JP5538941B2 - Resist underlayer film forming method, pattern forming method and composition, resist underlayer film forming material additive, cross-linking agent, and resist underlayer film - Google Patents

Description

  The present invention relates to a resist underlayer film forming method, a pattern forming method, a composition, an additive for a resist underlayer film forming material, a crosslinking agent, and a resist underlayer film.

  In the manufacturing method of an integrated circuit element, in order to obtain a higher degree of integration, the process size using a multilayer resist process is being miniaturized. In this process, a liquid resist underlayer film forming resin composition is first applied on a substrate, and then a liquid photoresist composition is further applied. Next, the mask pattern is transferred by a reduction projection exposure apparatus (stepper) and developed with an appropriate developer to obtain a photoresist pattern. Subsequently, this pattern is transferred to the resist underlayer film by dry etching. Finally, by transferring the resist underlayer film pattern to the substrate by dry etching, a substrate with a desired pattern can be obtained. At this time, a multilayer process using one type of resist underlayer film is sometimes referred to as a two-layer resist process, and a case of using two types is sometimes referred to as a three-layer resist process.

  In general, the resist underlayer film functions as an antireflection film that absorbs radiation reflected from the substrate. In general, a material having a high carbon content is used for the resist underlayer film directly on the substrate. When the carbon content is large, the etching selectivity at the time of substrate processing is improved, and more accurate pattern transfer is possible. As such an underlayer film, a thermosetting phenol novolak is particularly well known. In addition, it is known that a composition containing an acenaphthylene-based polymer exhibits good characteristics as a lower layer film (see, for example, Patent Documents 1 and 2).

JP 2000-143937 A JP 2001-40293 A

  However, with further miniaturization of the etching pattern, over-etching of the resist underlayer film has become a major problem, and there is a demand for improvement in precise pattern transfer performance and etching resistance. In particular, when transferring a fine pattern, it is required that the pattern of the resist underlayer film does not bend when the substrate is processed using the resist underlayer film as a photomask.

  The present invention has been made in view of the above circumstances, and a resist underlayer film forming method capable of forming a resist underlayer film having a function as an antireflection film and having good pattern transfer performance and etching resistance, and miniaturization To provide a pattern forming method that does not bend even during pattern transfer, a composition that can be suitably used for forming such a resist underlayer film, and an additive or a crosslinking agent for the resist underlayer film forming material. Objective.

  As a result of intensive studies, the present inventors have found that the above-mentioned object can be achieved by forming a resist underlayer film with a composition to which a compound having a specific structure is added, and the present invention has been completed. .

  According to the resist underlayer film forming method of the present invention, a resist underlayer film having a function as an antireflection film and having good pattern transfer performance and etching resistance can be easily formed. In addition, the resist underlayer film obtained by the resist underlayer film forming method of the present invention has excellent etching resistance, and when the substrate to be processed is etched, the underlayer film pattern is not easily bent even if the transferred pattern is fine. Therefore, this resist underlayer film has precise pattern transfer performance and good etching selectivity in the dry etching process, and there is little overetching of the resist underlayer film, and the resist pattern is faithfully reproduced on the substrate to be processed with good reproducibility. Can be transferred to. Furthermore, since the lower layer film pattern is not bent when the substrate to be processed is etched, an improvement in yield can be expected in microfabrication in the lithography process, particularly in the manufacture of highly integrated circuit elements. Further, according to the pattern forming method of the present invention, the resist pattern can be faithfully transferred to the substrate to be processed with good reproducibility. Furthermore, according to the composition of the present invention, it is possible to form a resist underlayer film on the substrate to be processed that is excellent in etching resistance and in which the underlayer film pattern is not easily bent when the substrate to be processed is etched.

Hereinafter, the present invention will be described in detail.
[1] Method for Forming Resist Underlayer Film The method for forming a resist underlayer film of the present invention comprises (A) a resin containing an aromatic ring (hereinafter also referred to as “resin (A)”), and (B) a specific structure. A step of applying a composition containing a compound having a compound (hereinafter also referred to as “compound (B)”) onto a substrate to be processed to form a coating film, and heating the resulting coating film together with the substrate to be processed And a step of forming a resist underlayer film on the substrate to be processed. The composition will be described later.

As the substrate to be processed, for example, a silicon wafer, a wafer coated with aluminum, or the like can be used.
Moreover, the application | coating method of the composition to a to-be-processed substrate is not specifically limited, For example, it can implement by appropriate methods, such as spin coating, cast coating, and roll coating.

Moreover, the said coating film is normally heated in air | atmosphere.
The heating temperature at this time is usually 150 to 500 ° C, preferably about 180 to 350 ° C.
The heating time at this time is 30 to 1200 seconds, and preferably 60 to 600 seconds.

  Furthermore, the oxygen concentration at the time of curing the coating film is desirably 5% by volume or more. When the oxygen concentration at the time of coating film formation is low, the oxidation cross-linking of the lower layer film does not sufficiently proceed, and there is a possibility that the characteristics necessary for the lower layer film cannot be expressed.

Moreover, before heating a coating film at the temperature of 300-500 degreeC, you may preheat at the temperature of 60-250 degreeC.
Although the heating time in preheating is not specifically limited, It is preferable that it is 10 to 300 second, More preferably, it is 30 to 180 second.
By performing this preheating, the dehydrogenation reaction can be efficiently advanced by vaporizing the solvent in advance and keeping the film dense.

  Moreover, in the method for forming a resist underlayer film of the present invention, the coating film is usually cured by heating the coating film to form a resist underlayer film, but the composition containing the resin (A) and the compound (B) By adding a predetermined photocuring agent (crosslinking agent) to the product, an exposure step for the heated coating film can be provided and photocured to form a resist underlayer film. The radiation to be exposed at this time is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ rays, molecular beams, ion beams, etc., depending on the type of acid generator blended in the composition. Selected.

[2] Pattern Forming Method The pattern forming method of the present invention comprises: (1) a resist underlayer film forming step in which a resist underlayer film is formed on a substrate to be processed with a composition containing a resin (A) and a compound (B) ( Hereinafter, also referred to as “step (1)”), and (2) a resist film forming step (hereinafter referred to as “a resist film forming step”) in which a resist composition is formed by applying a resist composition to a substrate on which the resist underlayer film is formed. (Also referred to as “step (2)”), and (3) an exposure step (hereinafter also referred to as “step (3)”) in which the resist film is selectively irradiated with radiation to expose the resist film. (4) developing the exposed resist film to form a resist pattern (hereinafter also referred to as “step (4)”), and (5) using the resist pattern as a mask, The Regis And a pattern forming step (hereinafter also referred to as “step (5)”) for forming a predetermined pattern on the substrate to be processed by dry etching the lower layer film and the substrate to be processed.

In the step (1), a resist underlayer film is formed on the substrate to be processed. The above description can be applied as it is for the method of forming the resist underlayer film.
The thickness of the resist underlayer film formed in this step (1) is usually 0.1 to 5 μm.

Moreover, in this pattern formation method, after the said process (1), the process (1 ') which forms an intermediate | middle layer (intermediate film) on a resist lower layer film may be further provided as needed.
This intermediate layer is a layer provided with these functions in order to further supplement the functions of the resist underlayer film and / or the resist film in the formation of the resist pattern, or to obtain the functions that they do not have. . For example, when the antireflection film is formed as an intermediate layer, the antireflection function of the resist underlayer film can be further supplemented.

