JP2015055821A - Positive resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymeric compound prepared by partially replacing hydrogen atoms of phenolic hydroxyl groups in an organosiloxane-modified novolac resin by a 1,2-naphtoquinone diazide sulfonyl group, the compound which has photosensitivity, shows solubility with an alkali in an exposed portion, causes no film reduction after development, and exhibits excellent plating durability during electrolytic plating.SOLUTION: A positive resist material comprising the following polymeric compound and an organic solvent is provided. The polymeric compound is a novolac resin prepared by partially replacing hydrogen atoms of phenolic hydroxyl groups in an organosiloxane-modified novolac resin having a structural unit of formula (1) by a 1,2-naphtoquinone diazide sulfonyl group, in which if necessary, a part of hydrogen atoms in the residual hydroxyl groups may be replaced by one or more specific functional groups. In the formula, Rrepresents an organosiloxy group in which a group bonded to a silicon atom is a monovalent hydrocarbon group; and Rrepresents a hydrogen atom or an alkyl group.

Description

  The present invention relates to a positive resist material containing an organosiloxane-modified novolac phenol resin and a pattern forming method using the resist material.

  In a conventional photoresist material using a novolak resin, as measures for improving cracks generated during or after electrolytic plating, Japanese Patent Laid-Open No. 10-207057 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2004-198915 (Patent Document). The method of relieving the stress of a film | membrane and suppressing the above-mentioned crack by containing an additive like 2) has been used. However, the above-described method uses a compound that exhibits water solubility or alkali solubility as the additive itself, so that resist film filming occurs during long-time development, resulting in desired plating. There are problems such that the thickness cannot be obtained, and the additive component is eluted in the plating solution during electrolytic plating. These are problems caused by trying to avoid structural defects of the resin itself with additives, and there has been a long-awaited material that has essentially improved the above-mentioned drawbacks.

  In addition, the following patent documents 3-5 are mentioned as a prior art about the novolak resin modified with silicone.

JP-A-10-207057 JP 2004-198915 A JP 58-122922 A Japanese Patent Laid-Open No. 3-97710 JP-A-5-59175

  An object of the present invention is to provide a positive resist material and a pattern formation method using an alkali-soluble organosiloxane-modified novolak resin which has no film slip after development and exhibits excellent plating resistance during electrolytic plating.

  As a result of intensive studies to achieve the above object, the present inventors have hydrosilylated a novolak resin made from phenol containing an allyl group and an organosiloxane having one hydrosilyl group in the molecule. In the organosiloxane-modified novolak resin having a structural unit represented by the following general formula (1) obtained by the method, a part of the hydrogen atom of the phenolic hydroxyl group in the novolak resin is substituted with a 1,2-naphthoquinonediazidosulfonyl group When a polymer compound is used as a resist material, it has been found that there is no film slippage after development and excellent plating resistance is exhibited, and the present invention has been made.

（式中、Ｒ¹はケイ素原子に結合する基が炭素数１〜１０の置換もしくは非置換の一価炭化水素基であるオルガノシロキシ基であり、Ｒ²は水素原子又は炭素数１〜４の置換もしくは非置換のアルキル基を示す。）

（式中、Ｒは炭素数１〜３０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基を示す。）
〔２〕
変性ノボラック樹脂が、そのフェノール性水酸基の水素原子を、水素原子１原子当たり、０．０２〜０．７０モルの割合で、１，２−ナフトキノンジアジドスルホニル基で置換した樹脂であることを特徴とする〔１〕記載のポジ型レジスト材料。
〔３〕
変性ノボラック樹脂が、残りのフェノール性水酸基の一部の水素原子を、水素原子１原子当たり、０．０１〜０．８０モルの割合で一般式（２）、（３）、（４）で示される官能基のうち１種又は２種以上の官能基で置換した樹脂であることを特徴とする〔１〕又は〔２〕記載のポジ型レジスト材料。
〔４〕
式（１）の変性ノボラック樹脂におけるＲ¹が下記式（５）で示されるオルガノシロキシ基である〔１〕〜〔３〕のいずれかに記載のポジ型レジスト材料。

