of b2, the following norbornadiene compound is used.

(R < ⁸ >, R < ¹² > shows a hydrogen atom, R < ⁹ > -R < ¹¹ >, R < ¹³ > -R < ¹⁴ > shows a hydrogen atom or a C1-C5 alkyl group.)

In order to synthesize the copolymer contained in the resist underlayer film material of the present invention, one method is to combine fluorinated styrenes and acenaphthylenes and / or norbornadiene in an organic solvent, radical initiator or cation. A polymerization initiator is added to carry out heat polymerization. The hydroxy group of the monomer containing a hydroxy group can be substituted with an acetyl group, and the resulting polymer compound can be subjected to alkaline hydrolysis in an organic solvent to deprotect the acetyl group.
Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropio). Nate), benzoyl peroxide, lauroyl peroxide, and the like, preferably polymerized by heating to 50 to 80 ° C. Examples of the cationic polymerization initiator include sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, hypochlorous acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, tosylic acid and the like, BF ₃ , AlCl _3, TiCl _4, SnCl ₄ other Friedel-Crafts catalyst such _{as, I 2, (C 6 H} 5) 3 generated material susceptible to cationic as CCl are used.

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

  In addition to the repeating units a, b1, and b2, a condensed hydrocarbon having 10 to 30 carbon atoms having a vinyl group, specifically, styrene, vinyl naphthalene, vinyl anthracene, vinyl pyrene, vinyl fluorene, vinyl phenanthrene, vinyl chrysene, vinyl naphthacene It is also possible to copolymerize repeating units c such as vinyl pentacene, vinyl acenaphthene and vinyl fluorene. The copolymerization ratio (molar ratio) of c is in the range of 0 ≦ c ≦ 0.5.

  Further, (meth) acrylates, vinyl ethers, maleic anhydride, itaconic anhydride, maleimides, vinyl pyrrolidone, vinyl ethers, divinyl ethers, di (meth) acrylates, divinylbenzenes, norbornenes, tricyclodecenes And other olefinic compounds d such as tetracyclododecenes, indenes, benzofurans, and benzothiophenes. The copolymerization ratio (molar ratio) of d is in the range of 0 ≦ d ≦ 0.5.

  The polystyrene-converted weight average molecular weight of the polymer according to the present invention by gel permeation chromatography (GPC) is preferably in the range of 1,500 to 200,000, more preferably in the range of 2,000 to 100,000. The molecular weight distribution is not particularly limited, and low molecular weight and high molecular weight substances can be removed by fractionation to reduce the degree of dispersion. Two or more general formulas (1) to (1) having different molecular weights and degrees of dispersion can be used. It is also possible to mix the polymers in 3) or two or more polymers having different composition ratios.

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

As described above, the base resin for the resist underlayer film material of the present invention can include a polymer obtained by copolymerizing an acenaphthylene derivative and / or a norbornadiene derivative in addition to a styrene derivative having at least a fluorine atom. However, it can also be blended with conventional polymers mentioned as the above-mentioned antireflection film materials.
Polyacenaphthylene has a glass transition point of 150 ° C. or higher, and this alone may have poor deep hole filling characteristics such as via holes. In order to embed holes without generating voids, a technique is employed in which a polymer having a low glass transition point is used and a resin is embedded to the bottom of the hole while heat-flowing at a temperature lower than the crosslinking temperature (for example, JP 2000-294504 gazette). Polymers having a low glass transition point, especially polymers having a glass transition point of 180 ° C. or lower, particularly 100 to 170 ° C., such as acrylic derivatives, vinyl alcohol, vinyl ethers, allyl ethers, styrene derivatives, allylbenzene derivatives, ethylene, propylene, butadiene Blends with one or more copolymer selected from olefins such as, polymers by metathesis ring-opening polymerization, novolak resins, dicyclopentadiene resins, phenolic low nuclei, calixarenes, fullerenes As a result, the glass transition point can be lowered, and the via hole filling characteristics can be improved.

  One of the performances required for the resist lower layer film is that there is no intermixing with the resist upper layer film and that there is no diffusion of low molecular components into the resist upper layer film (for example, Proc. SPIE vol. 2195, p225-229 (1994)). In order to prevent these problems, a method is generally employed in which a resist underlayer film is formed on a substrate by spin coating or the like and then thermally crosslinked by baking. Therefore, there are a method of adding a crosslinking agent as a component of the resist underlayer film material and a method of introducing a crosslinkable substituent into the polymer. Examples of a method for introducing a crosslinkable substituent into the polymer include a method in which the hydroxy group of the fluorinated hydroxystyrene represented by the general formula (1) is glycidyl etherified.

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

  Among specific examples of the crosslinking agent, examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like. Is done. Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, Examples thereof include compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

  Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, and tetramethylolguanamine. A compound in which ˜4 methylol groups are acyloxymethylated or a mixture thereof may be mentioned. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, and tetramethylolglycoluril. Examples thereof include compounds in which 1 to 4 methylol groups are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, a mixture thereof, tetramethoxyethyl urea, and the like.
Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. Examples of the azide compound include 1,1′-biphenyl-4,4′-bisazide and 4,4′-methylidenebis. Examples include azide and 4,4′-oxybisazide.

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

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

  The blending amount of the crosslinking agent in the resist underlayer film material of the present invention is preferably 5 to 50 parts, particularly preferably 10 to 40 parts, relative to 100 parts (parts by mass, the same applies hereinafter) of the base polymer (total resin). If it is 5 parts or more, there is no risk of mixing with the resist film, and if it is 50 parts or less, the antireflection effect is reduced, and there is no possibility of cracking in the crosslinked film.