  This intermediate layer can be formed of an organic compound or an inorganic oxide. As the organic compound, for example, a coating type antireflection film can be used. As the inorganic oxide, for example, coating type spin-on glass, polysiloxane formed by a CVD method, titanium oxide, alumina oxide, tungsten oxide, or the like can be used.

Although the method for forming the intermediate layer is not particularly limited, for example, a coating method, a CVD method, or the like can be used. Among these, the coating method is preferable. When the coating method is used, the intermediate layer can be formed continuously after forming the resist underlayer film.
Moreover, the film thickness of an intermediate | middle layer is not specifically limited, Although it selects suitably according to the function calculated | required by an intermediate | middle layer, the range of 10-3000 nm is preferable, More preferably, it is 20-300 nm.

In the step (2), a resist film is formed on the substrate to be processed on which the resist underlayer film is formed using the resist composition. Specifically, after a resist composition is applied so that the resulting resist film has a predetermined thickness, the solvent in the film is volatilized by pre-baking to form a resist film.
Examples of the resist composition include a positive or negative chemically amplified resist composition containing a photoacid generator, a positive resist composition comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, and an alkali-soluble resin and a crosslinking agent. And negative resist compositions composed of an agent.
Such a resist composition usually has a solid concentration of about 5 to 50% by mass, and is generally filtered through a filter having a pore diameter of about 0.2 μm and provided for formation of a resist film. In this step, a commercially available resist composition can be used as it is.

The method for applying the resist composition is not particularly limited, and can be carried out by, for example, a spin coating method.
The pre-baking temperature is appropriately adjusted according to the type of resist composition used and the like, but is usually about 30 to 200 ° C, preferably 50 to 150 ° C.

In the step (3), a predetermined region of the obtained resist film is irradiated with radiation and selectively exposed.
The radiation used for the exposure is appropriate from visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ rays, molecular beams, ion beams, etc., depending on the type of photoacid generator used in the resist composition. In particular, it is preferably far ultraviolet rays, and in particular, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (wavelength 157 nm), Kr ₂ excimer laser (wavelength 147 nm), ArKr excimer laser (Wavelength 134 nm), extreme ultraviolet light (wavelength 13 nm, etc.) and the like are preferable.
In addition, the resist pattern formation method in this invention may not pass through image development processes, such as a nanoimprint method.

In the step (4), a resist pattern is formed by developing the exposed resist film with a developer.
The developer used in this step is appropriately selected according to the type of resist composition used. Specifically, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanol Amine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3. 0] -5-nonene and the like.
In addition, an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant can be added to these alkaline aqueous solutions.

Further, after development with the developer, washing and drying are performed to form a predetermined resist pattern.
In this step, post-baking can be performed after the exposure before development in order to improve resolution, pattern profile, developability, and the like. The post-baking temperature is appropriately adjusted according to the type of resist composition used and the like, but is usually about 50 to 200 ° C, preferably 70 to 150 ° C.

  In the step (5), by using the obtained resist pattern as a mask and performing dry etching of the resist underlayer film using, for example, gas plasma such as oxygen plasma, a resist pattern for processing a predetermined substrate is obtained. .

[3] Composition The composition of the present invention comprises a resin (A) and a compound (B). Such a composition is particularly effective for forming a resist underlayer film.

[Resin (A)]
Examples of the resin (A) include novolac resins, resol resins, styrene resins, acenaphthylene resins, resins having a fullerene skeleton, and derivatives thereof.
Specific examples of novolak resins include phenols such as phenol, cresol, xylenol, resorcinol, bisphenol A, paratertiary butylphenol, paraoctylphenol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 2, One or more phenolic compounds selected from the group consisting of naphthols such as 7-dihydroxynaphthalene, and one or more aldehydes selected from aldehyde sources such as formaldehyde, paraformaldehyde, and trioxane; , And a resin obtained by reacting with an acidic catalyst.
Examples of such a resin include those represented by the following general formula (a1) and general formula (a2).

〔一般式（ａ１）及び（ａ２）において、Ｒ^２１及びＲ^２２は、相互に独立に、ヒドロキシル基、置換若しくは非置換の炭素数１〜６のアルキル基、置換若しくは非置換の炭素数１〜６のアルコキシル基、置換若しくは非置換の炭素数２〜１０のアルコキシカルボニル基、置換若しくは非置換の炭素数６〜１４のアリール基、置換若しくは非置換のグリシジルエーテル基、又は、置換若しくは非置換のアルキルグリシジルエーテル基（但し、アルキル部位の炭素数は１〜６である。）を示す。ｍ２は０〜６の整数である。但し、ｍ２が２〜６の整数である場合には、複数のＲ^２１は同一でも異なっていてもよい。ｍ３は０〜４の整数である。但し、ｍ３が２〜４の整数である場合には、複数のＲ^２２は同一でも異なっていてもよい。Ｚは、メチレン基、置換若しくは非置換の炭素数２〜２０のアルキレン基、置換若しくは非置換の炭素数６〜１４のアリーレン基、又は置換若しくは非置換のアルキレンエーテル基を示す。ｍ１は１〜８の整数である。ｍ１が２〜８の整数である場合には、複数のＺは同一でも異なっていてもよい。また、ｍ１〜ｍ３は、１≦ｍ１＋ｍ２≦８、１≦ｍ１＋ｍ３≦８を満たす。〕

[In General Formulas (a1) and (a2), R ²¹ and R ²² are each independently a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted carbon number 1 to 6 alkoxyl groups, substituted or unsubstituted alkoxycarbonyl groups having 2 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, substituted or unsubstituted glycidyl ether groups, or substituted or unsubstituted An alkyl glycidyl ether group (wherein the alkyl moiety has 1 to 6 carbon atoms) is shown. m2 is an integer of 0-6. However, when m2 is an integer of 2 to 6, a plurality of R ²¹ may be the same or different. m3 is an integer of 0-4. However, when m3 is an integer of 2 to 4, the plurality of R ²² may be the same or different. Z represents a methylene group, a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 14 carbon atoms, or a substituted or unsubstituted alkylene ether group. m1 is an integer of 1-8. When m1 is an integer of 2 to 8, a plurality of Z may be the same or different. M1 to m3 satisfy 1 ≦ m1 + m2 ≦ 8 and 1 ≦ m1 + m3 ≦ 8. ]

Examples of the unsubstituted alkyl group having 1 to 6 carbon atoms in R ²¹ and R ²² in the general formulas (a1) and (a2) include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- A butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned.

Examples of the unsubstituted C1-C6 alkoxyl group in R ²¹ and R ²² include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, 1 -Methylpropoxy group, t-butoxy group, 2-propynyloxy group, etc. are mentioned.

Examples of the unsubstituted C2-C10 alkoxycarbonyl group for R ²¹ and R ²² include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, 2 -Methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group and the like can be mentioned.

Examples of the unsubstituted aryl group having 6 to 14 carbon atoms in R ²¹ and R ²² include a phenyl group and a naphthyl group.

Examples of the unsubstituted alkyl glycidyl ether group in R ²¹ and R ²² include a methyl glycidyl ether group, an ethyl glycidyl ether group, a propyl glycidyl ether group, and a butyl glycidyl ether group.

  Examples of the unsubstituted alkylene group having 2 to 20 carbon atoms in Z in the general formulas (a1) and (a2) include, for example, an ethylene group; a propylene group such as a 1,3-propylene group and a 1,2-propylene group Tetramethylene group, pentamethylene group, hexamethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl- 1,4-butylene group, 2-methyl-1,4-butylene group and the like can be mentioned.

  Examples of the unsubstituted arylene group having 6 to 14 carbon atoms in Z include a phenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group.