［式中、Ｒ³、Ｒ⁴、Ｒ⁵は、それぞれ独立して炭素数１〜１０の置換もしくは非置換の一価炭化水素基、Ｘ、Ｙ、Ｚは単結合又は下記式（６）で示される二価のシロキサン構造であるが、Ｘ、Ｙ、Ｚの少なくとも一つは下記式（６）の二価のシロキサン構造である。

（式中、Ｒ⁶、Ｒ⁷は、それぞれ独立して炭素数１〜１０の置換もしくは非置換の一価炭化水素基、Ｍｅはメチル基であり、ｍ、ｎはそれぞれ０又は正数であるが、ｍ＋ｎは１以上の整数である。）］
〔５〕
変性ノボラック樹脂が、下記式（７）で示される構造単位を有するアリル基含有ノボラック樹脂と分子内にヒドロシリル基を一個含有するオルガノシロキサンとをヒドロシリル化反応させることにより得られるものである〔１〕〜〔４〕のいずれかに記載のポジ型レジスト材料。

（式中、Ｒ²は水素原子又は炭素数１〜４の置換もしくは非置換のアルキル基を示す。）
〔６〕
ｉ）〔１〕〜〔５〕のいずれかに記載のレジスト材料を基板上に塗布する工程、
ｉｉ）塗布した基板を加熱する工程、
ｉｉｉ）波長５００ｎｍ以下の紫外線を照射する工程、
ｉｖ）必要に応じて加熱処理した後、アルカリ現像液を用いて現像する工程
を含むことを特徴とするパターン形成方法。 That is, the present invention provides the following positive resist material and pattern forming method.
[1]
A part of the hydrogen atom of the phenolic hydroxyl group in the organosiloxane-modified novolak resin having the structural unit of the following formula (1) is substituted with a 1,2-naphthoquinonediazidosulfonyl group, and if necessary, a part of the remaining hydroxyl group A polymer compound which is a novolac resin in which the hydrogen atom of may be substituted with one or more of the monovalent functional groups represented by the following general formulas (2), (3) and (4) And a positive resist material containing an organic solvent.

(In the formula, R ¹ is an organosiloxy group in which a group bonded to a silicon atom is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or having 1 to 4 carbon atoms. Represents a substituted or unsubstituted alkyl group.)

(In the formula, R represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)
[2]
The modified novolak resin is a resin in which the hydrogen atoms of the phenolic hydroxyl group are substituted with 1,2-naphthoquinonediazidosulfonyl groups at a ratio of 0.02 to 0.70 mole per hydrogen atom. The positive resist material according to [1].
[3]
The modified novolak resin is represented by the general formulas (2), (3), and (4) at a ratio of 0.01 to 0.80 moles of hydrogen atoms as a part of the remaining phenolic hydroxyl groups. The positive resist material according to [1] or [2], which is a resin substituted with one or more functional groups among the functional groups.
[4]
The positive resist material according to any one of [1] to [3], wherein R ¹ in the modified novolak resin of the formula (1) is an organosiloxy group represented by the following formula (5).

Wherein R ³ , R ⁴ and R ⁵ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X, Y and Z are a single bond or the following formula (6) In the divalent siloxane structure shown, at least one of X, Y, and Z is a divalent siloxane structure of the following formula (6).

Wherein R ⁶ and R ⁷ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Me is a methyl group, and m and n are each 0 or a positive number. M + n is an integer of 1 or more.]]
[5]
The modified novolak resin is obtained by hydrosilylation reaction of an allyl group-containing novolak resin having a structural unit represented by the following formula (7) and an organosiloxane containing one hydrosilyl group in the molecule [1]. To [4]. The positive resist material according to any one of [4].

(In the formula, R ² represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.)
[6]
i) The process of apply | coating the resist material in any one of [1]-[5] on a board | substrate,
ii) heating the coated substrate;
iii) a step of irradiating ultraviolet rays having a wavelength of 500 nm or less;
iv) A pattern forming method comprising a step of performing heat treatment as necessary and then developing using an alkali developer.

  In the organosiloxane-modified novolak resin of the present invention, the polymer compound obtained by substituting a part of the hydrogen atom of the phenolic hydroxyl group in the novolak resin with a 1,2-naphthoquinonediazidesulfonyl group has photosensitivity and photosensitivity. The parts thus obtained are alkali-soluble, have no film slip after development, and exhibit excellent plating resistance during electrolytic plating.

