JP2009014816A - Resist lower layer film forming composition and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist lower layer film forming composition capable of forming a resist lower layer film capable of transferring a resist pattern with satisfactory fidelity and reproducibility to a substrate to be processed because the composition has a film curing property, superior etching resistance, and because the pattern formed by a dry etching process is hardly bent. <P>SOLUTION: The resist lower layer film forming composition includes (A) a resin including a group represented by general formula (1) and an aromatic hydrocarbon group and (B) a solvent. In the general formula (1), n represents 0 or 1, R<SP>1</SP>represents a methylene group, or the like, which may be substituted, and R<SP>2</SP>represents a hydrogen atom or the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resist underlayer film forming composition and a pattern forming method suitable for microfabrication in a lithography process, particularly for the manufacture of highly integrated circuit elements. More specifically, a resist underlayer that has a film curability, excellent etching resistance, and is difficult to bend a pattern formed by a dry etching process, so that the resist pattern can be faithfully and reproducibly transferred to a substrate to be processed. The present invention relates to a resist underlayer film forming composition capable of forming a film and a pattern forming method.

  2. Description of the Related Art A semiconductor device manufacturing process includes many steps of depositing a plurality of substances as a film to be processed on a silicon wafer and patterning the same into a desired pattern. In patterning a film to be processed, first, a photosensitive material generally called a resist is deposited on the film to be processed to form a resist film, and a predetermined region of the resist film is exposed. Next, the exposed or unexposed portion of the resist film is removed by development processing to form a resist pattern, and the processed film is dry-etched using the resist pattern as an etching mask.

  In such a process, ultraviolet light such as an ArF excimer laser is used as an exposure light source for exposing the resist film. Currently, there is an increasing demand for miniaturization of large-scale integrated circuits (LSIs), and the required resolution may be less than the wavelength of exposure light. As described above, when the resolution is less than the wavelength of the exposure light, the exposure process tolerance such as the exposure tolerance and the focus tolerance is insufficient. In order to make up for such a shortage of exposure process tolerance, it is effective to improve the resolution by reducing the film thickness of the resist film. On the other hand, the resist film thickness required for etching the film to be processed It becomes difficult to ensure.

  For this reason, a resist underlayer film (hereinafter sometimes simply referred to as “underlayer film”) is formed on the film to be processed, the resist pattern is transferred to the underlayer film, and a pattern (hereinafter “ In some cases, the process of transferring the lower layer film pattern to the film to be processed using the lower layer film on which the lower layer film pattern is formed as an etching mask is being studied (hereinafter referred to as “lower layer film pattern”) (hereinafter referred to as “lower layer film pattern”). It may be simply referred to as “multilayer resist process”). In such a process, the lower layer film is preferably made of a material having etching resistance. For example, as a material for forming such an underlayer film, a resin containing a benzene ring that absorbs energy during etching and is known to have etching resistance, in particular, a composition containing a thermosetting phenol novolac, acenaphthylene, A composition containing a polymer having a skeleton has been proposed (see, for example, Patent Documents 1 and 2).

JP 2001-40293 A JP 2000-143937 A

  However, with further miniaturization of the etching pattern, over-etching of the resist underlayer film becomes a big problem, and further improvement in etching resistance is required. As the etching pattern is further miniaturized, the aspect ratio of the lower layer film pattern (the ratio of the pattern width (line width) to the film thickness of the lower layer film pattern) is increased, and the lower layer film pattern is changed during etching of the substrate to be processed. There was a problem of bending. For example, since the composition described in Patent Document 1 has low bending resistance as an underlayer film pattern, the underlayer film pattern is bent during etching of the substrate to be processed, and the resist pattern is faithfully transferred to the substrate to be processed. I could not.

  Furthermore, since sufficient film curability cannot be obtained, it has been necessary to bake and harden at a high temperature when forming the lower layer film. Thus, since it is necessary to bake and harden (fire) at a high temperature, there is a problem that a restriction on the process occurs. In addition, since the baking is performed at a high temperature, the resist underlayer film is easily decomposed, and the decomposition product contaminates the film forming apparatus.

  The present invention has been made to solve the above-described problems of the prior art, and can be suitably used for microfabrication in a lithography process, has film curability, excellent etching resistance, Resist underlayer film that can form a resist underlayer film that can be faithfully and reproducibly transferred to a substrate to be processed because the pattern formed by the dry etching process is difficult to bend (has good bending resistance) A forming composition and a pattern forming method are provided.

  As a result of intensive studies to solve the above problems, the present inventors have (A) a resist formed by containing a resin represented by the following general formula (1) and a resin having an aromatic hydrocarbon group. Since the hydrogen content in the lower layer film can be lowered, it has film curability and excellent etching resistance while maintaining the function as a resist lower layer film, and the pattern formed by the dry etching process is not easily bent. As a result, the present invention has been completed.

  Specifically, the present invention provides the following resist underlayer film forming composition and pattern forming method.

[1] A composition for forming a resist underlayer film comprising (A) a resin having a group represented by the following general formula (1) and an aromatic hydrocarbon group, and (B) a solvent.

（前記一般式（１）において、ｎは０または１を示す。Ｒ^１は、置換されてもよいメチレン基、炭素数２〜２０の置換されてもよいアルキレン基、または炭素数６〜２０の置換されてもよいアリーレン基を示す。Ｒ^２は、水素原子、炭素数１〜２０の置換されてもよいアルキル基、または炭素数６〜２０の置換されてもよいアリール基を示す。）

(In the general formula (1), n represents 0 or 1. R ¹ represents an optionally substituted methylene group, an alkylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms. R ² represents an optionally substituted arylene group, and R ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms.

[2] The composition for forming a resist underlayer film according to [1], wherein the (A) resin has a structural unit represented by the following general formula (2).

（前記一般式（２）において、ｎは０または１を示す。Ｒ^１は、置換されてもよいメチレン基、炭素数２〜２０の置換されてもよいアルキレン基、または炭素数６〜２０の置換されてもよいアリーレン基を示す。Ｒ^２は、水素原子、炭素数１〜２０の置換されてもよいアルキル基、または炭素数６〜２０の置換されてもよいアリール基を示す。Ｒ^３〜Ｒ^７は、水酸基、炭素数１〜６の置換されてもよいアルキル基、炭素数１〜６の置換されてもよいアルコキシ基、炭素数２〜１０の置換されてもよいアルコキシカルボニル基、炭素数６〜１４の置換されてもよいアリール基、または炭素数２〜６の置換されてもよいグリシジルエーテル基を示す。Ｒ^９は、水素原子、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルキル基、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルキルエーテル基、または炭素数６〜１０のアリール基を示す。）

(In the general formula (2), n represents 0 or 1. R ¹ is an optionally substituted methylene group, an alkylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms. R ² represents an optionally substituted arylene group, R ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms R ³ to R ⁷ represents a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, optionally substituted alkoxy group having 1 to 6 carbon atoms, optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, An aryl group having 6 to 14 carbon atoms which may be substituted, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms, R ⁹ is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, branched Or cyclic alkyl group, carbon number 1 10 straight, branched or cyclic alkyl ether group, or an aryl group having 6 to 10 carbon atoms.)