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

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

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

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, and a part or all of hydrogen atoms of these groups may be substituted with an alkoxy group, etc. In addition, 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, R ^{101g is, R 101a, R 101b, .R} 101d , ^R 101e, shown by adding a hydrogen atom to ^{R 101c, R 10 d, R 101e} and ^{R 101f} and may also form a ring, when they form a ^{ring, R 101d, R 101e} and ^{R 101d, R 101e} and ^{R 101f} is an alkylene group having 3 to 10 carbon atoms, or (A heteroaromatic ring having a nitrogen atom in the ring is shown.)

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

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

In general formulas (K-1) and (K-2), ^R102 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an acyl group, or an alkenyl group having 2 to 20 carbon atoms. , An aryl group having 6 to 20 carbon atoms and an aryloxy group. R ¹⁰³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

In addition, R ^101d , R ^101e , R ^101f , and R ^{101g each} have a heteroaromatic ring having a nitrogen atom in the formula as 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-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 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 derivative, indoline derivative, quinoline derivative (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoki Phosphorus derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives Etc. are exemplified.

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

（式中、Ｒ^１０２ａ、Ｒ^１０２ｂはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ^１０３は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^１０４ａ、Ｒ^１０４ｂはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ⁻は非求核性対向イオンを表す。）

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

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

（式中、Ｒ^１０５、Ｒ^１０６は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

(Wherein R ¹⁰⁵ and R ^{106 each} represent a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, or a carbon number) 7 to 12 aralkyl groups are shown.)

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

（式中、Ｒ^１０７、Ｒ^１０８、Ｒ^１０９は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ^１０８、Ｒ^１０９は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ^１０８、Ｒ^１０９はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を示す。Ｒ^１０５は（Ｐ２）式のものと同様である。）

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

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

（式中、Ｒ^１０１ａ、Ｒ^１０１ｂは前記と同様である。）

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

（式中、Ｒ^１１０は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ^１１１は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The compounding amount of the basic compound is suitably 0.001 to 2 parts, particularly 0.01 to 1 part, based on 100 parts of the total base polymer. If the blending amount is 0.001 part or more, the blending effect is not likely to be reduced, and if it is 2 parts or less, it is preferable because all the acid generated by heat is not trapped and there is no fear of crosslinking.

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

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

  Furthermore, the present invention is a method of forming a pattern on a substrate by lithography, wherein at least a resist underlayer film material of the present invention is used to form a resist underlayer film on the substrate, and a photoresist is formed on the underlayer film. A resist upper layer film is formed using the composition to form a multilayer resist film, and after exposing the pattern circuit region of the multilayer resist film, the resist is developed with a developer to form a resist pattern on the resist upper layer film. Provided is a two-layer resist process in which a resist underlayer film is etched using a formed resist upper layer film as a mask, and a substrate is etched using a resist underlayer film having a pattern formed as a mask to form a pattern on the substrate.

  Further, as a three-layer resist process, a photoresist underlayer film material is applied on a substrate, a resist intermediate layer film material containing silicon atoms is applied on the obtained underlayer film, and the intermediate layer film material is applied on the intermediate layer film material. A resist upper layer material made of a photoresist composition is applied, the pattern circuit area of the resist upper layer film is irradiated with radiation, developed with a developer to form a resist pattern, and the resist pattern layer is masked with a dry etching apparatus. After the resist intermediate layer film is processed and the photoresist pattern layer is removed, the resist underlayer film layer and then the substrate can be processed using the processed resist intermediate layer film as a mask.

Hereinafter, the pattern forming method of the present invention will be described in more detail with reference to FIGS.
FIG. 13 is an explanatory diagram of the two-layer resist process.
As shown in FIG. 13, the substrate 1 to be processed includes a layer to be processed 1a and a base layer 1b. The base layer 1b of the substrate 1 is not particularly limited. Si 1, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, etc. Different materials may be used. The layer to be processed _{1a, Si, SiO 2, SiON} , SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si , etc. and various low dielectric films and etching stopper film It is usually used and can be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.

  First, the two-layer resist process of FIG. 13 will be described. The resist underlayer film 2 can be formed on the substrate 1 by a spin coat method or the like in the same manner as a normal photoresist film forming method. After the resist underlayer film 2 is formed by a spin coating method or the like, it is desirable to evaporate the organic solvent and perform baking to promote the crosslinking reaction in order to prevent mixing with the resist upper layer film 3. The baking temperature is preferably in the range of 80 to 300 ° C., and preferably in the range of 10 to 300 seconds. Although the thickness of the resist underlayer film 2 is appropriately selected, it is preferably 100 to 20,000 nm, particularly 150 to 15,000 nm. After the resist lower layer film 2 is formed, a resist upper layer film 3 is formed thereon (see FIG. 13A).

In this case, a known composition can be used as the photoresist composition for forming the resist upper layer film 3. From the point of oxygen gas etching resistance, etc., use a silicon atom-containing polymer such as polysilsesquioxane derivative or vinyl silane derivative as the base polymer, and further include a positive type containing an organic solvent, an acid generator, and a basic compound if necessary. The photoresist composition is used. In addition, as a silicon atom containing polymer, the well-known polymer used for this kind of resist composition can be used.
The thickness of the resist upper layer film 3 is not particularly limited, but is preferably 30 to 500 nm, particularly 50 to 400 nm.