2 is a ¹ H-NMR chart of an organopolysiloxane-modified novolak resin obtained in Synthesis Example 1. FIG. It is explanatory drawing of the crack confirmation part on a resist pattern.

  The positive resist material according to the present invention uses, as a base resin, a part of hydrogen atoms of a phenolic hydroxyl group in an organosiloxane-modified novolak resin having a structural unit of the following formula (1) as a 1,2-naphthoquinonediazide sulfonyl group. Further, if necessary, some hydrogen atoms of the remaining hydroxyl groups are substituted with one or more functional groups among the monovalent functional groups represented by the following general formulas (2), (3), and (4). A polymer compound which is a novolak resin which may be substituted with a group is used.

（式中、Ｒ¹はケイ素原子に結合する基が炭素数１〜１０の置換もしくは非置換の一価炭化水素基であるオルガノシロキシ基であり、Ｒ²は水素原子又は炭素数１〜４の置換もしくは非置換のアルキル基を示す。）

(In the formula, R ¹ is an organosiloxy group in which a group bonded to a silicon atom is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or having 1 to 4 carbon atoms. Represents a substituted or unsubstituted alkyl group.)

（式中、Ｒは炭素数１〜３０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基を示す。）

(In the formula, R represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)

（式中、Ｒ²は水素原子又は炭素数１〜４の置換もしくは非置換のアルキル基であり、置換アルキル基としては、フッ素化アルキル基等が挙げられる。） Here, the organosiloxane-modified novolak resin of the above formula (1) is a hydrosilylation reaction of an aryl group-containing novolak resin having a structural unit represented by the following formula (7) and an organosiloxane containing one hydrosilyl group in the molecule. Can be obtained.

(In the formula, R ² is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and examples of the substituted alkyl group include a fluorinated alkyl group.)

  That is, the novolac resin is a novolac resin using phenol having an allyl group as a raw material, and examples of phenol having an allyl group include 2-allylphenol, 4-allylphenol, 6-methyl-2-allylphenol, 4 -Allyl 2-methoxyphenol and the like can be mentioned, among which 2-allylphenol can be preferably used. The phenol having an allyl group is preferably 1 to 40 parts by mass, preferably 2 to 25 parts by mass in all phenols constituting the novolak resin.

  In addition, as another phenol raw material, well-known phenols can be used as a raw material, for example, phenol, m-cresol, o-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3 , 5-xylenol, xylenols such as 3,4-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4- tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 6-tert-butyl-3-methylphenol, etc. Alkylphenols, p-methoxyphenol, m Alkoxyphenols such as methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol, o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, Isopropenylphenols such as 2-ethyl-4-isopropenylphenol, polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, hydroquinone, pyrogallol, α-naphthol, β- Examples include naphthol and dihydroxynaphthalene. Among these phenols, it is particularly preferable to use phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, and 3,5-xylenol as raw materials.

  And novolak resin can be obtained by using a well-known method with respect to these phenols. A resin having a weight average molecular weight in terms of polyhydroxystyrene by GPC of the obtained novolak resin of 2,000 to 50,000, preferably 3,000 to 20,000 can be used.

  The group bonded to the silicon atom is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms with respect to the allyl group in the side chain contained in the novolak resin thus obtained, and An organosiloxane having one hydrosilyl group (SiH group) (organohydrogensiloxane) is added to this, and as the organohydrogensiloxane, those represented by the following formula (8) are preferably used.

［式中、Ｒ³、Ｒ⁴、Ｒ⁵は、それぞれ独立して炭素数１〜１０、好ましくは１〜３の置換もしくは非置換の一価炭化水素基、Ｘ、Ｙ、Ｚは単結合又は下記式（６）で示される二価のシロキサン構造であるが、Ｘ、Ｙ、Ｚの少なくとも一つは下記式（６）の二価のシロキサン構造である。

（式中、Ｒ⁶、Ｒ⁷は、それぞれ独立して炭素数１〜１０、好ましくは１〜３の置換もしくは非置換の一価炭化水素基、Ｍｅはメチル基であり、ｍ、ｎはそれぞれ０又は正数であるが、ｍ＋ｎは１以上の整数である。）］

[Wherein R ³ , R ⁴ and R ⁵ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, X, Y and Z are single bonds or Although it is a divalent siloxane structure represented by the following formula (6), at least one of X, Y, and Z is a divalent siloxane structure of the following formula (6).