[3] Formation of resist underlayer film according to [1] or [2] above, wherein the group represented by the general formula (1) is an ethynyloxy group or a (prop-1-in-1-yl) oxy group Composition.

[4] For forming a resist underlayer film according to any one of [1] to [3], further comprising at least one selected from the group consisting of (C) an acid generator and (D) a crosslinking agent. Composition.

[5] A step (1) of forming a resist underlayer film by applying the resist underlayer film forming composition according to any one of [1] to [4] on a substrate to be processed, and the obtained resist A step (2) of forming a resist film by applying a resist composition on the lower layer film, and a step (3) of exposing the resist film by irradiating light to the obtained resist film through a photomask. ), Developing the exposed resist film to form a resist pattern (4), and using the resist film on which the resist pattern is formed as a mask, dry-etching the resist underlayer film and the substrate to be processed And (5) a step of transferring the resist pattern to the resist underlayer film and the substrate to be processed.

  The composition for forming a resist underlayer film of the present invention contains (A) a resin represented by the above general formula (1) and a resin having an aromatic hydrocarbon group, and (B) a solvent. In addition, because it has film curability, excellent etching resistance, and the pattern formed by the dry etching process is difficult to bend, it forms a resist underlayer film that can transfer the resist pattern to the substrate to be processed with high reproducibility. The effect that it can be done is produced.

  Since the pattern forming method of the present invention uses the resist underlayer film forming composition of the present invention, it has the effect of being able to faithfully transfer the resist pattern to the substrate to be processed in a dry etching process. is there.

  Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments are also within the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should be.

[1] Composition for forming a resist underlayer film:
One embodiment of the composition for forming a resist underlayer film of the present invention is (A) a resin having a group represented by the general formula (1) and an aromatic hydrocarbon group (hereinafter referred to as “(A) resin”. In some cases) and (B) a solvent. As described above, (A) the hydrogen content in the resist underlayer film to be formed can be reduced by including the resin represented by the general formula (1) and the resin having an aromatic hydrocarbon group. In addition, while maintaining the function as a resist underlayer film, it has film curability, excellent etching resistance, and the pattern formed by the dry etching process is not easily bent (it is formed in the resist underlayer film during etching of the substrate to be processed) It is possible to form a resist underlayer film in which the underlayer film pattern is not easily bent.

  Since the resist underlayer film having film curability can be formed at a low temperature, there is an advantage that the amount of sublimation is small and contamination of the apparatus can be prevented. In addition, a resist underlayer film having excellent etching resistance has precise pattern transfer performance and good etching selectivity in a dry etching process, and there is little over-etching of the resist underlayer film, and a resist pattern is formed on a substrate to be processed. Transfers faithfully and with good reproducibility. Further, if the lower layer film pattern formed on the resist lower layer film is difficult to be bent during the etching of the substrate to be processed, the yield can be improved in microfabrication in the lithography process, particularly in the manufacture of highly integrated circuit elements.

  Conventional resist underlayer film forming compositions contain a resin containing a crosslinking group such as a hydroxyl group, a methylol group, and an epoxy group in order to obtain a resist underlayer film having properties such as etching resistance. The resist underlayer film formed by such a conventional resist underlayer film forming composition has properties such as etching resistance because the cross-linking group in the resin forms a cross-linked structure. The hydrogen content in the resist underlayer film was high due to the fact that the resin contains the above-mentioned crosslinking groups (hydroxyl group, methylol group, epoxy group, etc.). Thus, when the hydrogen content rate in a resist underlayer film is high, there existed a problem that the underlayer film pattern formed in the resist underlayer film would bend.

  On the other hand, the composition for forming a resist underlayer film of the present invention contains (A) a resin represented by the above general formula (1) and a resin having an aromatic hydrocarbon group. At the time of formation, a crosslinked structure is formed by the addition reaction of the group represented by the general formula (1). Thus, by containing the group represented by the general formula (1), it is possible to form a resist underlayer film having a low hydrogen content.

[1-1] (A) Resin:
The resin (A) contained in the resist underlayer film forming composition of the present embodiment includes a group represented by the following general formula (1) (hereinafter sometimes referred to as “alkynyloxy group”), and aromatic carbonization. It has a hydrogen group.

（前記一般式（１）において、ｎは０または１を示す。Ｒ^１は、置換されてもよいメチレン基、炭素数２〜２０の置換されてもよいアルキレン基、または炭素数６〜２０の置換されてもよいアリーレン基を示す。Ｒ^２は、水素原子、炭素数１〜２０の置換されてもよいアルキル基、または炭素数６〜２０の置換されてもよいアリール基を示す。）

(In the general formula (1), n represents 0 or 1. R ¹ represents an optionally substituted methylene group, an alkylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms. R ² represents an optionally substituted arylene group, and R ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms.

  Examples of the group represented by the general formula (1) include ethynyloxy group, (prop-1-in-1-yl) oxy group, (prop-2-yn-1-yl) oxy group, and (buta-1). -In-1-yl) oxy group, (but-3-yn-1-yl) oxy group, (1-methylprop-2-yn-1-yl) oxy, (pent-1-yn-1-yl) Oxy group, (pent-4-yn-1-yl) oxy group, (hex-1-yn-1-yl) oxy group, (hex-5-in-1-yl) oxy group, (hept-1- In-1-yl) oxy group, (hept-6-in-1-yl) oxy group, (oct-1-in-1-yl) oxy group, (oct-7-in-1-yl) oxy group , (Non-1-yn-1-yl) oxy group, (non-8-in-1-yl) oxy group, (deca 1-yn-1-yl) oxy group, (dec-9-yl) oxy group,

  (Undec-1-in-1-yl) oxy group, (undec-10-in-1-yl) oxy group, (dodec-1-in-1-yl) oxy group, (dodec-11-in-1) -Yl) oxy group, (tridec-1-in-1-yl) oxy group, (tridec-12-in-1-yl) oxy group, (tetradec-1-in-1-yl) oxy group, (tetradeca) -13-in-1-yl) oxy group, (pentadec-1-in-1-yl) oxy group, (pentadec-14-in-1-yl) oxy group, (hexadec-1-in-1-yl) Alkynyloxy groups such as) oxy group, (hexadec-15-in-1-yl) oxy group, (heptadec-1-in-1-yl) oxy group, and (heptadec-16-in-1-yl) oxy group And so on. Among these, an ethynyloxy group, a (prop-1-yn-1-yl) oxy group, and a (prop-2-yn-1-yl) oxy group are preferable.

  The resin having the group represented by the general formula (1) and the aromatic hydrocarbon group can be obtained by, for example, two kinds of methods (method 1 and method 2) shown in FIG.

  In Method 1, an aromatic hydrocarbon having a hydroxy group (hereinafter simply referred to as “aromatic hydrocarbon”) is polycondensed with a condensing agent (for example, aldehydes, ketones, divinyl compounds, etc.), A method of reacting the obtained resin having a hydroxy group with a compound having a group represented by the general formula (1) (hereinafter sometimes referred to as “alkynylating agent”) to alkynyloxylate It is.

  Aromatic hydrocarbons include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcin, pyrogallol, bisphenol, bisphenol-A, trisphenol, o-ethylphenol M-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-phenylph Nord, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol 5-methylresorcinol, catechol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, Phenols such as 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol;

  1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol and 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3- Examples include naphthols such as dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and binaphthol; hydroxyanthracene, hydroxypyrene, and the like. In addition, these can be used individually by 1 type or in mixture of 2 or more types.