When the resist upper layer film 3 is formed from the photoresist composition, a spin coating method or the like is preferably used as in the case of forming the resist lower layer film 2. Pre-baking is performed after the resist upper layer film 3 is formed by spin coating or the like, but it is preferably performed at 80 to 180 ° C. for 10 to 300 seconds.
Thereafter, the pattern circuit region of the multilayer resist film is exposed according to a conventional method (see FIG. 13B), post-exposure baking (PEB), and development is performed to obtain a resist pattern 3 ′ (FIG. 13C )reference).

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

Next, the resist underlayer film 2 is etched by dry etching mainly including oxygen gas using the obtained resist pattern 3 ′ as a mask to obtain a resist underlayer film pattern 2 ′ (see FIG. 13D). . This etching can be performed by a conventional method. In the case of dry etching mainly using oxygen gas, in addition to oxygen gas, it is also possible to add inert gas such as He, Ar, CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ gas. is there. In particular, the latter gas is used for side wall protection for preventing undercut of the pattern side wall.

Etching of the next substrate 1 can also be performed by a conventional method. For example, if the substrate is SiO ₂ or SiN, etching mainly using a fluorocarbon gas, polysilicon (p-Si), Al or W is chlorine, Etching mainly using bromine-based gas is performed to form a pattern 1 ′ on the substrate (see FIG. 13E). The resist underlayer film of the present invention is characterized by excellent etching resistance when etching these substrates. At this time, if necessary, the resist upper layer film may be removed and then the substrate may be etched, or the resist upper layer film may be left as it is and the substrate may be etched.

The present invention is used in a sidewall spacer method in which a SiO ₂ film is directly formed on a sidewall of a resist pattern (photoresist pattern), or in an image reversal method in which a SiO ₂ film material is spin-coated on a photoresist pattern to perform positive / negative reversal. It is effective as a resist underlayer film material for the resist underlayer film. In these methods, the resist underlayer becomes one layer of the resist underlayer film, and a resist pattern is formed directly on the resist underlayer film. However, if the resist underlayer film formed using the resist underlayer film material of the present invention is used, Even in the absence of an intermediate layer film or the like, an excellent antireflection effect can be exhibited and a good resist pattern can be formed.

  In the sidewall spacer method, first, a resist underlayer film 2 is formed on a substrate 1 using the resist underlayer film material of the present invention as in the above-described two-layer resist process (FIGS. 13A to 13C). Then, a resist upper layer film 3 is formed on the resist lower layer film 2 using a resist upper layer film material made of a photoresist composition, the pattern circuit region of the resist upper layer film 3 is exposed, and then developed with a developer. Then, a resist pattern 3 ′ is formed on the resist upper layer film 3. Thereafter, as shown in FIG. 14, a silicon oxide film 4 is formed on the obtained resist pattern 3 ′ by spin coating or CVD (FIGS. 14A and 14B), and the resist pattern sidewalls are formed. While leaving the silicon oxide film 4a, at least the silicon oxide film on the resist pattern upper portion 4b and the silicon oxide film on the space portion 4c are removed by etching (FIG. 14C), and the silicon oxide film 4a on the resist pattern side wall is masked by etching. Then, the resist underlayer film 2 is processed to form a resist underlayer film pattern 2s (FIG. 14D), and a pattern 1s is formed on the substrate using the obtained resist underlayer film pattern 2s as an etching mask (FIG. 14 ( E)) method.

  The resist underlayer film material of the present invention exhibits an excellent antireflection effect even when there is no silicon-containing intermediate layer film. Therefore, even when a sidewall spacer is directly formed on such a photoresist pattern, the anti-reflection effect can be obtained by one layer of the resist underlayer film, so that the shape of the photoresist pattern to be used is improved, and further, the throughput is improved and the cost is increased. Reduction can be achieved. Moreover, since it has the etching tolerance outstanding with respect to the board | substrate, a favorable pattern can be formed in a board | substrate.

  On the other hand, in the image reversal method for performing positive / negative reversal, first, as in the above-described two-layer resist process (FIGS. 13A to 13C), the resist underlayer film material of the present invention is used on the substrate 1 to form a resist underlayer. After forming the film 2, forming a resist upper film 3 on the resist lower film 2 using a resist upper film material made of a photoresist composition, and exposing the pattern circuit region of the resist upper film 3, Development with a developing solution forms a resist pattern 3 'on the resist upper layer film. Next, as shown in FIG. 15, a silicon oxide film 5 is formed on the obtained resist pattern 3 ′ (FIGS. 15A and 15B), leaving a silicon oxide film 5a between the resist patterns, At least the silicon oxide film on the resist pattern upper portion 5b is removed by etching (FIG. 15C), and the resist underlayer film is processed using the silicon oxide film 5a between the remaining resist patterns as a mask to form a resist underlayer film pattern 2p. (FIG. 15D), and using the obtained resist underlayer film pattern 2p as an etching mask, the pattern 1p is formed on the substrate.

The resist underlayer film material of the present invention exhibits an excellent antireflection effect even when there is no silicon-containing intermediate layer film, and a good photoresist pattern can be obtained. Therefore, even when a negative oxide inversion is performed by spin-coating a silicon oxide film (SiO ₂ film) material on the photoresist pattern, the photoresist pattern shape is improved, and the resist underlayer film has an antireflection effect. Thus, throughput improvement and cost reduction can be achieved. Moreover, since it has the etching tolerance outstanding with respect to the board | substrate, a favorable pattern can be formed in a board | substrate.