Wherein R ⁶ and R ⁷ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, Me is a methyl group, and m and n are each It is 0 or a positive number, but m + n is an integer of 1 or more.]]

Here, examples of the monovalent hydrocarbon group for R ³ , R ⁴ , R ^5, R ⁶ and R ⁷ include linear, branched or cyclic alkyl groups, and aryl groups such as a phenyl group. Examples of the substituted monovalent hydrocarbon group include a fluorinated alkyl group, specifically, a trifluoromethyl group.

  In Formula (6), m and n are each 0 or a positive number, and m + n is 1 or more, preferably 1 ≦ m + n ≦ 1,000, more preferably 10 ≦ m + n ≦ 200.

  In addition, any one having only one hydrosilyl structure in the molecule of the organopolysiloxane can be preferably used. The organopolysiloxane having only one hydrosilyl group in the molecule is 0.05 ≦ F / E ≦ 1.5 when the equivalent of the alkenyl group of the novolak resin is E and the equivalent of the hydrosilyl group is F. In particular, the reaction is preferably performed at 0.1 ≦ F / E ≦ 1.0. When F / E is less than 0.05, sufficient flexibility may not be obtained, and when it exceeds 1.5, excessive unreacted siloxane remains, resulting in a decrease in storage stability. There is a fear.

  The addition reaction (hydrosilylation reaction) between the novolak resin having an allyl group and the organohydrogensiloxane represented by the general formula (8) is performed in an organic solvent. The organic solvent that can be used in this case is not particularly limited as long as it dissolves both components and becomes a uniform solution, but for example, aromatic hydrocarbons such as benzene, toluene, xylene, diethyl, etc. Examples include ethers such as ether, dibutyl ether, tetrahydrofuran, cyclopentyl methyl ether, and dioxane; ketones such as methyl isobutyl ketone, methyl propyl ketone, and methyl pentyl ketone; and alcohols such as ethanol and isopropyl alcohol. Or a mixture of two or more. About the amount of the solvent, it is 1-500 mass parts with respect to 100 mass parts of novolak resin used as a raw material, Preferably it is 2-200 mass parts.

Then, conventionally known addition catalysts such as organic peroxides, tertiary amines, phosphines, platinum, palladium, rhodium-based transition metal compounds, and the like can be added to the solution in which both components are uniformly dissolved. Of these, a platinum-based catalyst such as chloroplatinic acid is preferable. In addition, the addition amount is a catalytic amount, and in the case of a platinum catalyst, it is 1 to 10,000 ppm with respect to the organosiloxane.
Moreover, you may irradiate with an ultraviolet-ray instead of adding said catalyst.

  After the addition of the catalyst, the aryl group in the side chain of the novolak resin is partly depending on the reaction temperature of usually 40 to 140 ° C., preferably 60 to 120 ° C., and the reaction time of 0.5 to 20 hours, preferably 1 to 10 hours. A novolak resin having a structural unit of the following formula (1) modified with organopolysiloxane can be obtained.

（式中、Ｒ¹はケイ素原子に結合する基が炭素数１〜１０の置換もしくは非置換の一価炭化水素基であるオルガノシロキシ基、好ましくは下記式（５）で示されるオルガノシロキシ基であり、Ｒ²は水素原子又は炭素数１〜４の置換もしくは非置換のアルキル基を示す。）

(In the formula, R ¹ is an organosiloxy group in which a group bonded to a silicon atom is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably an organosiloxy group represented by the following formula (5): And R ² represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.)

（式中、Ｒ³、Ｒ⁴、Ｒ⁵は、それぞれ独立して炭素数１〜１０の置換もしくは非置換の一価炭化水素基、Ｘ、Ｙ、Ｚは単結合又は上記式（６）で示される二価のシロキサン構造であるが、Ｘ、Ｙ、Ｚの少なくとも一つは上記式（６）の二価のシロキサン構造である。）

Wherein R ³ , R ⁴ and R ⁵ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X, Y and Z are a single bond or the above formula (6) The divalent siloxane structure shown is at least one of X, Y and Z is a divalent siloxane structure of the above formula (6).