  Among these, naphthols such as 1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol and 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene are preferable.

  Examples of aldehydes used as a condensing agent include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, phenylacetaldehyde, α-phenylpropyl aldehyde, β-phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural Etc.

  Examples of ketones used as the condensing agent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of divinyl compounds used as the condensing agent include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborn-2-ene, α-pinene, β-pinene, limonene, and 5-vinyl. And norbornadiene.

  Among these condensing agents, formaldehyde and furfural are preferable.

  When using an aldehyde as a condensing agent, it is preferable that the usage-amount of aldehyde is 1-1000 mass parts with respect to 100 mass parts of aromatic hydrocarbons, and is 10-100 mass parts. Is more preferable.

  The polycondensation reaction between the aromatic hydrocarbon and the condensing agent can be performed under an acidic catalyst. Examples of the acidic catalyst include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid; and carboxylic acids such as formic acid and oxalic acid. Although the usage-amount of an acidic catalyst can be suitably selected according to the kind of acid to be used, it is preferable that it is 0.001-100 mass parts with respect to 100 mass parts of aromatic hydrocarbons, 0.01-10 More preferably, it is part by mass. The reaction temperature during the polycondensation reaction is preferably 20 to 200 ° C. The reaction time can be appropriately selected depending on the reaction temperature, but is preferably 20 minutes to 72 hours.

  Specifically as an alkynylating agent, the compound shown by following General formula (3) can be mentioned.

（前記一般式（３）において、ｎは０または１を示す。ｎ＝１の場合、Ｒ^１は、置換されてもよいメチレン基、炭素数２〜２０の置換されてもよいアルキレン基、炭素数６〜２０の置換されてもよいアリール基を示す。Ｒ^２は、水素原子、炭素数１〜２０置換されてもよいアルキル基、炭素数６〜２０置換されてもよいアリール基を示す。Ｘは脱離基を示す。）

(In the general formula (3), n represents 0 or 1. When n = 1, R ¹ represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, carbon. R ² represents an optionally substituted aryl group having 6 to 20. R ² represents a hydrogen atom, an alkyl group that may be substituted with 1 to 20 carbon atoms, or an aryl group that may be substituted with 6 to 20 carbon atoms. X represents a leaving group.)

  Specific examples of X that is a leaving group include a chloro group, a bromo group, a tosyl group, a mesyl group, and a trifluoromethylsulfonyl group.

  For the alkynyloxylation reaction, a general synthesis method (for example, JP 2003-533502 A) can be appropriately selected. Specifically, there is a method in which a resin having a hydroxy group, an aromatic hydrocarbon, and an alkynylating agent are dissolved in a solvent such as tetrahydrofuran and reacted under a base catalyst.

  Examples of the base catalyst include amines, metal hydroxides, metal carbonates, and metal alkoxides. Among these, amines are preferable, and examples of the amines include triethylamine, N, N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine, N-methyl-morpholine, and the like.

  The polystyrene-converted weight average molecular weight (Mw) of the resin having a hydroxyl group obtained as described above, as measured by gel permeation chromatography, is preferably 1,000 to 15,000, and preferably 1,500 to 10,000. More preferably, it is 000.

  In Method 2, an aromatic hydrocarbon and an alkynylating agent are reacted to obtain an aromatic hydrocarbon having an alkynyloxy group (hereinafter referred to as “alkynyloxylated aromatic hydrocarbon”), and the obtained alkynyloxylation is obtained. This is a method of polycondensing aromatic hydrocarbons.

  As the aromatic hydrocarbon and alkynylating agent used in this method, the same aromatic hydrocarbon and alkynylating agent as used in Method 1 can be used. The polycondensation reaction of the alkynyloxylated aromatic hydrocarbon can be the same as the polycondensation reaction of Method 1.

  The resin (A) contained in the resist underlayer film forming composition of the present embodiment preferably has a structural unit represented by the following general formula (2). Thus, by having the structural unit represented by the general formula (2), there is an advantage that the hydrogen content in the resist underlayer film to be formed can be further reduced. A compound having a naphthalene skeleton for constituting the structural unit represented by the general formula (2) is easily available.

  The resin (A) contained in the resist underlayer film forming composition of the present embodiment is a structural unit containing a benzene skeleton instead of the naphthalene skeleton in the structural unit represented by the general formula (2), or It may have a structural unit containing an anthracene skeleton. (A) When the resin has a structural unit containing an anthracene skeleton, there is an advantage that the hydrogen content can be further reduced.

  Examples of the substituent of the benzene skeleton and the anthracene skeleton include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may be substituted, an alkoxy group having 1 to 6 carbon atoms which may be substituted, and a substituent having 2 to 10 carbon atoms. An alkoxycarbonyl group, an aryl group having 6 to 14 carbon atoms which may be substituted, or a glycidyl ether group having 2 to 6 carbon atoms which may be substituted, and may contain one or more of these substituents, One or more can be included.

  The resin (A) is selected from the group consisting of a structural unit represented by the general formula (2) (a structural unit containing a naphthalene skeleton), a structural unit containing a benzene skeleton, and a structural unit containing an anthracene skeleton. It may have at least one kind.

（前記一般式（２）において、ｎは０または１を示す。Ｒ^１は、置換されてもよいメチレン基、炭素数２〜２０の置換されてもよいアルキレン基、または炭素数６〜２０の置換されてもよいアリーレン基を示す。Ｒ^２は、水素原子、炭素数１〜２０の置換されてもよいアルキル基、または炭素数６〜２０の置換されてもよいアリール基を示す。Ｒ^３〜Ｒ^７は、水酸基、炭素数１〜６の置換されてもよいアルキル基、炭素数１〜６の置換されてもよいアルコキシ基、炭素数２〜１０の置換されてもよいアルコキシカルボニル基、炭素数６〜１４の置換されてもよいアリール基、または炭素数２〜６の置換されてもよいグリシジルエーテル基を示す。Ｒ^９は、水素原子、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルキル基、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルキルエーテル基、または炭素数６〜１０のアリール基を示す。）

(In the general formula (2), n represents 0 or 1. R ¹ is an optionally substituted methylene group, an alkylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms. R ² represents an optionally substituted arylene group, R ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms R ³ to R ⁷ represents a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, optionally substituted alkoxy group having 1 to 6 carbon atoms, optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, An aryl group having 6 to 14 carbon atoms which may be substituted, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms, R ⁹ is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, branched Or cyclic alkyl group, carbon number 1 10 straight, branched or cyclic alkyl ether group, or an aryl group having 6 to 10 carbon atoms.)

In addition, in the naphthalene skeleton of the general formula (2), the group represented by the general formula (1) and the substitution positions of R ^{3 to} R ⁷ can be any positions.

  Specific examples of the structural unit represented by the general formula (2) include compounds represented by the following general formulas (4) to (12).

[1-2] (B) Solvent:
The (B) solvent contained in the resist underlayer film forming composition of the present embodiment can dissolve (A) the resin. By containing such a solvent (B), the coatability is improved, so that the resist underlayer film can be easily formed.