In the case of the three-layer resist process, as shown in FIG. 16, a resist intermediate layer film 14 containing silicon atoms is interposed between the resist lower layer film 12 and the resist upper layer film 13 on the substrate 11 (FIG. 16 ( A)). In this case, as a material for forming the resist intermediate layer film 14, a film made by spin coating such as a silicone polymer based on polysilsesquioxane or tetraorthosilicate glass (TEOS), or made by CVD. A SiO ₂ , SiN, or SiON film can be used.
The thickness of the resist intermediate layer film 14 is preferably 10 to 1,000 nm.
Other configurations are the same as those in the case of the two-layer resist process of FIG.

Next, a resist pattern 13 ′ is formed in the same manner as in FIG. 13 (see FIG. 16B).
Next, using the obtained resist pattern 13 ′ as a mask, the resist intermediate layer film 14 is etched by dry etching or the like mainly composed of chlorofluorocarbon gas to obtain a resist intermediate layer film pattern 14 ′ (see FIG. 16C). ). This etching can be performed by a conventional method. In the case of dry etching mainly using a chlorofluorocarbon gas, CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F _{10 and the} like can be generally used.

Further, after the resist intermediate layer film 14 is etched, the resist lower layer film is subjected to 12 etching using the obtained resist intermediate layer film pattern 14 ′ as an etching mask by dry etching mainly including O ₂ or H _2. A film pattern 12 ′ is obtained (see FIG. 16D). In this case, in addition to O ₂ and H ₂ gases, inert gases such as He and Ar, and CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , and NO ₂ gases can be added. In particular, the latter gas is used for side wall protection for preventing undercut of the pattern side wall.

Etching of the next substrate 11 can also be performed by a conventional method. Similarly to the case of FIG. 13, for example, if the substrate is SiO ₂ or SiN, etching mainly using a fluorocarbon gas, polysilicon (p-Si) In the case of Al, W, or the like, etching mainly using a chlorine-based or bromine-based gas is performed to form a pattern 11 ′ on the substrate (see FIG. 16E). The resist underlayer film obtained by using the resist underlayer film material of the present invention is characterized by excellent etching resistance when etching these substrates. At this time, if necessary, the resist upper layer film may be removed and then the substrate may be etched, or the resist upper layer film may be left as it is and the substrate may be etched.

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

(Synthesis Example 1)
To a 200 mL flask, 4.5 g of 2-fluoro-4-acetoxystyrene, 11.4 g of acenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2-Fluoro-4-acetoxystyrene: acenaphthylene = 25: 75
Weight average molecular weight (Mw) = 6,900
Molecular weight distribution (Mw / Mn) = 1.86
This polymer is referred to as polymer 1.

(Synthesis Example 2)
To a 200 mL flask, 4.9 g of 2-fluoro-4-tbutoxystyrene, 11.4 g of acenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2-Fluoro-4-tbutoxystyrene: acenaphthylene = 25: 75
Weight average molecular weight (Mw) = 7,600
Molecular weight distribution (Mw / Mn) = 1.89
This polymer is designated as Polymer 2.

(Synthesis Example 3)
To a 200 mL flask, 6.4 g of 2,3-difluoro-4-tbutoxystyrene, 10.6 g of acenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,3-difluoro-4-tbutoxystyrene: acenaphthylene = 30: 70
Weight average molecular weight (Mw) = 7,600
Molecular weight distribution (Mw / Mn) = 1.89
This polymer is designated as Polymer 3.

(Synthesis Example 4)
To a 200 mL flask, 6.4 g of 2,6-difluoro-4-tbutoxystyrene, 14.7 g of 5-acetoxyacenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-tbutoxystyrene: 5-acetoxyacenaphthylene = 30: 70
Weight average molecular weight (Mw) = 7,600
Molecular weight distribution (Mw / Mn) = 1.89
This polymer is designated as polymer 4.

(Synthesis Example 5)
To a 200 mL flask, 5.9 g of 2,6-difluoro-4-acetoxystyrene, 10.6 g of acenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-acetoxystyrene: acenaphthylene = 30: 70
Weight average molecular weight (Mw) = 6,200
Molecular weight distribution (Mw / Mn) = 1.77
This polymer is designated as polymer 5.

(Synthesis Example 6)
To a 200 mL flask, 4.2 g of 2,6-difluorosistyrene, 12.7 g of 5-hydroxymethylacenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluorostyrene: 5-hydroxymethylacenaphthylene = 30: 70
Weight average molecular weight (Mw) = 6,400
Molecular weight distribution (Mw / Mn) = 1.79
This polymer is designated as polymer 6.

(Synthesis Example 7)
To a 200 mL flask, 5.9 g of 2,6-difluoro-4-acetoxystyrene, 6.4 g of 2,5-norbornadiene, and 20 g of 1,2-dichloroethane as a solvent were added. In a nitrogen atmosphere, 0.5 g of trifluoroboron as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 2.5 L of methanol and 0.2 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer. .
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-acetoxystyrene: 2,5-norbornadiene = 30: 70
Weight average molecular weight (Mw) = 12,500
Molecular weight distribution (Mw / Mn) = 2.25
This polymer is designated as polymer 7.