  As a method for introducing a 1,2-naphthoquinonediazidosulfonyl group into a part of the hydrogen atoms of the hydroxyl group of the resulting organosiloxane-modified novolak resin (1), a conventional method of partial esterification can be used. For example, the following methods can be mentioned.

  The obtained novolak resin modified with organosiloxane is dissolved in a solvent such as 1,4-dioxane, tetrahydrofuran, cyclopentylmethyl ether, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, toluene and the like. Under the present circumstances, the kind of solvent can be used 1 type or in mixture of 2 or more types.

  In the above solution, one or two of 1,2-naphthoquinonediazide-4-sulfonyl halide, 1,2-naphthoquinonediazide-5-sulfonyl halide (in this case, the halogen is any one of chlorine, bromine and iodine atoms) The seeds may be dissolved, and if necessary, one or more of the halogen compounds represented by the following general formulas (9), (10), and (11) may be dissolved. Then, the method of making it react for about 0.2 to 10 hours at 5-50 degreeC under a basic catalyst is employable.

  By replacing any of the halogen compounds (9) to (11) with a part of the hydrogen atom of the hydroxyl group of the novolak resin as described above, the novolak resin substituted with the 1,2-naphthoquinonediazidesulfonyl group as described above. The monovalent functional groups of the following formulas (2) to (4) can be introduced into the novolak resin.

（式中、Ｒは炭素数１〜３０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基を示す。Ｔは、塩素、臭素、ヨウ素のいずれかのハロゲン原子を示す。）

(In the formula, R represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. T represents a halogen atom of chlorine, bromine, or iodine. Show.)

  As R in the above formulas (2) to (4) and formulas (9) to (11), an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms is particularly preferable. A methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a tolyl group, etc. are mentioned, Especially a C1-C6 alkyl group is preferable. T is preferably a chlorine atom.

  Examples of the basic catalyst used in the reaction include nitrogen-containing heterocyclic compounds such as pyridine and dimethylaminopyridine; amines such as triethylamine, tripropylamine, N-methylpiperidine, DBU (diazabicycloundecene); sodium methoxide, Alkali metal alkoxides such as sodium ethoxide; carboxylic acid alkali metal salts such as sodium acetate; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal carbonates such as sodium hydrogen carbonate Examples thereof include hydrogen salts; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide. Although the basic catalyst is appropriately adjusted and used, it can be used in an amount of about 0.01 to 100 mol% with respect to the novolak resin.

  At this time, the substitution rate of 1,2-naphthoquinonediazide sulfonyl halide is 0.02 to 0.70 mol, preferably 0.04 to 0.50 per hydrogen atom of the phenolic hydroxyl group contained in the novolak resin. Is a mole. The substitution rate of the substituted carbonyl group or the substituted sulfonyl group is 0 to 1 mol, preferably 0.01 to 0.80 mol, per one hydrogen atom of the phenolic hydroxyl group contained in the novolak resin. When these substitution ratios increase, hydrophobic effects appear and the development speed is greatly reduced, which may be undesirable. In addition, when the substitution rate is low, the unexposed area is also eluted in the developer, which may not be preferable.

  In the obtained organosiloxane-modified novolak resin, a polymer compound in which a part of the hydrogen atom of the phenolic hydroxyl group in the novolak resin is substituted with a 1,2-naphthoquinonediazidesulfonyl group is necessary for neutralization reaction. In accordance with the above, it can be used as a resist material by performing a purification step and dissolving in an organic solvent.

  Examples of the organic solvent used as a resist material in the present invention include butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, 3-ethoxyethyl propionate, 3- Ethoxymethyl propionate, 3-methoxymethyl propionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether pro Pionate, propylene glycol monoethyl ether propionate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether Dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide Γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, and the like, but are not limited thereto. Particularly preferred are dipropylene glycol alkyl ether and lactic acid alkyl ester. These solvents may be used alone or in combination of two or more. The amount of the organic solvent that can be used in the present invention is 20 with respect to 100 parts by mass of the polymer compound in which a part of the hydrogen atoms of the phenolic hydroxyl group in the novolak resin is substituted with 1,2-naphthoquinonediazidosulfonyl group. ˜2,000 parts by mass, preferably 40 to 200 parts by mass.