  (B) Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate Ethylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether Diethylene glycol di-n-butyl ether, etc. Ethylene glycol dialkyl ethers; triethylene glycol dimethyl ether, triethylene glycol dialkyl ethers such as triethylene glycol diethyl ether;

  Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n Propylene glycol dialkyl ethers such as propyl ether and propylene glycol di-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol such as Roh alkyl ether acetates;

  Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, n-butyl lactate, i-butyl lactate; methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-formate Butyl, i-butyl formate, n-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i -Amyl, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate Aliphatic carboxylic acid esters such as i-propyl butyrate, n-butyl butyrate and i-butyl butyrate;

  Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3 -Other esters such as methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; methyl ethyl ketone, methyl-n-propyl ketone, methyl- n-butyl ketone, 2 Ketones such as heptanone, 3-heptanone, 4-heptanone, cyclohexanone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; γ -Lactones such as butyrolactone can be mentioned.

  Among these, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethyl lactate, n-butyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, and γ-butyrolactone are preferable. In addition, (B) solvent can be used individually or in mixture of 2 or more types.

  (B) Although the usage-amount of a solvent does not have a restriction | limiting in particular, For example, it is preferable that it is the quantity from which the solid content concentration of the composition for resist underlayer film formation of this embodiment will be 5-30 mass%, 5-15 It is more preferable that the amount is mass%. When the solid content concentration of the resist underlayer film forming composition is 5 to 30% by mass, the resist underlayer film forming composition can be applied more satisfactorily on the substrate to be processed.

  The resist underlayer film forming composition of the present embodiment is at least selected from the group consisting of (C) an acid generator and (D) a crosslinking agent in addition to (A) the resin and (B) the solvent. It is preferable to contain one.

[1-3] (C) Acid generator:
(C) The acid generator is a component that generates an acid upon exposure or heating. By including such (C) acid generator, the poisoning problem can be solved. That is, a substance that inhibits the chemical reaction of the resist (for example, a base such as OH—, CH ₃ —, and NH ₂ —) may be generated from the substrate (in particular, the low dielectric film). When this substance (inhibiting substance) diffuses into the resist, the acid in the resist is deactivated, and there is a problem that the pattern shape is footed in the positive resist (poisoning problem). In order to prevent this problem, the (C) acid generator contained in the resist underlayer film reacts with the inhibitor to prevent the inhibitor from diffusing into the resist. Can do.

  Examples of the acid generator that generates an acid upon exposure (hereinafter referred to as “photoacid generator”) include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrenesulfonate, and diphenyliodonium n. -Dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalenesulfonate, diphenyliodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro N-butanesulfonate, bis (4-tert-butylphenyl) iodonium n-dodecylbenzenesulfonate Bis (4-tert-butylphenyl) iodonium 10-camphorsulfonate, bis (4-tert-butylphenyl) iodonium naphthalenesulfonate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate , Triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium hexafluoroantimonate, 4-hydroxyphenyl phenyl Methylsulfonium p-toluenesulfonate, 4-hydroxyphenyl benzyl methyls Honiumu p- toluenesulfonate,

  Cyclohexylmethyl 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldicyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoro Lome Sulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethyl Sulfonium trifluoromethanesulfonate,

  1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalene-1- Yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane Sulfonate, 1- [4- (1-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-methoxyethoxy) naphthalene 1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothio Phenium trifluoromethanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,

  1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1 -(4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1 -[4- (2-tetrahydropyranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-benzyloxy) tetrahydrothiophenium trifluoro Tan sulfonate, 1- (naphthyl acetamide methyl) onium salt photoacid generators such as tetrahydrothiophenium trifluoromethanesulfonate;

  Halogen-containing compound-based photoacid generators such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine; 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,3,4-naphthoquinonediazide-4-sulfonic acid ester of 2,3,4,4′-tetrahydroxybenzophenone or 1, Diazoketone compound photoacid generators such as 2-naphthoquinonediazide-5-sulfonic acid ester; sulfone compound photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane Benzoin tosylate, pyrogallol Tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide Examples include sulfonic acid compound photoacid generators such as trifluoromethanesulfonate and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

  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-butylpheny ) Iodonium naphthalene sulfonate is preferred. In addition, these photo-acid generators can be used individually or in mixture of 2 or more types.

  Examples of the acid generator that generates an acid upon 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. These thermal acid generators can be used alone or in admixture of two or more. Note that (C) a photoacid generator and a thermal acid generator may be used in combination as the acid generator.

  (C) The amount of the acid generator used is preferably 100 parts by mass or less, more preferably 0.1 to 30 parts by mass, and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of (A) resin. 10 parts by mass is particularly preferred. If the amount used is less than 0.1 parts by mass, the poisoning problem may not be sufficiently solved. On the other hand, if it exceeds 30 parts by mass, the bottom of the lower layer film pattern may be lost and the lower layer film pattern may easily fall over (be easily bent).

[1-4] (D) Crosslinking agent:
(D) By including a crosslinking agent, the resist underlayer film can be cured at a low temperature. (D) As a crosslinking agent, polynuclear phenols and a hardening | curing agent can be used, for example.

  Examples of polynuclear phenols include dinuclear phenols such as 4,4′-biphenyldiol, 4,4′-methylene bisphenol, 4,4′-ethylidene bisphenol, and bisphenol A; 4,4 ′, 4 ″ -methyl Trinuclear phenols such as reddentrisphenol, 4,4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol; polyphenols such as novolac Among these, 4,4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol and novolak are preferable. A kind can be used individually or in mixture of 2 or more types.

  Examples of the curing agent include 2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 3,4-tolylene diisocyanate, 3,5-tolylene diisocyanate, and 4,4′-diphenylmethane diester. Diisocyanates such as isocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, etc., and commercially available products with the following trade names: Epicoat 812, 815, 826, 828, 834, 836, 871, 1001, 1004, 1007, 1009, 1031 (Oilized Shell Epoxy), Araldite 6600, 6700, 6800, 502, 6071, 6084, 6097, 6099 (above, manufactured by Ciba Geigy), DER331, 332, 333, 661, 644, 667 (above, manufactured by Dow Chemical Co., Ltd.); Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Melamine-based curing agents such as 701, 272, 202, My Coat 506, 508 (Mitsui Chemicals Aqua Polymer (former Mitsui Cyanamid)); Cymel 1123, 1123-10, 1128, My Coat 102, 105, 106, 130 (above, Mitsui Chemicals Aqua Polymer (former Mitsui Cyanamid)) and other benzoguanamine-based curing agents; Cymel 1170, 1172 (above, Mitsui Chemicals Aqua Polymer (former Mitsui Cyanamid)) Manufactured), Nicarak N-2702 (manufactured by Sanwa Chemical Co., Ltd.) It can gel. Among these, melamine type curing agents and glycoluril type curing agents are preferred. In addition, these hardening | curing agents can be used individually or in mixture of 2 or more types. Moreover, (D) polynuclear phenols and a hardening | curing agent can also be used together as a crosslinking agent.

  (D) It is preferable that the usage-amount of a crosslinking agent is 100 mass parts or less with respect to 100 mass parts of (A) resin, It is still more preferable that it is 1-20 mass parts, It is 1-10 mass parts. It is particularly preferred. When the amount used is 100 parts by mass or less, the performance of the resist underlayer film can be maintained satisfactorily.