(Synthesis Example 8)
To a 200 mL flask, 6.9 g of 2,6-difluoro-4-acetoxystyrene, 11.4 g of 2,5-norbornadiene-2-acetoxymethyl, and 20 g of 1,2-dichloroethane as a solvent were added. In a nitrogen atmosphere, 0.5 g of trifluoroboron as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 2.5 L of methanol and 0.2 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer. .
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-acetoxystyrene: 2,5-norbornadiene-2-acetoxymethyl = 30: 70
Weight average molecular weight (Mw) = 12,500
Molecular weight distribution (Mw / Mn) = 2.25
This polymer is designated as polymer 8.

(Synthesis Example 9)
10 g of the polymer 5 was dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran, 10 g of triethylamine and 10 g of water were added, the acetyl group was deprotected at 70 ° C. for 5 hours, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-hydroxystyrene: acenaphthylene = 30: 70
Weight average molecular weight (Mw) = 6,000
Molecular weight distribution (Mw / Mn) = 1.77
This polymer is designated as polymer 9.

(Synthesis Example 10)
10 g of the polymer 8 was dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran, 10 g of triethylamine and 10 g of water were added, the acetyl group was deprotected at 70 ° C. for 5 hours, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-hydroxystyrene: 2,5-norbornadiene-2-hydroxymethyl = 30: 70
Weight average molecular weight (Mw) = 12,200
Molecular weight distribution (Mw / Mn) = 2.24
This polymer is designated as polymer 10.

(Synthesis Example 11)
To a 200 mL flask, 7.6 g of 2,6-difluoro-4-trifluoroacetoxystyrene, 11.5 g of 2,5-norbornadiene-2-acetoxymethyl, and 20 g of 1,2-dichloroethane as a solvent were added. In a nitrogen atmosphere, 0.5 g of trifluoroboron as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 2.5 L of methanol and 0.2 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer. .
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-trifluoroacetoxystyrene: 2,5-norbornadiene-2-acetoxymethyl = 30: 70
Weight average molecular weight (Mw) = 9,500
Molecular weight distribution (Mw / Mn) = 2.01
This polymer is designated as polymer 11.

(Synthesis Example 12)
To a 200 mL flask, 8.0 g of 2,6-difluoro-4-trifluoroethylcarbonyloxystyrene, 11.5 g of 2,5-norbornadiene-2-acetoxymethyl, and 20 g of 1,2-dichloroethane as a solvent were added. In a nitrogen atmosphere, 0.5 g of trifluoroboron as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 2.5 L of methanol and 0.2 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer. .
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-trifluoroethylcarbonyloxystyrene: 2,5-norbornadiene-2-acetoxymethyl = 30: 70
Weight average molecular weight (Mw) = 9,500
Molecular weight distribution (Mw / Mn) = 2.01
This polymer is designated as polymer 12.

(Synthesis Example 13)
To a 200 mL flask, 7.7 g of 2,6-difluoro-4-tbutoxycarbonyloxystyrene, 12.6 g of methoxymethyl 2,5-norbornadiene-2-carboxylate, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-tbutoxycarbonyloxystyrene: methoxymethyl 2,5-norbornadiene-2-carboxylate = 30: 70
Weight average molecular weight (Mw) = 7,600
Molecular weight distribution (Mw / Mn) = 1.63
This polymer is designated as polymer 13.

(Synthesis Example 14)
To a 200 mL flask, 6.4 g of 2,6-difluoro-4-glycidyl ether styrene, 12.6 g of methoxymethyl 2,5-norbornadiene-2-carboxylate, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-glycidyl ether styrene: methoxymethyl 2,5-norbornadiene-2-carboxylate = 30: 70
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.89
This polymer is designated as polymer 14.

(Synthesis Example 15)
In a 200 mL flask, 8.0 g of 2,6-difluoro-4-trifluoroethylcarbonyloxystyrene, 7.6 g of trifluoroethyl 2,5-norbornadiene-2-carboxylate, 5.3 g of acenaphthylene, and 20 g of toluene as a solvent were added. did. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-trifluoroethylcarbonyloxystyrene: trifluoroethyl 2,5-norbornadiene-2-carboxylate: acenaphthylene = 30: 35: 35
Weight average molecular weight (Mw) = 7,500
Molecular weight distribution (Mw / Mn) = 1.65
This polymer is designated as polymer 15.

(Synthesis Example 16)
To a 200 mL flask, 5.1 g of 2,6-difluoro-4-hydroxymethylstyrene, 7.6 g of trifluoroethyl 2,5-norbornadiene-2-carboxylate, 5.3 g of acenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,6-difluoro-4-hydroxymethylstyrene: trifluoroethyl 2,5-norbornadiene-2-carboxylate: acenaphthylene = 30: 35: 35
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.79
This polymer is designated as polymer 16.

(Synthesis Example 17)
To a 200 mL flask, 7.4 g of 2,3,5,6-tetrafluoro-4-tbutoxystyrene, 10.6 g of acenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
2,3,5,6-tetrafluoro-4-tbutoxystyrene: acenaphthylene = 30: 70
Weight average molecular weight (Mw) = 9,600
Molecular weight distribution (Mw / Mn) = 1.80
This polymer is designated as polymer 17.

(Synthesis Example 18)
To a 200 mL flask, 7.8 g of pentafluorostyrene, 10.8 g of methoxymethyl 2,5-norbornadiene-2-carboxylate, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
Pentafluorostyrene: methoxymethyl 2,5-norbornadiene-2-carboxylate = 40: 60
Weight average molecular weight (Mw) = 9,600
Molecular weight distribution (Mw / Mn) = 2.03
This polymer is designated as polymer 18.