  In the organopolysiloxane-modified novolak resin of the present invention, when a polymer compound in which a part of the hydrogen atom of the phenolic hydroxyl group in the novolak resin is substituted with a 1,2-naphthoquinonediazidesulfonyl group is used as a resist composition. Can be added with a surfactant for improving coatability. Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, Polyoxyethylene alkyl aryl ethers such as oxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate , Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan Non-ionic surfactants of polyoxyethylene sorbitan fatty acid esters such as nostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Mega Fuck F171, F172, F173 (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Corporation), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Fluorosurfactants such as Surfynol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass Co., Ltd.), organosiloxane polymer KP341, X- 0-092, (manufactured by Shin-Etsu Chemical Co., Ltd.) X-70-093, acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These can be used alone or in combination of two or more. As the addition amount of the surfactant used in the present invention, the lower limit is 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, and the upper limit is 100 parts by mass of the solid content of the polymer compound. It is preferably 3 parts by mass or less, more preferably 1 part by mass or less.

  Furthermore, in this invention, well-known additives, such as a crosslinking agent, dye, a dissolution accelerator, an adhesion improver, a stabilizer, can be included as needed.

  Next, the resist pattern forming method of the present invention will be described. When the resist material of the present invention is used for various semiconductor production, a known lithography technique can be used, although not particularly limited. Specifically, the resist material is applied to a substrate, heat-treated, exposed to radiation or electron beam through a photomask, and further heat-treated as necessary, followed by development using a developer. Thus, the resist pattern of the present invention is formed.

As the substrate, in addition to a substrate such as Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, and SOG, a metal substrate such as Au, Ti, W, Cu, Ni—Fe, Ta, Zn, Co, and Pb, or A substrate such as an organic antireflection film is preferably used. The resist film is coated on the substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating, etc., and the coating film thickness is 0.1 to 100 μm, particularly preferably 1.0. Apply to ˜50 μm. Thereafter, heat treatment (pre-baking) is performed at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 120 ° C. for 1 to 5 minutes, using a heating device such as a hot plate. Next, using a radiation or electron beam selected from ultraviolet rays, far ultraviolet rays, X-rays, excimer lasers, γ rays, synchrotron radiation, etc., preferably with an exposure wavelength of 500 nm or less, particularly 350-450 nm ultraviolet rays, through a predetermined photomask Perform exposure. The exposure amount is 10 to 5,000 mJ / cm ² , preferably 100 to 4,000 mJ / cm ² . Furthermore, if necessary, heat treatment (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 120 ° C. for 1 to 5 minutes. Subsequently, immersion is performed for 1 to 60 minutes, preferably 2 to 20 minutes using a developer of an alkaline aqueous solution such as 0.1 to 5% by mass, preferably 2 to 3% by mass of tetramethylammonium hydroxide (TMAH). By developing according to a conventional method such as a Dip method, a paddle method, or a spray method, a target fine resist pattern is formed on the substrate.

  Furthermore, the plating pattern formation method of this invention is demonstrated. Specifically, using the resist pattern formed by the above resist pattern forming method as a mask, a conductor pattern is deposited and formed by an electrolytic plating method or an electroless plating method by a conventional method, and then the resist pattern is removed. . In this case, a substrate having at least a surface formed of metal is used as the substrate. For example, it is preferable to use a silicon substrate formed with a film of copper or the like by means such as sputtering. Electrolytic plating or electroless plating includes electrolytic Cu plating, electroless Cu plating, electrolytic Fe-Ni plating, electrolytic Au plating, and the like, and plating can be performed using a known plating bath and plating conditions. The plating thickness is generally 80 to 100% of the resist pattern thickness. For example, the seed layer is copper, a resist pattern having a thickness of 10 μm is formed thereon, and then a copper plating pattern having a thickness of 8 to 10 μm is formed by electrolytic copper plating. By the way, in the case of manufacturing a semiconductor device, the resist pattern is removed after the semiconductor substrate is etched according to a conventional method using the formed resist pattern as a mask.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

その後、９０℃で４時間の反応を行い、ストリップにて脱溶剤後、固形分を回収した。得られた樹脂の重量平均分子量（ＧＰＣ測定）は７，２００で、その樹脂の¹Ｈ−ＮＭＲを測定し、目的とするオルガノポリシロキサン変性ノボラック樹脂の合成を確認した。図１に¹Ｈ−ＮＭＲのチャートを示す。 [Synthesis Example 1]
50 g of novolak resin having a weight average molecular weight of 4,500 consisting of m-cresol / p-cresol / 2-allylphenol = 36/54/10 in a 1 L four-necked flask equipped with a condenser and a stirrer And 150 g of cyclopentyl methyl ether were added, and 34 g of SiH-containing polysiloxane of the following formula (12) was further added, followed by heating to 60 ° C. and 0.08 g of an isopropyl alcohol solution containing 0.5% by mass of chloroplatinic acid.