[1-5] Other additives:
The composition for forming a resist underlayer film of the present embodiment contains various additives such as a thermosetting resin, a radiation absorber, and a surfactant, as necessary, as long as the desired effect in the present invention is not impaired. May be.

  Various thermosetting resins can be used as the thermosetting resin. The thermosetting resin is a component that has an action of preventing intermixing between the resist underlayer film obtained and the resist film formed thereon, which is cured by heating and becomes insoluble in a solvent. Examples of such thermosetting resins include acrylic resins (thermosetting acrylic resins), phenol resins, urea resins, melamine resins, amino resins, aromatic hydrocarbon resins, epoxy Examples thereof include resins and alkyd resins. Among these, urea resins, melamine resins, and aromatic hydrocarbon resins are preferable.

  It is preferable that the usage-amount of a thermosetting resin is 10 mass parts or less with respect to 100 mass parts of (A) resin, and it is still more preferable that it is 1-5 mass parts.

  Examples of the radiation absorber include oil-soluble dyes, disperse dyes, basic dyes, methine dyes, pyrazole dyes, imidazole dyes, hydroxyazo dyes, and the like; bixin derivatives, norbixine, stilbene, 4,4 Fluorescent brighteners such as' -diaminostilbene derivatives, coumarin derivatives, pyrazoline derivatives; hydroxyazo dyes, commercially available products such as “Tinuvin 234” and “Tinuvin 1130” (above, manufactured by Ciba Geigy) Agents; aromatic compounds such as anthracene derivatives and anthraquinone derivatives can be exemplified. In addition, these radiation absorbers can be used individually or in mixture of 2 or more types.

  The amount of the radiation absorber used is preferably 50 parts by mass or less, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin (A).

  The surfactant is a component having an action of improving coating properties, striation, wettability, developability and the like. Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, and polyethylene. Nonionic surfactants such as glycol dilaurate and polyethylene glycol distearate, and commercially available products are all trade names below: KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Ftop EF101, EF204, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F172, F173 (above, Dainippon Ink and Chemicals, Inc.) Manufactured by Kogyo Co., Ltd.), Florard FC430, FC431, FC135, FC93 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 ( As mentioned above, Asahi Glass Co., Ltd.) can be mentioned. In addition, these surfactant can be used individually or in mixture of 2 or more types.

  The amount of the surfactant used is preferably 15 parts by mass or less, and more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the (A) resin.

  Furthermore, the resist underlayer film forming composition of the present embodiment contains other additives such as a storage stabilizer, an antifoaming agent, and an adhesion aid in addition to the radiation absorber and the surfactant described above. You can also.

[1-6] Preparation of resist underlayer film forming composition:
In the resist underlayer film forming composition of the present embodiment, for example, (A) resin, (B) solvent, and “other additives” as necessary are mixed, and the total solid content concentration is 5 to 30. It can be prepared by obtaining a uniform mixed solution of mass% (preferably 5 to 15 mass%) and filtering the obtained mixed solution with a filter having a pore size of about 0.1 μm.

[2] Pattern formation method:
Next, an embodiment of the pattern forming method of the present invention will be described. The pattern forming method of the present embodiment includes a step (1) of applying the above-described composition for forming a resist underlayer film of the present invention on a substrate to be processed to form a resist underlayer film, and on the obtained resist underlayer film. , A step (2) of forming a resist film by applying a resist composition, a step (3) of exposing the resist film by irradiating the obtained resist film with light through a photomask, and an exposed resist Step (4) of developing the film to form a resist pattern, and using the resist film on which the resist pattern is formed as a mask (etching mask), the resist underlayer film and the substrate to be processed are dry-etched to form the resist underlayer film and the workpiece And (5) a step of transferring a resist pattern to the substrate.

  As described above, since the resist underlayer film forming composition of the present invention is used, the resist pattern can be faithfully transferred with high reproducibility to the substrate to be processed in the dry etching process. Hereinafter, each process in the pattern formation method of this embodiment is demonstrated.

[2-1] Step (1):
Step (1) of the pattern forming method of the present embodiment is a step of forming the resist underlayer film by applying the resist underlayer film forming composition of the present invention described above on the substrate to be processed. Through these steps, a “substrate with a resist underlayer film” in which a resist underlayer film is formed on a substrate to be processed can be obtained.

  Since the resist underlayer film forming composition contains a resin having an alkynyloxy group and an aromatic hydrocarbon group, a resist underlayer film having a low hydrogen content is formed when the resist underlayer film in this step is formed. be able to. For this reason, the resist underlayer film has film curability, excellent etching resistance, and the underlayer film pattern at the time of etching the substrate to be processed is not easily bent.

  As the substrate to be processed, for example, an inorganic film made of silicon oxide, silicon nitride, silicon oxynitride, polysiloxane, or the like can be used. In addition, as commercial products, all of the following trade names are used for interlayers such as wafers covered with a low dielectric insulating film such as black diamond (manufactured by AMAT), silk (manufactured by Dow Chemical), or LKD5109 (manufactured by JSR). An insulating film (substrate to be processed) can be used. Note that a substrate on which a pattern such as a wiring course (trench), a plug groove (via), or the like is formed in advance can be used as the substrate to be processed.

  There is no restriction | limiting in particular about the method of apply | coating the composition for resist underlayer film formation on a to-be-processed substrate, For example, a spin coat method etc. can be mentioned. Since the resist underlayer film forming composition can fill the groove of the substrate to be processed, when the substrate to be processed is processed by dry etching using the resist underlayer film as a mask, the sidewall of the substrate to be processed (groove) The side wall portion) can be protected from the plasma gas. Therefore, when the predetermined pattern is patterned on the substrate to be processed in the step (5), the predetermined pattern can be formed without damaging the groove side wall portion of the substrate to be processed.

  The resist underlayer film forming composition can be applied on a substrate to be processed, and the formed coating film can be cured by exposure and / or heating to form a resist underlayer film. For example, when (C) an acid generator is contained in the composition for forming a resist underlayer film, the light used for exposure is visible light, ultraviolet light, far ultraviolet light, X, depending on the type of (C) acid generator. It can be appropriately selected from a beam, electron beam, γ-ray, molecular beam, ion beam, and the like.

  Moreover, the temperature at the time of heating a coating film is although it does not specifically limit, It is preferable that it is 90-450 degreeC, It is more preferable that it is 90-350 degreeC, It is 90-250 degreeC. Particularly preferred.

  Although there is no restriction | limiting in particular about the film thickness of a resist underlayer film, It is preferable that it is 100-1000 nm, and it is still more preferable that it is 200-500 nm.

  Moreover, the pattern formation method of this embodiment may further include a step (1a) of forming an intermediate layer on the resist underlayer film as necessary after this step (1). This intermediate layer supplements the functions of the resist underlayer film and / or the resist film in the resist pattern formation process, obtains a function that they do not have, or a predetermined predetermined number required for both of these purposes. It is a layer that has been given a function. For example, when an antireflection film is formed as the intermediate layer, the antireflection function of the resist underlayer film can be further supplemented by the intermediate layer.