(Synthesis Example 19)
To a 200 mL flask was added 7.8 g of pentafluorostyrene, 12.6 g of 5-acetoxyacenaphthylene, and 20 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
Pentafluorostyrene: 5-acetoxyacenaphthylene = 40: 60
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.99
This polymer is designated as polymer 19.

(Synthesis Example 20)
To a 200 mL flask, 7.8 g of pentafluorostyrene, 9.0 g of methoxymethyl 2,5-norbornadiene-2-carboxylate, 22.8 g of 1-vinylpyrene and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
Pentafluorostyrene: methoxymethyl 2,5-norbornadiene-2-carboxylate: 1-vinylpyrene = 40: 50: 10
Weight average molecular weight (Mw) = 9,900
Molecular weight distribution (Mw / Mn) = 2.22
This polymer is designated as polymer 20.

(Comparative Synthesis Example 1)
To a 200 mL flask, 4.8 g of 4-acetoxystyrene, 10.6 g of acenaphthylene, and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer, 100 mL of methanol, tetrahydrofuran The sample was dissolved again in 200 mL, 10 g of triethylamine and 10 g of water were added, the acetyl group was deprotected at 70 ° C. for 5 hours, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
4-hydroxystyrene: acenaphthylene = 30: 70
Weight average molecular weight (Mw) = 8,500
Molecular weight distribution (Mw / Mn) = 1.89
This polymer is referred to as comparative polymer 1.

(Comparative Synthesis Example 2)
To a 200 mL flask, 4.8 g of 4-acetoxystyrene, 6.4 g of 2,5-norbornadiene, and 20 g of 1,2-dichloroethane as a solvent were added. In a nitrogen atmosphere, 0.5 g of trifluoroboron as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 2.5 L of methanol and 0.2 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer. Redissolved in 100 mL of methanol and 200 mL of tetrahydrofuran, 10 g of triethylamine and 10 g of water were added, the acetyl group was deprotected at 70 ° C. for 5 hours, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
4-hydroxystyrene: 2,5-norbornadiene = 30: 70
Weight average molecular weight (Mw) = 12,500
Molecular weight distribution (Mw / Mn) = 2.25
This polymer is referred to as comparative polymer 2.

(Comparative Synthesis Example 3)
To a 200 mL flask, 3.3 g of 4-ethoxyethoxystyrene, 11.4 g of glycidyl methacrylate and 20 g of toluene as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 1.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 80 ° C., followed by reaction for 24 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 300 mL of methanol and 50 mL of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.

Copolymer composition ratio (molar ratio)
4-Ethoxyethoxystyrene: Methacrylic acid glycidyl ester = 20: 80
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.93
This polymer is referred to as comparative polymer 3.

Preparation of resist underlayer film materials (UDL1-25, comparative UDL1-3)
The resin represented by the above polymers 1 to 20, the resin represented by comparative polymers 1 to 3, the acid generator represented by AG1 to 3 below, and the crosslinking agent represented by CR1 and 2 below were prepared from FC-4430 (manufactured by Sumitomo 3M Limited). ) Resist underlayer film materials (UDL1 to 25, comparative UDL1 to 3) are dissolved in an organic solvent containing 0.1% by mass and filtered through a 0.02 μm fluororesin filter. Each was prepared.
Polymers 1-20: Polymers obtained in Synthesis Examples 1-20 Comparative polymers 1-3: Polymers obtained in Comparative Synthesis Examples 1-3

Acid generator: AG1, 2, 3 (see the following structural formula)

Cross-linking agent: CR1, 2 (see structural formula below)

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

A solution of the resist underlayer film material (UDL1-25, comparative UDL1-3) prepared above was applied onto a silicon substrate and baked at 300 ° C. for 60 seconds to form a resist underlayer film having a thickness of 100 nm.
After formation of the resist underlayer film, J.P. A. The refractive index (n, k) at a wavelength of 193 nm was determined using a spectroscopic ellipsometer (VASE) with variable incident angle from Woollam, and the results are shown in Table 1.

  As shown in Table 1, in UDL1 to 25 and Comparative Example UDL3, the n value of the refractive index of the resist underlayer film is in the range of 1.65 to 1.8, and the k value is in the range of 0.15 to 0.38. In particular, it can be seen that the film has an optimum refractive index (n) and extinction coefficient (k) that can exhibit a sufficient antireflection effect even in immersion lithography with a film thickness of 100 nm or more.

Next, a dry etching resistance test was performed. First, using the same resist underlayer film material (UDL1 to 25, comparative UDL1 to 3) used for the refractive index measurement, a resist underlayer film is prepared in the same manner, and CF ₄ / CHF ₃ of these underlayer films is used. As an etching test using a system gas, the test was performed under the following conditions (1). In this case, the thickness difference of the resist underlayer film before and after etching was measured using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Limited. The results are shown in Table 2.
(1) Etching test with CF ₄ / CHF ₃ gas The etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,000W
Gearup 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec

Preparation of resist upper layer film material / resist intermediate layer film material For use in the following three-layer resist process patterning test, an ArF single layer resist material (SL resist for ArF) having the composition shown in Table 3 is FC-4430 (Sumitomo 3M). (Product made) ArF single layer resist material was prepared by dissolving in the organic solvent containing 0.1 mass% in the ratio shown in the following Table 3, and filtering with a 0.02 micrometer fluororesin filter.