  It is preferable that carbon number of the alkylene part of the alkylene ether group in Z is 2-20. Specific alkylene ether groups include, for example, ethylene ether groups; propylene ether groups such as 1,3-propylene ether groups and 1,2-propylene ether groups; tetramethylene ether groups, pentamethylene ether groups, hexamethylene ether groups. Etc.

Moreover, R < ²¹ >, R <^22> and Z in general formula (a1) and (a2) may have a substituent. As this substituent, a halogen atom, a hydroxyl group, a C1-C9 alkyl group, a C6-C22 aryl group, etc. are mentioned, for example.
Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Etc.
Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t -A butyl group etc. are mentioned.
Furthermore, examples of the aryl group having 6 to 22 carbon atoms include a phenyl group and a naphthyl group.

  Specific examples of the resole resin include a resin obtained by reacting the above-described phenolic compound with the above-mentioned aldehyde using an alkaline catalyst.

  As an acenaphthylene-type resin, what contains the repeating unit represented by the following general formula (a3), the repeating unit represented by the following general formula (a4), etc. are mentioned, for example.

〔一般式（ａ３）及び（ａ４）において、Ｒ^２３及びＲ^２４は、相互に独立に、水素原子、ハロゲン原子、置換若しくは非置換の炭素数１〜６のアルキル基、置換若しくは非置換の炭素数１〜６のアルコキシル基、置換若しくは非置換の炭素数２〜１０のアルコキシカルボニル基、又は、置換若しくは非置換の炭素数６〜１４のアリール基を示す。Ｒ^２５は水素原子、置換若しくは非置換の炭素数１〜６のアルキル基、置換若しくは非置換の炭素数１〜６のアルコキシル基、置換若しくは非置換の炭素数２〜１０のアルコキシカルボニル基、又は、置換若しくは非置換の炭素数６〜１４のアリール基を示す。〕

[In General Formulas (a3) and (a4), R ²³ and R ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted carbon atom, A C1-C6 alkoxyl group, a substituted or unsubstituted C2-C10 alkoxycarbonyl group, or a substituted or unsubstituted C6-C14 aryl group is shown. R ²⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, or Represents a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. ]

As an unsubstituted C1-C6 alkyl group in R < ²³ > -R < ²⁵ > of general formula (a3) and (a4), a methyl group, an ethyl group, n-propyl group, i-propyl group, n-, for example A butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned.

The unsubstituted alkoxyl group having 1 to 6 carbon atoms in R ²³ to R ^25, for example, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy group, 2-methyl-propoxy group, 1 -Methylpropoxy group, t-butoxy group and the like.

The alkoxycarbonyl group unsubstituted 2 to 10 carbon atoms for R ²³ to R ^25, for example, a methoxycarbonyl group, an ethoxycarbonyl group, n- propoxycarbonyl group, i- propoxycarbonyl group, n- butoxycarbonyl group, 2 -Methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group and the like can be mentioned.

Examples of the unsubstituted aryl group having 6 to 14 carbon atoms in R ^{23 to} R ²⁵ include a phenyl group and a naphthyl group.

As the halogen atom in ^{R 23} and ^{R 24} in the general formula (a3) and (a4), for example, fluorine, chlorine, bromine, and iodine.

Moreover, R < ²³ > -R < ²⁵ > in general formula (a3) and (a4) may have a substituent. As this substituent, a halogen atom, a hydroxyl group, a C1-C9 alkyl group, a C6-C22 aryl group, etc. are mentioned, for example.
Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Etc.
Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t -A butyl group etc. are mentioned.
Furthermore, examples of the aryl group having 6 to 22 carbon atoms include a phenyl group and a naphthyl group.

  Such a resin can be obtained by reacting a polymer of a compound having an acenaphthylene skeleton with paraformaldehyde under acidic conditions.

  As a styrene resin or this derivative, the thing represented by the following general formula (a5) is mentioned, for example.

〔一般式（ａ５）において、Ｍはラジカル重合性の単量体を示す。ｍは正の数であり、ｎは０又は正の数であり、５≦ｍ＋ｎ≦２００、ｍ／（ｍ＋ｎ）≧０．５を満たす。Ｒ^３１及びＲ^３２は、相互に独立に、水素原子、アルキル基、ヒドロキシル基、酸素原子、アリール基、又はエステル基を示す。〕

[In general formula (a5), M represents a radical polymerizable monomer. m is a positive number, n is 0 or a positive number, and satisfies 5 ≦ m + n ≦ 200 and m / (m + n) ≧ 0.5. R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, a hydroxyl group, an oxygen atom, an aryl group, or an ester group. ]

  The radical polymerizable monomer in the general formula (a5) is not particularly limited, and examples thereof include compounds having various polymerizable unsaturated bonds. Specifically, for example, styrene monomers such as styrene and α-methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid, (meth) acrylic acid esters such as methyl (meth) acrylate, acrylamide, etc. Acrylic monomers, vinyl ethers such as ethyl vinyl ether, maleic anhydride, vinyl acetate, vinyl pyridine and the like. In the present specification, “(meth) acryl” means “acryl” or “methacryl”.

As an alkyl group in R < ³¹ > and R < ³² > in general formula (a5), a C1-C10 alkyl group is mentioned. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group.
^The aryl group for ^{R 31} and ^{R 32,} an aryl group having 6 to 30 carbon atoms. Specifically, a phenyl group, a naphthyl group, etc. are mentioned, for example.
R ³¹ and R ³² each take a para position, an ortho position, or a meta position with respect to the main chain.

  Further, the structural unit derived from M (radically polymerizable monomer) which is a copolymerization component in the general formula (a5) is 50 moles when the total of the structural units constituting the polymer is 100 mole%. It is preferable that it is less than%.

  As such a styrene resin or a derivative thereof (particularly a polyvinylphenol polymer), a commercially available product can be used. For example, “Marca Linker M” (poly-p-vinylphenol), “Maruzen Petrochemical”, “ "Linker MB" (brominated poly-p-vinylphenol), "Linker CMM" (p-vinylphenol / methyl methacrylate copolymer), "Linker CHM" (p-vinylphenol / 2-hydroxyethyl methacrylate copolymer) Combination), “linker CST” (p-vinylphenol / styrene copolymer), and the like.

Moreover, it is preferable that the polystyrene conversion weight average molecular weight (henceforth "Mw") measured by the gel permeation chromatography (GPC) of resin (A) is 500-100,000, More preferably, 000 to 50,000, more preferably 1,200 to 40,000.
Furthermore, the ratio (Mw / Mn) of Mw of the polymer (A) and polystyrene-reduced number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 ~ 3.

  Moreover, the composition of this invention may contain 1 type of resin (A), and may contain 2 or more types.

[Compound (B)]
The compound (B) is represented by the following general formula (i).
The composition of the present invention is considered that the compound (B) and the resin (A) undergo an oxidative cross-linking reaction accompanied by a dehydrogenation reaction, thereby reducing the hydrogen content of the entire material and increasing the curability. It is done. For this reason, it is considered that the bending resistance of the formed resist underlayer film is improved. Therefore, the compound (B) is effective as an additive for the resist underlayer film forming material. Furthermore, from such a function of the compound (B), it is effective as a crosslinking agent.