  The intermediate layer can be formed using an organic compound or an inorganic oxide. Examples of the organic compound include commercially available materials such as “DUV-42”, “DUV-44”, “ARC-28”, and “ARC-29” manufactured by Brewer Science. Alternatively, materials commercially available under trade names such as “AR-3” and “AR-19” manufactured by Rohm and Haas can be used. Examples of the inorganic oxide include materials commercially available under trade names such as “NFC SOG01” and “NFC SOG04” manufactured by JSR, polysiloxane formed by a CVD method, titanium oxide, alumina oxide, Tungsten oxide or the like can be used.

  The method for forming the intermediate layer is not particularly limited, and examples thereof include a coating method and a CVD method. Among these, a coating method is preferable. This is because when the coating method is used, the intermediate layer can be formed continuously after the resist underlayer film is formed.

  The thickness of the intermediate layer is not particularly limited and can be appropriately selected according to the function required for the intermediate layer. For example, in a general lithography process, the thickness is preferably 10 to 3000 nm. More preferably, it is 300 nm. If the thickness of the intermediate layer is less than 10 nm, the intermediate layer may not be removed during the etching of the resist underlayer film. On the other hand, if it exceeds 3000 nm, there is a possibility that the processing conversion difference becomes large when the pattern formed on the resist film is transferred to the intermediate layer.

[2-2] Step (2):
Step (2) is a step of forming a resist film by applying a resist composition on the resist underlayer film obtained in step (1). As described above, when an intermediate layer is further formed on the resist underlayer film, a resist film is formed on the intermediate layer.

  Examples of the resist composition used in the step (2) include a positive or negative chemically amplified resist composition containing a photoacid generator, and a positive resist composition comprising an alkali-soluble resin and a quinonediazide photosensitizer. Preferable examples include a negative resist composition comprising a product, an alkali-soluble resin and a crosslinking agent, a silicon-containing resist containing silicon atoms as a main component, and the like.

  The solid content concentration of the resist composition is not particularly limited, but is preferably 5 to 50% by mass, for example. In addition, a resist composition that has been filtered using a filter having a pore diameter of about 0.2 μm can be suitably used. In the pattern forming method of the present invention, a commercially available resist composition can be used as it is as the resist composition.

  There is no restriction | limiting in particular in the method of apply | coating a resist composition, For example, conventional methods, such as a spin coat method, can be mentioned. In addition, when apply | coating a resist composition, it is preferable to adjust the quantity of the resist composition to apply | coat so that the resist film obtained may become a predetermined film thickness.

  After forming a coating film by applying the resist composition, the coating film is pre-baked to volatilize the solvent in the coating film (that is, the solvent contained in the resist composition) to form a resist coating film. can do. Although the temperature at the time of prebaking can be suitably selected according to the kind etc. of resist composition to be used, it is preferable that it is 30-200 degreeC, and it is still more preferable that it is 50-150 degreeC.

[2-3] Step (3):
Step (3) is a step of exposing the resist film by irradiating the resist film obtained in step (2) with light through a photomask. The light used in this step is appropriately selected according to the type of acid generator used in the resist composition. For example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ-rays, molecules A line, an ion beam, etc. can be mentioned. Among these, far ultraviolet rays are preferable, 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 ( Preferred examples include wavelength 134 nm), extreme ultraviolet light (wavelength 13 nm, etc.), and the like. The exposure method is not particularly limited, and can be performed in accordance with a method performed in a conventionally known pattern forming method.

[2-4] Step (4):
Step (4) is a step of developing the exposed resist film to form a resist pattern. The developer used for development can be appropriately selected according to the type of resist composition used. In the case of using a positive chemically amplified resist composition or a positive resist composition containing an alkali-soluble resin, examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, and sodium metasilicate. , Ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, 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 can be used. These alkaline aqueous solutions may be those obtained by adding an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant.

  Further, when using a negative chemically amplified resist composition or a negative resist composition containing an alkali-soluble resin, examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, Inorganic alkalis such as sodium silicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethyl Alcohol amines such as ethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and alkaline aqueous solutions such as cyclic amines such as pyrrole and piperidine should be used. Can do.

  In this step (4), in order to improve resolution, pattern profile, developability, etc., the exposed resist film is post-baked before development (that is, after exposure in step (3)). It is preferable. The post-baking temperature can be appropriately selected according to the type of resist composition used, but is preferably 50 to 200 ° C, and more preferably 80 to 150 ° C.

[2-5] Step (5):
In step (5), the resist underlayer film and the substrate to be processed are sequentially dry-etched using the resist film on which the resist pattern is formed as a mask (etching mask), and the resist pattern is sequentially transferred to the resist underlayer film and the substrate to be processed. It is a process to do. When the intermediate layer is formed on the resist underlayer film, the intermediate layer is also dry etched together with the resist underlayer film and the substrate to be processed.

Dry etching can be performed using a known dry etching apparatus. As a source gas at the time of dry etching, although it depends on the elemental composition of the film to be etched (resist underlayer film, substrate to be processed, intermediate layer), a gas containing oxygen atoms such as O ₂ , CO, and CO ₂ , He An inert gas such as N ₂ , Ar, a chlorine-based gas such as Cl ₂ or BCl ₄ , a gas such as H ₂ or NH ₄ , or the like can be used. In addition, these gases can also be mixed and used.

  FIG. 2 shows dry etching using a substrate 1, a low dielectric insulating film (substrate to be processed) 2 formed on the substrate 1, and a resist film formed on the low dielectric insulating film 2 and having a resist pattern as a mask. It is sectional drawing which shows the resist lower layer film 3 to which the resist pattern was transcribe | transferred by. A resist film on which a resist pattern is formed is disposed on the resist underlayer film 3 but is not shown.

  FIG. 3 shows a substrate 1, a low dielectric insulating film (substrate to be processed) 2 formed on the substrate 1 and formed with a resist pattern, and a resist formed on the low dielectric insulating film 2 and formed with a resist pattern. It is sectional drawing which shows the resist underlayer film 3 as a film. 3 is a cross-sectional view showing a state after the resist pattern is transferred to the low dielectric insulating film 2 by dry etching using the resist underlayer film 3 of FIG. 2 as a mask. A resist film on which a resist pattern is formed is disposed on the resist underlayer film 3 but is not shown. The resist underlayer film 3 formed by the resist underlayer film forming composition of the present embodiment is excellent in etching resistance, so that there is little overetching by dry etching, the underlayer film pattern is hardly bent, and has film curability. .

  In addition, by repeating the steps (1) to (5) described so far, a multilayer substrate to be processed (dual damascene) on which a predetermined pattern such as a wiring course (trench) or a plug groove (via) is formed. The substrate to be processed on which the structure is formed can be obtained satisfactorily.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. “Parts” in Examples and Comparative Examples are based on mass unless otherwise specified. The introduction rate of the alkynyloxy group in the synthesis examples was measured by the following method.

<Measurement of introduction rate of alkynyloxy group>
The introduction rate (mol%) of the alkynyloxy group (group represented by the general formula (1)) in the resins (A-1) to (A-11) is ¹³ C-NMR (500 MHz-NMR: manufactured by JEOL Ltd., ECP-500, heavy solvent: CDCl ₃₎ was used for the measurement.