  ArF silicon-containing intermediate layer material (SOG) having the composition shown in Table 4 was dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M) at a ratio shown in Table 4, and 0.02 μm fluorine An ArF silicon-containing intermediate layer material was prepared by filtering through a resin filter.

Three-layer resist process patterning test (Examples 1-1 to 25, Comparative Examples 1-1 to 3)
A resist underlayer film material solution (UDL1-25, Comparative Examples UDL1-3) was applied onto a 300 mm Si wafer substrate on which a 50 nm thick SiO ₂ film was formed, and baked at 300 ° C. for 60 seconds to have a thickness of 100 nm. A resist underlayer film was formed.
The above-mentioned silicon-containing intermediate layer material solution SOG for ArF is applied thereon and baked at 200 ° C. for 60 seconds to form a resist intermediate layer film (SOG film) having a film thickness of 20 nm. A resist solution was applied and baked at 105 ° C. for 60 seconds to form a 90 nm-thick photoresist layer (resist upper layer film).

  Next, exposure is performed with an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase shift mask), and 90 The film was baked (PEB) at 60 ° C. for 60 seconds and developed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 30 seconds to obtain a 40 nm 1: 1 positive line and space pattern.

Next, using the etching apparatus Telius manufactured by Tokyo Electron, using the obtained resist pattern as a mask, the silicon-containing resist intermediate layer film is processed by dry etching, and the resulting silicon-containing resist intermediate layer film pattern is used as an etching mask. Processing of the film and processing of the SiO ₂ film were performed using the obtained resist underlayer film pattern as a mask.

Etching conditions are as shown below.
Transfer conditions of resist pattern to SOG film.
Chamber pressure 10.0Pa
RF power 1,500W
CF ₄ gas flow rate 15sccm
O ₂ gas flow rate 75sccm
Time 15sec

Transfer conditions of the obtained SOG film pattern to the resist underlayer film.
Chamber pressure 2.0Pa
RF power 500W
Ar gas flow rate 75sccm
O ₂ gas flow rate 45sccm
Time 120sec

Transfer conditions of the obtained resist underlayer film pattern to the SiO ₂ film.
Chamber pressure 2.0Pa
RF power 2,200W
C ₅ F ₁₂ gas flow rate 20 sccm
C ₂ F ₆ gas flow rate 10 sccm
Ar gas flow rate 300sccm
O ₂ 60 sccm
90 seconds

The cross sections of the patterns were observed with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared and summarized in Table 5.

Two-layer resist process patterning test (Examples 2-1 to 25, Comparative examples 2-1 to 3)
Assuming the sidewall spacer method to directly form the SiO ₂ film on the sidewall of the resist pattern, or the image reversal method in which the SiO ₂ film material is spin coated on the resist pattern and the positive / negative reversal is performed, the resist pattern is directly formed on the resist underlayer film. Experiments to form

The resist underlayer film material solution (UDL-1 to 25, comparative example UDL-1 to 3) is applied onto a 300 mm Si wafer substrate on which a 50 nm-thickness SiO ₂ film is formed, and baked at 300 ° C. for 60 seconds. Thus, a lower layer film having a thickness of 100 nm was formed.
An ArF SL resist solution was applied thereon, and baked at 105 ° C. for 60 seconds to form a 90 nm-thick photoresist layer (resist upper layer film).

  Next, exposure is performed with an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase shift mask), and 90 Bake at PE for 60 seconds (PEB) and develop with 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 40 nm 1: 1 positive line and space pattern. They were observed with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared and summarized in Table 6.

As shown in Table 2, the CF ₄ / CHF ₃ gas etching rate of the lower layer film of the present invention is the same as that of Comparative Examples 1 and 2, and is slower than the etching rate of Comparative Example 3. Further, since the refractive index has a high value near 1.7, which is the same as that of a photoresist, the antireflection effect is high, and even when the silicon-containing intermediate layer film is thinned and the reflection is increased, silicon Even in the absence of the contained intermediate layer, it exhibits an excellent antireflection effect. As shown in Table 5, the resist shape after development, the shape of the lower layer film after oxygen etching, and the substrate processing etching are also good, and as shown in Table 6, there is no silicon-containing intermediate layer, and photo Even when a resist pattern was formed, it was recognized that the pattern shape after development was good.

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

DESCRIPTION OF SYMBOLS 1, 11 ... Substrate to be processed, 1a ... Layer to be processed, 1b ... Base layer, 1 ', 1s, 1p, 11' ... Pattern formed on substrate, 2, 12 ... Under resist film, 2 ', 2s, 2p , 12 '... resist lower layer film pattern, 3, 13 ... resist upper layer film, 3', 13 '... resist pattern, 4, 5 ... silicon oxide film, 4a ... silicon oxide film on the resist pattern side wall, 4b, 5b ... resist pattern Upper part, 4c ... Space part, 5a ... Silicon oxide film between resist patterns, 14 ... Resist intermediate layer film, 14 '... Resist intermediate layer film pattern.

Claims (10)

A resist underlayer film material for forming a resist underlayer film of a multilayer resist film used in lithography, comprising a polymer containing at least a styrene derivative unit having a fluorine atom as a repeating unit ,
A resist underlayer film material, wherein the polymer is a copolymer of at least a styrene derivative having a fluorine atom and acenaphthylene (derivative) and / or norbornadiene (derivative). 2. The resist underlayer film material according to claim 1, wherein the polymer contains a styrene derivative unit having at least a fluorine atom represented by the following general formula (1).