一般式（ｉ）において、Ｒはそれぞれ独立に水素原子、Ｒ^１またはＲ^３を示し、Ｒのうち少なくとも２つはＲ^１である。Ｒ^１は炭素数２〜１３のアルキルエステル基、炭素数７〜１３のアリールエステル基、ヒドロキシメチル基、炭素数２〜１３のアルコキシメチル基、炭素数７〜１３のアリーロキシメチル基、または炭素数３〜１４のアシロキシメチル基を示し、Ｒ^１が複数存在する場合はそれぞれ同一でも異なっていてもよい。Ｒ^３はヒドロキシル基、炭素数１〜９のアルキル基、または炭素数６〜３０のアリール基を示し、Ｒ^３が複数存在する場合はそれぞれ同一でも異なっていてもよい。

In general formula (i), each R independently represents a hydrogen atom, R ¹ or R ^3, and at least two of R are R ¹ . R ¹ is an alkyl ester group having 2 to 13 carbon atoms, an aryl ester group having 7 to 13 carbon atoms, a hydroxymethyl group, an alkoxymethyl group having 2 to 13 carbon atoms, an aryloxymethyl group having 7 to 13 carbon atoms, or carbon When an acyloxymethyl group of 3 to ¹⁴ is shown and a plurality of R ¹ are present, they may be the same or different. R ³ represents a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and when a plurality of R ³ are present, they may be the same or different.

Examples of the alkyl ester group having 2 to 13 carbon atoms in R ¹ of the general formula (i) include a methyl ester group, an ethyl ester group, an n-propyl ester group, an i-propyl ester group, an n-butyl ester group, 2 -Methylpropyl ester group, 1-methylpropyl group, t-butyl ester group, pentyl ester group, hexyl ester group, heptyl ester group, octyl ester group, nonyl ester group, decyl ester group, undecyl ester group, dodecyl ester group Etc.

Examples of the aryl ester group having 2 to 13 carbon atoms in R ¹ of the general formula (i) include a phenyl ester group and a naphthyl ester group.

Examples of the alkoxymethyl group having 2 to 13 carbon atoms in R ¹ of the general formula (i) include a methoxymethyl group, an ethoxyethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, 2 -Methylpropoxymethyl group, 1-methylpropoxymethyl group, t-butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, octyloxymethyl group, nonyloxymethyl group, decyloxymethyl group, un A decyloxymethyl group, a dodecyloxymethyl group, etc. are mentioned.

Examples of the acyloxymethyl group having 3 to 14 carbon atoms in R ¹ of the general formula (i) include an acetoxymethyl group, a propionyloxymethyl group, a butyroxymethyl group, an i-butyroxymethyl group, and a pentanoyloxymethyl group. Group, hexanoyloxymethyl group, heptanoyloxymethyl group, octanoyloxymethyl group, nonanoyloxymethyl group, decanoyloxymethyl group, undecanoyloxymethyl group, dodecanoyloxymethyl group, benzoyloxymethyl group, etc. Is mentioned.

In general formula (i), at least two of R are R ¹ , and preferably four of R are R ¹ .

Examples of the alkyl group having 1 to 9 carbon atoms in R ³ of the general formula (i) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, t- A butyl group etc. are mentioned.
The aryl group having 6 to 30 carbon atoms in R ^3, a phenyl group, a naphthyl group, methylphenyl group, ethylphenyl group, and the like.

  As a compound (B) which has the above-mentioned structure, the compound represented by the following general formula (b1-1), the compound represented by the following general formula (b2-1), etc. can be mentioned, for example.

〔一般式（ｂ１−１）において、ｎ_２１〜ｎ_２４はそれぞれ独立に１〜３の整数を示す。ｎ_３１〜ｎ_３４はそれぞれ独立に０〜２の整数を示す。また、１≦ｎ_２１＋ｎ_３１≦３、１≦ｎ_２２＋ｎ_３２≦３、１≦ｎ_２３＋ｎ_３３≦３、１≦ｎ_２４＋ｎ_３４≦３である。Ｒ^２は炭素数１〜１２のアルキル基、又は炭素数６〜１２のアリール基を示し、Ｒ^２が複数存在する場合はそれぞれ同一でも異なっていてもよい。Ｒ^３はヒドロキシル基、炭素数１〜９のアルキル基、又は炭素数６〜３０のアリール基を示し、Ｒ^３が複数存在する場合はそれぞれ同一でも異なっていてもよい。〕

[In General Formula (b1-1), n _{21 to} n ₂₄ each independently represents an integer of 1 to 3. n _{31 to} n ₃₄ each independently represents an integer of 0 to 2. Also, 1 ≦ n ₂₁ + n ₃₁ ≦ 3, 1 ≦ n ₂₂₊ n ₃₂ ≦ 3, 1 ≦ n ₂₃₊ n ₃₃ ≦ 3, 1 ≦ n ₂₄₊ n ₃₄ ≦ 3. R ² represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and when a plurality of R ² are present, they may be the same or different. R ³ represents a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. ]

〔一般式（ｂ２−１）において、ｎ_４１〜ｎ_４４はそれぞれ独立に１〜３の整数を示す。ｎ_３１〜ｎ_３４はそれぞれ独立に０〜２の整数を示す。また、１≦ｎ_４１＋ｎ_３１≦３、１≦ｎ_４２＋ｎ_３２≦３、１≦ｎ_４３＋ｎ_３３≦３、１≦ｎ_４４＋ｎ_３４≦３である。Ｒ^３はヒドロキシル基、炭素数１〜９のアルキル基、又は炭素数６〜３０のアリール基を示し、Ｒ^３が複数存在する場合はそれぞれ同一でも異なっていてもよい。Ｒ^４は水素原子、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、炭素数２〜１３のアシル基を示し、Ｒ^４が複数存在する場合はそれぞれ同一でも異なっていてもよい。〕

In [Formula _(b2-1), n 41 _{~n 44} each independently represent an 1-3 integer. n _{31 to} n ₃₄ each independently represents an integer of 0 to 2. Further, 1 ≦ n ₄₁ + n ₃₁ ≦ 3, 1 ≦ n ₄₂₊ n ₃₂ ≦ 3, 1 ≦ n ₄₃₊ n ₃₃ ≦ 3, 1 ≦ n ₄₄₊ n ₃₄ ≦ 3. R ³ represents a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an acyl group having 2 to 13 carbon atoms, and when a plurality of R ⁴ are present, they may be the same or different. Good. ]

Examples of the alkyl group having 1 to 12 carbon atoms in R ² of the general formula (b1-1) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, Examples include t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
The aryl group having 6 to 12 carbon atoms for R ^2, for example, a phenyl group, a naphthyl group, methylphenyl group, ethylphenyl group, and the like.

As R ^{3 in the} general formula (b1-1), the description of R ³ in the general formula (i) can be applied.

In formula (b1-1), n ₂₁ , n ₂₂ , n ₂₃ and n ₂₄ are each independently an integer of 1 to 3, and more preferably an integer of 1 to 2.
N ₃₁ , n ₃₂ , n ₃₃ and n ₃₄ are each independently an integer of 0 to 2, and more preferably an integer of 0 to 1.
Further, 1 ≦ n ₂₁ + n ₃₁ ≦ 3, 1 ≦ n ₂₂₊ n ₃₂ ≦ 3, 1 ≦ n ₂₃₊ n ₃₃ ≦ 3, 1 ≦ n ₂₄₊ n ₃₄ ≦ 3, and 1 ≦ n ₂₁ + n ₃₁ ≦ 2, 1 It is more preferable that ≦ n ₂₂₊ n ₃₂ ≦ 2, 1 ≦ n ₂₃₊ n ₃₃ ≦ 2, 1 ≦ n ₂₄₊ n ₃₄ ≦ 2.

As R ³ of the general formula (b2-1), the description of R ³ in the general formula (i) can be applied.