(Synthesis Example 1)
Synthesis of Resin (A-1):
In a separable flask equipped with a thermometer, 10 parts of 1-naphthol / formaldehyde condensate (resin having a hydroxy group), propargyl bromide (compound having a group represented by the general formula (1) (alkynylating agent)) 10 Parts, 10 parts of triethylamine, and 40 parts of tetrahydrofuran were added and reacted at 50 ° C. for 12 hours while stirring. After completion of the reaction, the reaction solution was cooled to 30 ° C. or lower by water cooling. After cooling, this polymerization solution was put into a large amount of n-heptane. Thereafter, the precipitated solid was separated by a decantation method and washed with a large amount of n-heptane. Subsequently, the solid was dissolved in methyl isobutyl ketone and washed with 1% by mass of oxalic acid and pure water to remove the remaining triethylamine. Thereafter, the organic layer was dried at 50 ° C. for 17 hours to obtain a resin (A-1). In addition, the introduction rate of the alkynyloxy group in the resin (A-1) was 90 mol%.

(Synthesis Examples 2 to 11)
Synthesis of Resins (A-2) to (A-11):
Resins (A-2) to (A-11) were synthesized in the same manner as in Synthesis Example 1 except that the resin having a hydroxy group shown in Table 1 was used. In addition, Table 1 shows the introduction rate of the alkynyloxy group in the resins (A-2) to (A-11).

Example 1
10 parts of the resin (A-1) obtained in Synthesis Example 1 was dissolved in 90 parts of propylene glycol monomethyl acetate ((B) solvent) to obtain a mixed solution. Thereafter, this mixed solution was filtered through a membrane filter having a pore diameter of 0.1 μm to prepare a resist underlayer film forming composition (U-1).

  A resist underlayer film is formed from the prepared resist underlayer film forming composition (U-1), and for this resist underlayer film, the elemental composition (hydrogen content) of the resist underlayer film is measured and the film is cured by the following method. Evaluation of property, etching resistance, and bending resistance were performed.

<Elemental composition of resist underlayer film>
The prepared resist underlayer film forming composition (U-1) was applied to a silicon wafer (substrate to be processed) by a spin coating method. Thereafter, baking is performed (baked) at 250 ° C./60 seconds in an air atmosphere to form a resist underlayer film having a thickness of 300 nm, and the resist underlayer film is formed on the substrate to be processed. Obtained substrate ". In the obtained substrate with resist underlayer film, the resist underlayer film was peeled off from the silicon wafer, and then the hydrogen content (% by mass) of the resist underlayer film was measured. This measurement was performed using an organic element analyzer (trade name “CHN Coder JM10”) manufactured by J-Science.

<Film curability>
In the same manner as in the above <Element composition of resist underlayer film>, a “substrate with a resist underlayer film” was obtained. In the obtained substrate with a resist underlayer film, the resist underlayer film was peeled off from the silicon wafer. Thereafter, this resist underlayer film (film thickness 300 nm) was immersed in propyl glycol monomethyl ether acetate (room temperature) for 1 minute. The film thickness before and after immersion was measured using a spectroscopic ellipsometer UV1280E (manufactured by KLA-TENCOR), and the film thickness change rate was calculated from the measured value and evaluated. The evaluation criterion was “◯” when the film thickness change rate was 0%. The case where the film thickness change rate exceeded 0% was defined as “x”.

<Etching resistance>
In the same manner as in the above <Element composition of resist underlayer film>, a “substrate with a resist underlayer film” was obtained. CF ₄ / Ar / O ₂ (CF ₄ : 40 mL) of the resist underlayer film (film thickness 300 nm) of the obtained substrate with a resist underlayer film was used using an etching apparatus (manufactured by Shinko Seiki Co., Ltd., trade name “EXAM”). / Min, Ar: 20 mL / min, O ₂ : 5 mL / min; pressure: 20 Pa; RF power: 200 W; treatment time: 40 seconds; temperature: 15 ° C.), and the resist underlayer film before and after the etching treatment The thickness was measured, the etching rate was calculated, and the etching resistance was evaluated. The etching rate was calculated by forming a resist underlayer film from a composition for forming a resist underlayer film (trade name “NFC CT08”) manufactured by JSR, and using this resist underlayer film as a reference resist underlayer film. The evaluation criteria are “◎” when the etching rate is less than −10%, “◯” when the etching rate is less than −10%, less than 0%, and “×” when the etching rate is 0% or more. "

<Bending resistance>
A TEOS substrate was used as a substrate to be processed, and a resist underlayer film having a thickness of 500 nm was formed on the TEOS substrate to obtain a “substrate with a resist underlayer film”. On the resist underlayer film (film thickness 500 nm) of the obtained “substrate with resist underlayer film”, a three-layer resist process intermediate layer solution (trade name “NFC SOG080” manufactured by JSR Corporation) is spin-coated, and 200 The mixture was heated at 60 ° C. for 60 seconds, and further heated on a hot plate at 300 ° C. for 60 seconds to form an intermediate layer having a thickness of 50 nm. Next, an ArF resist composition solution obtained by preparing an ArF resist composition (trade name “AR1682J”, manufactured by JSR Corporation) is spin-coated on this intermediate layer, and then heated on a 130 ° C. hot plate. A 200-nm-thick photoresist film (resist film) was formed by pre-baking for 90 seconds.

  Then, it exposed for only the optimal exposure time through the photomask using the ArF excimer laser exposure apparatus (lens numerical aperture 0.78, exposure wavelength 193nm) by Nikon (NIKON). After the exposure, the film was post-baked for 90 seconds on a 130 ° C. hot plate, and then developed at 25 ° C. for 1 minute using a 2.38 mass% aqueous tetramethylammonium hydroxide solution. After development, it was washed with water and dried to obtain a resist film on which a positive resist pattern for ArF was formed.

Using the obtained resist film as a mask, the pattern of the resist film was transferred to the intermediate layer using a dry etching method to form a pattern (intermediate layer pattern) on the intermediate layer. Using this intermediate layer as a mask, the pattern of the intermediate layer was transferred to the resist underlayer film using a dry etching method to form a pattern (resist underlayer film pattern) on the resist underlayer film. Further, using this resist underlayer film as a mask, a pattern having a depth of 300 nm was formed on a TEOS substrate (substrate to be processed) with CF ₄ / Ar / O ₂ .

  After forming the pattern on the TEOS substrate, the shape of the resist underlayer film pattern is observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Tech Co., Ltd.), and the degree of bending of the resist underlayer film on which the pattern is formed (bending resistance) Evaluated. The evaluation criteria were “◯” when no bending was observed in the shape of the resist underlayer film pattern, and “X” when bending was observed in the shape of the resist underlayer film pattern.

  The resist underlayer film formed by the resist underlayer film forming composition of this example has an element composition (hydrogen content) of the resist underlayer film of 31% by mass, a film curability of “◯”, and an etching resistance. Was “◯” and the bending resistance was “◯”.

(Examples 2 to 15)
Resist underlayer film forming compositions (U-2) to (U-11) were prepared in the same manner as in Example 1 except that the formulation shown in Table 2 was used. In Table 2, (C) acid generator indicates bis (4-t-butylphenyl) iodonium-camphorsulfonate (trade name “BBI-109” manufactured by Midori Chemical Co., Ltd.), and (D) crosslinker is And tetramethoxymethyl glycoluril.