(In the general formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrogen atom, a hydroxy group, a carboxyl group, a hydroxymethyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group. Group, an alkoxymethyl group having 1 to 11 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an alkoxyethyl group having 1 to 12 carbon atoms, and a glycidyl ether group. It may be substituted with any of a stabilizing group, an alkyl group substituted with fluorine, and an acyl group substituted with fluorine, m is an integer of 1 to 5, n is an integer of 0 to 3. a is ( The range is 0 <a <1.0 .) The resist underlayer film material according to claim 1 or 2, wherein the polymer is represented by the following general formula (2).

(In the general formula (2), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrogen atom, a hydroxy group, a carboxyl group, a hydroxymethyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group. Group, an alkoxymethyl group having 1 to 11 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an alkoxyethyl group having 1 to 12 carbon atoms, and a glycidyl ether group. R ³ and R ⁴ may be substituted with any of a stable group, an alkyl group substituted with fluorine, and an acyl group substituted with fluorine, wherein R ³ and R ⁴ are a hydrogen atom, a fluorine atom, a hydroxy group, a carboxyl group, and hydroxymethyl. Group, an alkyl group having 1 to 6 carbon atoms, an acyloxy group, an alkoxycarbonyl group, an acetoxymethyl group, and an alkoxy group. It is any of a methyl group, and the hydrogen of the carboxyl group may be substituted with an alkyl group which may contain a fluorine atom or an oxygen atom, m is an integer of 1 to 5, and n is an integer of 0 to 3. A, b1, and b2 are ranges of 0 <a <1.0, 0 ≦ b1 <1.0, 0 ≦ b2 <1.0, and 0 <b1 + b2 <1.0, respectively. The resist underlayer film material according to claim 3 , wherein the polymer is represented by the following general formula (3).

(In the general formula (3), R ¹ , R ³ , R ⁴ , m, n, a, b1, b2 are as described above, and R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an acyl group , An acyl group substituted with fluorine, and an acid labile group.) The said resist underlayer film material contains any one or more among an organic solvent, an acid generator, and a crosslinking agent further, The Claim 1 thru | or 4 characterized by the above-mentioned. Resist underlayer film material. A method for forming a resist underlayer film of a multilayer resist film used in lithography, wherein the resist underlayer film material according to any one of claims 1 to 5 is coated on a substrate by a spin coat method. A method of forming a resist underlayer film, comprising forming an underlayer film. A method of forming a pattern on a substrate by lithography, wherein a resist underlayer film is formed on the substrate by using the resist underlayer film material according to any one of claims 1 to 5 , and the resist underlayer A resist intermediate layer film is formed on the film using a resist intermediate layer film material containing silicon atoms, and a resist upper layer film is formed on the resist intermediate layer film using a resist upper layer film material made of a photoresist composition. After forming and exposing the pattern circuit area of the resist upper layer film, developing with a developer to form a resist pattern on the resist upper layer film, and using the obtained resist pattern as an etching mask, the resist intermediate layer film is formed. The resist underlayer film is etched using the obtained resist intermediate layer film pattern as an etching mask. Pattern forming method and forming a pattern on a substrate the door underlayer film pattern by etching the substrate with an etching mask. A method of forming a pattern on a substrate by lithography, wherein a resist underlayer film is formed on the substrate by using the resist underlayer film material according to any one of claims 1 to 5 , and the resist underlayer A resist upper layer film made of a photoresist composition is used to form a resist upper layer film on the film, the pattern circuit region of the resist upper layer film is exposed, and then developed with a developing solution to form a resist on the resist upper layer film. Forming a pattern, etching the resist underlayer film using the obtained resist pattern as an etching mask, etching the substrate using the obtained resist underlayer film pattern as an etching mask, and forming a pattern on the substrate Pattern forming method. A method of forming a pattern on a substrate by lithography, wherein a resist underlayer film is formed on the substrate by using the resist underlayer film material according to any one of claims 1 to 5 , and the resist underlayer A resist upper layer film made of a photoresist composition is used to form a resist upper layer film on the film, the pattern circuit region of the resist upper layer film is exposed, and then developed with a developing solution to form a resist on the resist upper layer film. A silicon oxide film is formed on the obtained resist pattern by spin coating or CVD, and the silicon oxide film on the side wall of the resist pattern is left while etching, and at least the silicon oxide film at the upper part of the resist pattern and in the space portion by etching. The resist underlayer film is removed by etching and using the silicon oxide film on the side wall of the resist pattern as a mask. Pattern forming method processed, the resist underlayer film pattern obtained by an etching mask and forming a pattern on a substrate. A method of forming a pattern on a substrate by lithography, wherein a resist underlayer film is formed on the substrate by using the resist underlayer film material according to any one of claims 1 to 5 , and the resist underlayer A resist upper layer film made of a photoresist composition is used to form a resist upper layer film on the film, the pattern circuit region of the resist upper layer film is exposed, and then developed with a developing solution to form a resist on the resist upper layer film. A pattern is formed, a silicon oxide film is formed on the obtained resist pattern, and at least the silicon oxide film above the resist pattern is removed by etching while leaving a silicon oxide film between the resist patterns. The resist underlayer film is processed using the silicon oxide film as a mask, and the resulting resist underlayer film pattern is used as an etching mask. Pattern forming method and forming a pattern on a substrate by.

Images