Examples of the alkyl group having 1 to 12 carbon atoms in R ⁴ of the general formula (b2-1) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, Examples include t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.

As a C6-C12 aryl group in R < ⁴ > of general formula (b2-1), a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group etc. are mentioned, for example.

Examples of the acyl group having 2 to 13 carbon atoms in R ⁴ of the general formula (b2-1) include an acetyl group, a propionyl group, an n-butyryl group, an i-butyryl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, and octanoyl. Group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, benzoyl group and the like.

The _{n 3} in the general formula (b2-1) is an integer of 0 to 2, and more preferably an integer of 0-1.
Further, _{n 4} is an integer of 1 to 3, and more preferably an integer of 1-2.
Further, 1 ≦ n ₄₁ + n ₃₁ ≦ 3, 1 ≦ n ₄₂₊ n ₃₂ ≦ 3, 1 ≦ n ₄₃₊ n ₃₃ ≦ 3, 1 ≦ n ₄₄₊ n ₃₄ ≦ 3, and 1 ≦ n ₄₁ + n ₃₁ ≦ 2, 1 It is more preferable that ≦ n ₄₂₊ n ₃₂ ≦ 2, 1 ≦ n ₄₃₊ n ₃₃ ≦ 2, 1 ≦ n ₄₄₊ n ₃₄ ≦ 2.

  Moreover, it is preferable that a compound (B) is a compound represented by the following general formula (b1-2).

〔一般式（ｂ１−２）において、Ｒ^５は、相互に独立して、炭素数１〜１２のアルキル基、又は炭素数６〜１２のアリール基を示す。〕

[In General Formula (b1-2), R ⁵ independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

Examples of the alkyl group having 1 to 12 carbon atoms in R ⁵ of the general formula (b1-2) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, Examples include t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
The aryl group having 6 to 12 carbon atoms in R ^5, for example, a phenyl group, a naphthyl group, methylphenyl group, ethylphenyl group, and the like.

  In particular, the compound (B) is preferably a compound represented by the following general formula (b2-2) or (b2-3).

〔一般式（ｂ２−２）において、Ｒ^６は、相互に独立して、水素原子、炭素数１〜１２のアルキル基、又は炭素数６〜１２のアリール基を示す。〕

[In General Formula (b2-2), R ⁶ independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ]

〔一般式（ｂ２−３）において、Ｒ^７は、相互に独立して、炭素数１〜１２のアルキル基、又は炭素数６〜１２のアリール基を示す。〕

[In General Formula (b2-3), R ⁷ independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

Examples of the alkyl group having 1 to 12 carbon atoms in R ⁶ of the general formula (b2-2) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, t- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
The aryl group having 6 to 12 carbon atoms in R ^6, for example, a phenyl group, a naphthyl group, methylphenyl group, ethylphenyl group, and the like.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁷ in the general formula (b2-3) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, t- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
The aryl group having 6 to 12 carbon atoms in R ^7, for example, a phenyl group, a naphthyl group, methylphenyl group, ethylphenyl group, and the like.

  Here, specific compounds (B) include, for example, tetramethyl perylene-3,4,9,10-tetracarboxylate, tetraethyl perylene-3,4,9,10-tetracarboxylate, perylene-3,4,9. , 10-tetracarboxylic acid tetra-n-propyl, perylene-3,4,9,10-tetracarboxylic acid tetra-i-propyl, perylene-3,4,9,10-tetracarboxylic acid tetra-n-butyl, perylene-3,4 9,10-tetracarboxylic acid tetrakis (2-methylpropyl), perylene-3,4,9,10-tetracarboxylic acid tetrakis (1-methylpropyl), perylene-3,4,9,10-tetracarboxylic acid tetra-t- Butyl, perylene-3,4,9,10-tetracarboxylic acid tetrapentyl, perylene-3,4,9,10-tetraca Tetrahexyl borate, tetraheptyl perylene-3,4,9,10-tetracarboxylic acid, tetraoctyl perylene-3,4,9,10-tetracarboxylic acid, tetranonyl perylene-3,4,9,10-tetracarboxylic acid, perylene- Perylenetetracarboxylic acid tetradecyl such as tetradecyl 3,4,9,10-tetracarboxylic acid, tetraundecyl perylene-3,4,9,10-tetracarboxylic acid, tetradodecyl perylene-3,4,9,10-tetracarboxylic acid Esters;

  3,4,9,10-tetrakis (methoxymethyl) perylene, 3,4,9,10-tetrakis (ethoxymethyl) perylene, 3,4,9,10-tetrakis (n-propoxymethyl) perylene, 3,4 , 9,10-tetrakis (i-propoxymethyl) perylene, 3,4,9,10-tetrakis (n-butoxymethyl) perylene, 3,4,9,10-tetrakis (2-methylpropoxymethyl) perylene, 3, , 4,9,10-tetrakis (1-methylpropoxymethyl) perylene, 3,4,9,10-tetrakis (t-butoxymethyl) perylene, 3,4,9,10-tetrakis (pentyloxymethyl) perylene, 3,4,9,10-tetrakis (hexyloxymethyl) perylene, 3,4,9,10-tetrakis (heptyloxymethyl) Perylene, 3,4,9,10-tetrakis (octyloxymethyl) perylene, 3,4,9,10-tetrakis (nonyloxymethyl) perylene, 3,4,9,10-tetrakis (decyloxymethyl) perylene, Tetrakis (alkoxymethyl) perylenes such as 3,4,9,10-tetrakis (undecyloxymethyl) perylene, 3,4,9,10-tetrakis (dodecyloxymethyl) perylene;

  Perylene-3,4,9,10-tetrayltetrakis (methylene) tetraacetate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetrapropionate, perylene-3,4,9,10- Tetrayltetrakis (methylene) tetra n-butyrate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetrai-butyrate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetrapenta Noate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetrahexanoate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetraheptanoate, perylene-3,4 , 9,10-Tetrayltetrakis (methylene) tetraoctanoate, perylene-3, , 9,10-tetrayltetrakis (methylene) tetranonanoate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetradecanoate, perylene-3,4,9,10-tetrayltetrakis ( Perylenetetra such as methylene) tetraundecanoate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetradodecanoate, perylene-3,4,9,10-tetrayltetrakis (methylene) tetrabenzoate Iltetrakis (methylene) carboxylates and the like can be mentioned.

  These compounds (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compounding quantity of a compound (B) is 0.1 to 500 mass parts normally per 100 mass parts of resin (A) of a composition, Preferably it is 1 to 100 mass parts.

[Other cross-linking agents]
In the composition of the present invention, other crosslinking agent may be blended in addition to the above-mentioned compound (B).
Examples of other crosslinking agents include polynuclear phenols and various commercially available curing agents. As such other crosslinking agents, for example, those described in paragraphs [0085] to [0086] in JP-A No. 2004-168748 can be used.
These other crosslinking agents may be used singly or in combination of two or more, and polynuclear phenols and a curing agent may be used in combination.

  The amount of the other crosslinking agent is usually 0.1 parts by mass or more and 500 parts by mass or less, preferably 1 part by mass or more and 100 parts by mass or less per 100 parts by mass of the resin (A) of the composition.

[(C) Solvent]
The composition of the present invention contains the above-mentioned resin (A) and compound (B). This composition is usually a solvent that dissolves resin (A) and compound (B) (hereinafter referred to as “solvent (C ) ")).
The solvent (C) is not particularly limited as long as it can dissolve the resin (A) and the compound (B). For example, the solvent (C) described in paragraphs [0070] to [0073] of JP-A No. 2004-168748 A thing etc. can be used.