  Using the prepared resist underlayer film forming compositions (U-2) to (U-11), a “substrate with resist underlayer film” was obtained in the same manner as in Example 1, and the obtained “substrate with resist underlayer film” As for the resist underlayer, the element composition (hydrogen content) of the resist underlayer film, the film curability evaluation, the etching resistance evaluation, and the bending resistance evaluation were performed. The evaluation results are shown in Table 3.

(Comparative Examples 1-8)
Resist underlayer film forming composition in the same manner as in Example 1 except that the resins having a hydroxy group (UA-1) to (UA-5) shown in Table 4 were used, respectively, and the formulation was shown in Table 5. Products (UC-1) to (UC-8) were prepared.

  Using the prepared resist underlayer film forming compositions (UC-1) to (UC-8), a “substrate with resist underlayer film” was obtained in the same manner as in Example 1, and the obtained “substrate with resist underlayer film” ”Was measured for the element composition (hydrogen content) of the resist underlayer film, evaluated for film curability, evaluated for etching resistance, and evaluated for bending resistance. The evaluation results are shown in Table 6.

[Discussion]
As shown in Tables 3 and 6, the resist underlayer film forming compositions of Examples 1 to 15 were all evaluated for film curability as “◯” and evaluated for bending resistance as “◯”. Further, in the evaluation of etching resistance, all were “◯” (however, “◎” in Example 9). On the other hand, none of the compositions for forming a resist underlayer film of Comparative Examples 1 to 8 had “◯” for all evaluation items. That is, the evaluation of the film curability is “x” for the resist underlayer film forming compositions of Comparative Examples 1, 5, and 7, and the evaluation of the bending resistance is the resist underlayer film forming composition of Comparative Examples 5 and 7. Except for “x”, the evaluation of etching resistance was “x” in the resist underlayer film forming compositions of Comparative Examples 3 and 7.

  The following reasons can be considered as a cause of obtaining such a result. Since the resist underlayer film formed by the resist underlayer film forming compositions of Examples 1 to 15 is formed by the resist underlayer film composition containing a resin (A) having a low hydrogen content, Low hydrogen content. Therefore, it is considered that the resist underlayer films formed by the resist underlayer film forming compositions of Examples 1 to 15 had bending resistance. Similarly, since the resist underlayer film formed by the resist underlayer film forming composition of Comparative Examples 5 and 7 is formed by the resist underlayer film forming composition containing the novolak resin, the hydrogen content is low. Has bending resistance. However, unlike the resist underlayer films formed by the resist underlayer film forming compositions of Examples 1 to 15, since the alkynyloxy group was not contained, the film curability was evaluated as “x”.

  The reason why the resist underlayer film formed by the resist underlayer film forming compositions of Examples 1 to 15 has film curability is the (A) resin contained in the resist underlayer film forming composition. Is considered to be due to having an alkynyloxy group which is a feature of the present invention. Since the alkynyloxy group does not increase the hydrogen content when the crosslinked structure is formed, the resist underlayer film formed by the resist underlayer film forming compositions of Examples 1 to 15 maintains the bending resistance. However, it is presumed to have film curability.

  On the other hand, since the resin contained in the resist underlayer film forming compositions of Comparative Examples 5 and 7 did not contain an alkynyloxy group, it was estimated that the evaluation of film curability was “x”. Is done. In the composition for forming a resist underlayer film of Comparative Examples 6 and 8, the use amount of the (D) crosslinking agent is increased for the purpose of making the film curability evaluation “◯”. By increasing the amount used, (D) the hydrogen atoms contained in the crosslinking agent increase the hydrogen content of the resist underlayer film, and the resist formed by the resist underlayer film forming composition of Comparative Examples 6 and 8 The lower layer film has a high hydrogen content. Since the hydrogen content is thus high, it is presumed that the resist underlayer film formed by the resist underlayer film forming compositions of Comparative Examples 6 and 8 has an evaluation of bending resistance of “x”.

  Moreover, since the composition for forming a resist underlayer film of Comparative Examples 1 to 4 does not contain a resin having a low hydrogen content, the hydrogen content of the resist underlayer film to be formed is high, and the evaluation of bending resistance is “ It is estimated that “x” was obtained.

  From the above, the resist underlayer film formed by the composition for forming a resist underlayer film of the present invention containing (A) a resin and (B) a solvent has good film curability, etching resistance, and bending resistance. It was confirmed that the

  According to the resist underlayer film forming composition of the present invention, it has film curability, is excellent in etching resistance, and can form a resist underlayer film in which an underlayer film pattern is not easily bent when etching a substrate to be processed. It can be used very suitably for microfabrication 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 during the etching of the substrate to be processed, an improvement in yield can be expected in microfabrication in the lithography process, particularly in the manufacture of highly integrated circuit elements.

  The pattern forming method of the present invention is extremely useful as a lithographic process, particularly as a process for manufacturing highly integrated circuit elements.

It is a flowchart which shows the method of obtaining resin which has group shown by General formula (1) contained in one Embodiment of the composition for resist underlayer film formation of this invention, and an aromatic hydrocarbon group. It is a schematic diagram explaining 1 process of one Embodiment of the formation method of the pattern of this invention. It is a schematic diagram explaining 1 process of one Embodiment of the formation method of the pattern of this invention.

Explanation of symbols

1: substrate, 2: low dielectric insulating film, 3: resist underlayer film.

Claims (5)

(A) a resin having a group represented by the following general formula (1) and an aromatic hydrocarbon group;
(B) a solvent;
A composition for forming a resist underlayer film.

(In the general formula (1), n represents 0 or 1. R ¹ represents an optionally substituted methylene group, an alkylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms. R ² represents an optionally substituted arylene group, and R ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. The composition for forming a resist underlayer film according to claim 1, wherein the (A) resin has a structural unit represented by the following general formula (2).

(In the general formula (2), n represents 0 or 1. R ¹ is an optionally substituted methylene group, an alkylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms. R ² represents an optionally substituted arylene group, R ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms R ³ to R ⁷ represents a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, optionally substituted alkoxy group having 1 to 6 carbon atoms, optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, An aryl group having 6 to 14 carbon atoms which may be substituted, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms, R ⁹ is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, branched Or cyclic alkyl group, carbon number 1 10 straight, branched or cyclic alkyl ether group, or an aryl group having 6 to 10 carbon atoms.)   The composition for forming a resist underlayer film according to claim 1 or 2, wherein the group represented by the general formula (1) is an ethynyloxy group or a (prop-1-yn-1-yl) oxy group.   The composition for forming a resist underlayer film according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of (C) an acid generator and (D) a crosslinking agent. Applying the composition for forming a resist underlayer film according to any one of claims 1 to 4 on a substrate to be processed to form a resist underlayer film (1);
(2) forming a resist film by applying a resist composition on the obtained resist underlayer film;
(3) exposing the resist film by irradiating light through a photomask to the obtained resist film;
Developing the exposed resist film to form a resist pattern (4);
Using the resist film on which the resist pattern is formed as a mask, dry-etching the resist underlayer film and the substrate to be processed, and transferring the resist pattern to the resist underlayer film and the substrate to be processed (5);
A pattern forming method comprising:

Images