Thereafter, the reaction was carried out at 90 ° C. for 4 hours, and after removing the solvent with a strip, the solid content was recovered. The weight average molecular weight (GPC measurement) of the obtained resin was 7,200, and ¹ H-NMR of the resin was measured to confirm the synthesis of the desired organopolysiloxane-modified novolak resin. FIG. 1 shows a ¹ H-NMR chart.

その後、９０℃で４時間の反応を行い、ストリップにて脱溶剤後、固形分を回収した。得られた樹脂の重量平均分子量は９，３００で、合成例１と同様に¹Ｈ−ＮＭＲを測定し、目的とするオルガノポリシロキサン変性ノボラック樹脂の合成を確認した。 [Synthesis Example 2]
In a 1 L four-necked flask equipped with a condenser and a stirrer, 50 g of the same novolak resin as in Synthesis Example 1 and 1,500 g of cyclopentyl methyl ether were added, and after addition of 195 g of SiH-containing polysiloxane of the following formula (13), 60 g The mixture was heated to 0 ° C., and 0.40 g of an isopropyl alcohol solution containing 0.5% by mass of chloroplatinic acid was added.

Thereafter, the reaction was carried out at 90 ° C. for 4 hours, and after removing the solvent with a strip, the solid content was recovered. The weight average molecular weight of the obtained resin was 9,300, and ¹ H-NMR was measured in the same manner as in Synthesis Example 1 to confirm the synthesis of the desired organopolysiloxane-modified novolak resin.

その後、９０℃で４時間の反応を行い、ストリップにて脱溶剤後、固形分を回収した。得られた樹脂の重量平均分子量は５，３００で、その樹脂の¹Ｈ−ＮＭＲを測定し、目的とするオルガノポリシロキサン変性ノボラック樹脂の合成を確認した。 [Synthesis Example 3]
In a 1 L four-necked flask equipped with a condenser and a stirrer, 50 g of the same novolak resin as in Synthesis Example 1 and 150 g of cyclopentyl methyl ether were added, and 9.0 g of a SiH-containing polysiloxane of the following formula (14) was added, and then 60 The mixture was heated to 0 ° C., and 0.08 g of an isopropyl alcohol solution containing 0.5% by mass of chloroplatinic acid was added.

Thereafter, the reaction was carried out at 90 ° C. for 4 hours, and after removing the solvent with a strip, the solid content was recovered. The weight average molecular weight of the obtained resin was 5,300, and ¹ H-NMR of the resin was measured to confirm the synthesis of the desired organopolysiloxane-modified novolak resin.

[Example 1]
100 g of the novolak resin modified with organosiloxane obtained in Synthesis Example 1 was dissolved in 200 g of a solution of acetone / cyclopentylmethyl ether = 1/1, and 5.38 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride (NQD5). Then, 2.0 g of triethylamine was added dropwise so that the internal temperature did not exceed 40 ° C., and then aged for 1 hour. Then, it was poured into 2,000 ml of 0.1N hydrochloric acid, and the precipitate was collected, redissolved in 300 ml of methyl isobutyl ketone, subjected to a reduced pressure strip at 40 ° C., and the resulting solid was collected.

[Examples 2 to 10]
Using the same method as in Example 1, synthesis was carried out at the blending ratio shown in Table 1 below.