Among these solvents (C), propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethyl lactate, n-butyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; 2-heptanone, cyclohexanone, etc. Ketones; aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, and cymene; and γ-butyrolactone are preferred.
In addition, a solvent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the solvent (C) used is such that the solid content concentration of the resulting composition is usually 1 to 80% by mass, preferably 3 to 40% by mass, more preferably 5 to 30% by mass.

  In the composition of the present invention, an acid generator (D), an accelerator (E), and an additive (F) can be blended as necessary as long as the desired effect in the present invention is not impaired. Among these, it is preferable that the accelerator (E) is blended.

[Acid generator (D)]
The acid generator (D) is a component that generates an acid upon exposure or heating. By containing this acid generator (D), the composition of the present invention can effectively cause a crosslinking reaction between the molecular chains of the resin at a relatively low temperature including normal temperature.
Examples of the acid generator that generates an acid upon exposure (hereinafter referred to as “photoacid generator”) include those described in paragraphs [0077] to [0081] of JP-A No. 2004-168748. Can do.

Among these photoacid generators, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalenesulfonate Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-Butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenol) Le) or the like iodonium naphthalene sulfonate is preferred.
In addition, these photo-acid generators may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the acid generator that generates an acid by heating (hereinafter referred to as “thermal acid generator”) include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl, and the like. Tosylate, alkyl sulfonates and the like can be mentioned.
In addition, these thermal acid generators may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, you may use together a photo-acid generator and a thermal acid generator as an acid generator (D).

  The compounding amount of the acid generator (D) is usually 5000 parts by mass or less, preferably 0.1 to 1000 parts by mass, more preferably 0.1 to 100 parts by mass per 100 parts by mass of the resin (A) of the composition. It is.

[Accelerator (E)]
The accelerator (E) represents a one-electron oxidant or the like for sufficiently causing a dehydrogenation reaction necessary for oxidative crosslinking. One-electron oxidant means an oxidant that itself undergoes one-electron transfer. For example, in the case of cerium (IV) ammonium nitrate, cerium ion (IV) obtains one electron and changes to cerium ion (III). In addition, radical oxidizing agents such as halogen obtain one electron and convert it to an anion. In this way, the phenomenon of oxidizing the oxide by taking one electron from the oxide (substrate, catalyst, etc.) is called one-electron oxidation, and the component that receives one electron at this time is called a one-electron oxidant.
Typical examples of the one-electron oxidant include (a) metal compound, (b) peroxide, (c) diazo compound, (d) halogen or halogen acid.

Examples of the metal compound (a) include metal compounds containing cerium, lead, silver, manganese, osmium, ruthenium, vanadium, thallium, copper, iron, bismuth, and nickel. Specifically, (a1) cerium salts (such as cerium (IV) ammonium nitrate (CAN; ammonium hexanitratocerium (IV)), cerium (IV) acetate, cerium (IV) nitrate, cerium (IV) sulfate ( For example, tetravalent cerium salt), (a2) lead tetraacetate, lead oxide such as lead (IV) oxide (eg, tetravalent lead compound), (a3) silver (I) oxide, silver (II) oxide, Silver carbonate (Fetizon reagent), silver compounds such as silver nitrate, (a4) manganese compounds such as permanganate, activated manganese dioxide, manganese (III) salts, (a5) osmium compounds such as osmium tetroxide, (a6) Ruthenium compounds such as ruthenium oxide, (a7) Vanadium compounds such as VOCl ₃ , VOF ₃ , V ₂ O ₅ , NH ₄ VO ₃ , NaVO ₃ , (a8) Tariu acetate (III), thallium compounds such as thallium (III) trifluoroacetate, thallium (III) nitrate, (a9) copper (II) acetate, copper (II) trifluoromethanesulfonate, copper (II) trifluoroborate, copper chloride (II), copper compounds such as copper (I) acetate, (a10) iron compounds such as iron (III) chloride and potassium hexacyanoferrate (III), (a11) bismuth compounds such as sodium bismuth, (a12) Examples thereof include nickel compounds such as nickel oxide.

Examples of the (b) peroxide include peracids such as peracetic acid and m-chloroperbenzoic acid; hydroxyperoxides such as hydrogen peroxide and alkylhydroxyperoxides such as t-butyl hydroperoxide; diacyl peroxide , Peracid ester, peracid ketal, peroxydicarbonate, dialkyl peroxide, peracid ketone and the like.
Examples of the (c) diazo compound include 2,2′-azobisisobutyronitrile.
Examples of the (d) halogen or halogen acid include halogens selected from chlorine, bromine, and iodine, and perhalogen acids, halogen acids, halogen acids, hypohalous acids, and salts thereof. Examples of the halogen in the halogen acid include chlorine, bromine and iodine. Specific examples of the halogen acid or a salt thereof include sodium perchlorate and sodium bromate.

Among these one-electron oxidants, (b) peroxides and (c) diazo compounds are preferable, and in particular, m-chloroperbenzoic acid, t-butyl hydroperoxide, 2,2′-azobisisobutyro Nitriles are preferred. When these are used, there is no possibility that metal residues or the like adhere to the substrate, which is preferable.
In addition, these accelerators (E), such as a one-electron oxidizer, may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the accelerator (E) is usually 1000 parts by mass or less, preferably 0.01 to 500 parts by mass, more preferably 0.1 to 100 parts by mass per 100 parts by mass of the resin (A) of the composition. is there.

[Additive (F)]
As said additive (F), binder resin, a radiation absorber, surfactant, etc. are mentioned.
As these additives (F), for example, those described in paragraphs [0088] to [0093] in JP-A No. 2004-168748 can be used.
As the binder resin, various thermoplastic resins and thermosetting resins (excluding the above-described resin (A)) can be used. A thermoplastic resin is a component which has the effect | action which provides the fluidity | liquidity, mechanical characteristic, etc. of the added thermoplastic resin to a lower layer film | membrane. The thermosetting resin is a component that is cured by heating and becomes insoluble in a solvent, and has a function of preventing intermixing between the resulting resist underlayer film and the resist film formed thereon. It can be preferably used as a resin. Among these, thermosetting resins such as urea resins, melamine resins, and aromatic hydrocarbon resins are preferable.
In addition, these binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compounding quantity of binder resin is 20 mass parts or less normally per 100 mass parts of resin (A) in a composition, Preferably it is 10 mass parts or less.

  The blending amount of the radiation absorber is usually 100 parts by mass or less, preferably 50 parts by mass or less per 100 parts by mass of the resin (A) of the composition.

The surfactant is a component having an action of improving coatability, striation, wettability, developability and the like.
These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compounding quantity of surfactant is normally 15 mass parts or less per 100 mass parts of resin (A) of a composition, Preferably it is 10 mass parts or less.

  In addition to the above-mentioned additives, other additives such as a storage stabilizer, an antifoaming agent, and an adhesion aid can be blended with the composition in the present invention.

[4] Resist Underlayer Film The resist underlayer film of the present invention is formed by a composition containing the resin (A) and the compound (B). For the composition, the above description of the composition of the present invention can be applied as it is.
This resist underlayer film is formed by forming a resist underlayer film on a substrate to be processed, forming a resist pattern on the resist underlayer film, and then transferring the resist pattern to the resist underlayer film to form an underlayer film pattern. It can be suitably used for a multilayer resist process in which an underlayer film pattern is used as an etching mask and transferred to a substrate to be processed.

The hydrogen content of the resist underlayer film is 0 to 50 atom%, preferably 0 to 35 atom%. The method for measuring the hydrogen content in the resist underlayer film is the same as in the examples described later.
The method for forming such a resist underlayer film is not particularly limited, and can be obtained by, for example, the resist underlayer film forming method of the present invention described later.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” and “%” are based on mass unless otherwise specified.

[1] Synthesis of resin containing aromatic ring <Synthesis Example 1>
A reactor equipped with a condenser, a thermometer and a stirrer was charged with 100 parts of 2,7-dihydroxynaphthalene, 100 parts of propylene glycol monomethyl ether acetate and 50 parts of paraformaldehyde, 2 parts of oxalic acid was added, and dehydration was carried out at 120 ° C. After heating up and making it react for 5 hours, resin (A-1) which has the following structural unit was obtained.
Moreover, the weight average molecular weight (Mw) of obtained resin (A-1) was 3,000.

  In addition, the measurement of the weight average molecular weight (Mw) in a present Example uses the "GPC column" (G2000HXL: 2 pieces, G3000HXL: 1 piece) by Tosoh Corporation, flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, Column temperature: It was measured by a gel permeation chromatograph (detector: differential refractometer) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C.

<Synthesis Example 2>
A reactor equipped with a condenser, a thermometer and a sales expansion device was charged with 100 parts of phenol, 100 parts of propylene glycol monomethyl ether acetate and 50 parts of paraformaldehyde, 2 parts of oxalic acid was added, and the temperature was raised to 120 ° C. while dehydrating, After reacting for 5 hours, a resin (A-2) having the following structural units was obtained.
Moreover, the weight average molecular weight (Mw) of obtained resin (A-2) was 7,000.

<Synthesis Example 3>
A separable flask equipped with a thermometer was charged with 100 parts of acenaphthylene, 78 parts of toluene, 52 parts of dioxane and 3 parts of azobisisobutyronitrile under nitrogen and stirred at 70 ° C. for 5 hours. To the obtained resin having a molecular weight of 10,000, 5.2 parts of p-toluenesulfonic acid monohydrate and 40 parts of paraformaldehyde were added, the temperature was raised to 120 ° C., and the mixture was further stirred for 6 hours. Thereafter, the reaction solution was poured into a large amount of isopropanol, and the precipitated resin was filtered to obtain a resin (A-3).
Moreover, the weight average molecular weight (Mw) of obtained resin (A-3) was 20,000.

[2] Preparation of composition (2-1) Examples 1 to 9
<Example 1>
As shown in Table 1, 10 parts of the resin (A-1) described above was added to 1 part of a cross-linking agent [tetramethyl 3,4,9,10-tetracarboxylate tetramethyl (the following compound (B-1))], It melt | dissolved in 0.1 part of thermal acid generators [diphenyliodonium trifluoromethanesulfonate (C-1)] and 90 parts of solvent [propylene glycol monomethyl ether acetate (D-1)]. This solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare the composition of Example 1.

<Examples 2 to 14>
Except having set it as the composition and compounding quantity shown in Table 1, it carried out similarly to Example 1, and prepared each composition of Examples 2-9.

  In addition, resin (A-2)-(A-3) used by Examples 2-3 in Table 1 is resin obtained by the above-mentioned synthesis examples 2-3. The details of the crosslinking agents (B-1) to (B-7) in Table 1 are as follows.

(2-2) Comparative Examples 1-3
<Comparative Example 1>
As shown in Table 1, 10 parts of the resin (A-1) described above was added to 1 part of a crosslinking agent [1,3,4,6-tetrakis (methoxymethyl) glycoluril (the following compound (b-1))], It melt | dissolved in 0.1 part of thermal acid generators [diphenyliodonium trifluoromethanesulfonate (C-1)] and 90 parts of solvent [propylene glycol monomethyl ether acetate (D-1)]. This solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare the composition of Comparative Example 1.

<Comparative Examples 2-3>
The compositions of Comparative Examples 2 and 3 were prepared in the same manner as Comparative Example 1 except that the compositions and amounts shown in Table 1 were used.

  The details of the other crosslinking agents (b-1) to (b-3) in Table 1 are as follows.

[3] Evaluation of composition The following evaluation was performed about each composition of Examples 1-14 and Comparative Examples 1-3. The results are shown in Table 2.

<Pattern shape after substrate processing>
Each composition of Examples and Comparative Examples was spin-coated on a silicon wafer having a diameter of 8 inches, and then heated at 180 ° C. for 60 seconds in a hot plate with an oxygen concentration of 20% by volume, and then continuously at 350 ° C. for 120 seconds. By heating, a resist underlayer film having a film thickness of 0.3 μm was formed.
Thereafter, a spin-on-glass composition solution for a three-layer resist process (manufactured by JSR Corporation) is spin-coated on the obtained resist underlayer film, and heated on a hot plate at 200 ° C. and 300 ° C. for 60 seconds, respectively. An intermediate layer film having a thickness of 0.05 μm was formed. Next, an ArF resist composition solution [acrylic ArF photoresist, manufactured by JSR Co., Ltd.] is spin-coated on the obtained intermediate layer coating, and prebaked on a hot plate at 130 ° C. for 90 seconds to form a film. A resist film having a thickness of 0.2 μm was formed. Thereafter, a 40 nm line and space pattern (1L / 1S) is formed through the mask pattern using an ArF excimer laser immersion exposure apparatus “S610C” (lens numerical aperture 1.3, exposure wavelength 193 nm) manufactured by NIKON. Thus, exposure was performed for the optimum exposure time. Next, after post-baking on a hot plate at 130 ° C. for 90 seconds, using a 2.38% concentration tetramethylammonium hydroxide aqueous solution, developing at 25 ° C. for 1 minute, washing with water and drying, a positive type for ArF A resist pattern was obtained. Thereafter, the resist film was used as a mask to process the intermediate film, and then the resist underlayer film was processed using the processed intermediate film as a mask. Next, the processed substrate was processed using the processed resist underlayer film as a mask.
And the pattern shape after a board | substrate process was observed with the scanning electron microscope, and the following reference | standard evaluated.
“○”: Underlayer pattern standing “×”: Underlayer pattern falling or bent

<Etching resistance>
Each composition of Examples and Comparative Examples was spin-coated on a silicon wafer having a diameter of 8 inches, and then heated at 180 ° C. for 60 seconds in a hot plate with an oxygen concentration of 20% by volume, and then continuously at 350 ° C. for 120 seconds. By heating, a resist underlayer film having a thickness of 0.3 μm is formed, and this resist underlayer film is etched using an etching apparatus “EXAM” (manufactured by Shinko Seiki Co., Ltd.) with CF ₄ / Ar / O ₂ (CF ₄ : 40 mL / Etching was performed at min, Ar: 20 mL / min, O ₂ : 5 mL / min; pressure: 20 Pa; RF power: 200 W; treatment time: 40 seconds;
And the film thickness before and behind an etching process was measured, the etching rate was computed, and the etching tolerance was evaluated on the following reference | standard.
“◯”: When the etching rate is 150 nm / min or less “Δ”: When the etching rate is 150 to 200 nm / min “X”: When the etching rate is 200 nm / min or more

<Elemental composition>
Each composition of Examples and Comparative Examples was spin-coated on a silicon wafer having a diameter of 8 inches, and then heated at 180 ° C. for 60 seconds in a hot plate with an oxygen concentration of 20% by volume, and then continuously at 350 ° C. for 120 seconds. By heating, a resist underlayer film having a thickness of 0.3 μm is formed. About this resist underlayer film, a carbon / hydrogen / nitrogen simultaneous quantification apparatus “JM10” (manufactured by J-Science Laboratories) is used. The weight conversion value was calculated.
Then, the number of atoms of each element contained in the film is calculated by [weight converted value of each element (% by weight) / mass of each element (g)], and then [number of hydrogen atoms in film / in film] From the total number of atoms, the hydrogen content (atom%) after the dehydrogenation reaction was determined.
The hydrogen content before the dehydrogenation reaction was 200 ° C. in a hot plate having an oxygen concentration of 20% by volume after spin-coating the compositions of Examples and Comparative Examples on a silicon wafer having a diameter of 8 inches. Measurement was performed using a resist underlayer film formed by heating for 60 seconds.

  According to Table 2, according to each composition of Examples 1-9, it has confirmed that a resist underlayer film with favorable pattern transfer performance and etching tolerance could be formed.

According to the resist underlayer film forming method of the present invention, it is possible to form a resist underlayer film that has excellent etching resistance and does not bend the underlayer film pattern when etching a substrate to be processed. Therefore, it can be used very suitably for fine processing in a lithography process. In particular, in a dry etching process, it has precise pattern transfer performance and good etching selectivity, and there is little over-etching of the resist underlayer film, and the resist pattern can be faithfully transferred to the substrate to be processed with good reproducibility. . In addition, since the lower layer film pattern is not bent when the substrate to be processed is etched, an improvement in yield can be expected in microfabrication in the lithography process, particularly in the manufacture of highly integrated circuit elements.
In addition, the composition of the present invention and the additive for forming a resist underlayer film are extremely useful as materials for forming a resist underlayer film.

Claims (12)

Applying a composition containing (A) a resin containing an aromatic ring and (B) a compound represented by the following general formula (i) on a substrate to be processed to form a coating film;
Heating the coating film together with the substrate to be processed to form a resist underlayer film on the substrate to be processed;
A method for forming a resist underlayer film.

[In General Formula (i), each R independently represents a hydrogen atom, R ¹ or R ^3, and at least two of R are R ¹ .
R ¹ is an alkoxycarbonyl group having 2 to 13 carbon atoms, an aryloxycarbonyl group having 7 to 13 carbon atoms, a hydroxymethyl group, an alkoxymethyl group having 2 to 13 carbon atoms, an aryloxymethyl group having 7 to 13 carbon atoms, or An acyloxymethyl group having 3 to 14 carbon atoms is shown, and when there are a plurality of R ^{1 s} , they may be the same or different.
R ³ represents a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. ] (1) A resist underlayer film forming step of forming a resist underlayer film on the substrate to be processed by the resist underlayer film forming method according to claim 1;
(2) a resist film forming step of forming a resist film by applying a resist composition to the substrate to be processed on which the resist underlayer film is formed;
(3) An exposure step of selectively irradiating the resist film with radiation to expose the resist film;
(4) A resist pattern forming step of developing the exposed resist film to form a resist pattern;
(5) A pattern forming step of using the resist pattern as a mask, dry-etching the resist underlayer film and the substrate to be processed, and forming a predetermined pattern on the substrate to be processed;
A pattern forming method comprising:   The pattern forming method according to claim 2, further comprising a step (1 ') of forming an intermediate layer on the resist underlayer film after the (1) resist underlayer film forming step. (A) a resin containing an aromatic ring;
(B) The composition containing the compound represented by the following general formula (i).

[In General Formula (i), each R independently represents a hydrogen atom, R ¹ or R ^3, and at least two of R are R ¹ .
R ¹ is an unbranched alkoxy group having 2 to 13 carbon atoms, an aryloxycarbonyl group having 7 to 13 carbon atoms, a hydroxymethyl group, an alkoxymethyl group having 2 to 13 carbon atoms, or an aryl having 7 to 13 carbon atoms. A loxymethyl group or an acyloxymethyl group having 3 to 14 carbon atoms is shown, and when a plurality of R ¹ are present, they may be the same or different.
R ³ represents a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. ] (A) a resin containing an aromatic ring;
(B) a compound represented by the following general formula (b1-1), and including sets Narubutsu at least one of the compounds represented by the following general formula (b2-1).

[In General Formula (b1-1), n _{21 to} n ₂₄ each independently represents an integer of 1 to 3. n _{31 to} n ₃₄ each independently represents an integer of 0 to 2. Further, 1 ≦ n ₂₁ + n ₃₁ ≦ 3, 1 ≦ n ₂₂ + n ₃₂ ≦ 3, 1 ≦ n ₂₃ + n ₃₃ ≦ 3, 1 ≦ n ₂₄ + n ₃₄ ≦ 3. R ² represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and when a plurality of R ² are present, they may be the same or different. R < ³ > is synonymous with General formula (i), and when two or more R < ³ > exists, it may be same or different, respectively. ]

In [Formula _(b2-1), n 41 _{~n 44} each independently represent an 1-3 integer. n _{31 to} n ₃₄ each independently represents an integer of 0 to 2. Further, 1 ≦ n ₄₁ + n ₃₁ ≦ 3, 1 ≦ n ₄₂ + n ₃₂ ≦ 3, 1 ≦ n ₄₃ + n ₃₃ ≦ 3, and 1 ≦ n ₄₄ + n ₃₄ ≦ 3. R < ³ > is synonymous with General formula (i), and when two or more R < ³ > exists, it may be same or different, respectively. R ⁴ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 2 to 13 carbon atoms, even the same as or different from each other if R ⁴ there are a plurality of Good. ] (B) the compound, the compositions according to 請 Motomeko 5 Ru compound der represented by the following general formula (b1-2).

[In General Formula (b1-2), R ⁵ independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. ] The composition according to claim 5 , wherein the compound (B) is at least one of compounds represented by the following general formula (b2-2) and the following general formula (b2-3).

[In General Formula (b2-2), R ⁶ independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[In General Formula (b2-3), R ⁷ independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]   The composition according to any one of claims 4 to 7, wherein the (A) resin is a novolak resin, a resole resin, a styrene resin, an acenaphthylene resin, or a resin having a fullerene skeleton.   Furthermore, the composition as described in any one of Claims 4-8 containing (C) solvent. An additive for a resist underlayer film forming material comprising a compound represented by the following general formula (i).

[In General Formula (i), each R independently represents a hydrogen atom, R ¹ or R ^3, and at least two of R are R ¹ .
R ¹ is an alkyl ester group having 2 to 13 carbon atoms, an aryl ester group having 7 to 13 carbon atoms, a hydroxymethyl group, an alkoxymethyl group having 2 to 13 carbon atoms, an aryloxymethyl group having 7 to 13 carbon atoms, or carbon When an acyloxymethyl group of 3 to ¹⁴ is shown and a plurality of R ¹ are present, they may be the same or different.
R ³ represents a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. ] The crosslinking agent which consists of a compound represented by the following general formula (i).

[In General Formula (i), each R independently represents a hydrogen atom, R ¹ or R ^3, and at least two of R are R ¹ .
R ¹ is an alkyl ester group having 2 to 13 carbon atoms, an aryl ester group having 7 to 13 carbon atoms, a hydroxymethyl group, an alkoxymethyl group having 2 to 13 carbon atoms, an aryloxymethyl group having 7 to 13 carbon atoms, or carbon When an acyloxymethyl group of 3 to ¹⁴ is shown and a plurality of R ¹ are present, they may be the same or different.
R ³ represents a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. ]   The resist underlayer film formed with the composition of any one of Claims 4-9.