To the obtained polymer compounds of Examples 1 to 10, surfactant X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added at 1,000 ppm in a blending ratio of dipropylene glycol dimethyl ether / ethyl lactate = 7/3 ( Mass) was added to a solid content concentration of 70% by mass, and after confirming that the solution became uniform, filtration was performed with a 1 μm glass filter. The obtained filtrate was applied on a substrate on which a Cu sputter layer of about 200 nm was formed using a spin coater at a rotation speed of 30 μm. After pre-baking at 100 ° C./120 seconds, an i-line stepper (Co., Ltd.) was applied. Nikon NSR-2205i11D) was used for exposure, and then development was performed for 50 seconds × 15 times using a TMAH = 2.38 mass% developer. In addition, the thickness of the resist film after development was confirmed, and a 30 μm line and space repetitive pattern on the resist film formed on the obtained substrate after coating was examined with an electron microscope (Hitachi High-Tech Fielding, S- 4100), the optimum exposure amount at which the width of the line and the space becomes 1: 1 was calculated, and the exposure amount was defined as Eop. The obtained results are shown in Table 2.
Calculation of the remaining film rate was performed by the following formula.
Residual film ratio = (resist film thickness after development) / (resist film thickness after pre-baking)
Each film thickness was measured with a light interference film thickness meter.

[Comparative Examples 1 and 2]
Next, as shown in Table 3, as a comparative example, a novolak resin having a weight average molecular weight of 6,000 having m-cresol / p-cresol / formaldehyde = mass ratio of 4/6/5 was used as in Example 1. The following resins were prepared using the method described above.

[Comparative Examples 3 to 5]
Furthermore, with respect to the resins of Comparative Examples 1 and 2, alkali soluble cellulose A (hydroxypropyl methylcellulose phthalate manufactured by Shin-Etsu Chemical Co., Ltd .: acid value 92, containing 20 mol% of carboxybenzoyl group) was introduced as additive 1 in Table 4 below. A sample was made.

  Table 5 shows the results of the same evaluation as in the examples.

Next, as an evaluation of plating patterns for all Examples and Comparative Examples, using a dry etching apparatus (manufactured by Nidec Anelva: DEM-451), the resist pattern and the substrate surface were ashed with oxygen plasma at 100 W for 30 seconds. It was immersed in the mass% sulfuric acid water for 30 seconds. Then, it was immersed in Cu plating liquid (Nippon Electroplating Engineers Co., Ltd. product: Microfab Cu200), Cu was plated by flowing a constant current at 25 ° C. for 60 minutes, and Cu having a thickness of 28 μm was laminated. Next, the substrate surface after electrolytic plating was washed with pure water and then blown with nitrogen to dry the substrate surface. The substrate surface was observed with an optical microscope, and it was confirmed whether cracks were generated on the pattern. In the crack resistance, the number of cracks generated is counted by observing the corner portion 4,500 points shown in FIG. It is judged that being less than 100 points out of the points is rich in crack resistance, and the evaluation results are shown in Table 6.
In FIG. 2, A is 30 crack confirmation portions, and this confirmation portion has a pattern width of 50 μm to 10 μm, and therefore, the confirmation portions for B for one shot are 30 × 5 = 150 in total. . And since it confirmed in 30 shots C, the confirmation location is a total of 150x30 = 4500 locations.

Claims (6)

A part of the hydrogen atom of the phenolic hydroxyl group in the organosiloxane-modified novolak resin having the structural unit of the following formula (1) is substituted with a 1,2-naphthoquinonediazidosulfonyl group, and if necessary, a part of the remaining hydroxyl group A polymer compound which is a novolac resin in which the hydrogen atom of may be substituted with one or more of the monovalent functional groups represented by the following general formulas (2), (3) and (4) And a positive resist material containing an organic solvent.

(In the formula, R ¹ is an organosiloxy group in which a group bonded to a silicon atom is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or having 1 to 4 carbon atoms. Represents a substituted or unsubstituted alkyl group.)

(In the formula, R represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)   The modified novolak resin is a resin in which the hydrogen atoms of the phenolic hydroxyl group are substituted with 1,2-naphthoquinonediazidosulfonyl groups at a ratio of 0.02 to 0.70 mole per hydrogen atom. The positive resist material according to claim 1.   The modified novolak resin is represented by the general formulas (2), (3), and (4) at a ratio of 0.01 to 0.80 moles of hydrogen atoms as a part of the remaining phenolic hydroxyl groups. 3. The positive resist material according to claim 1, wherein the positive resist material is a resin substituted with one or more functional groups among functional groups. The positive resist material according to claim 1, wherein R ¹ in the modified novolak resin of the formula (1) is an organosiloxy group represented by the following formula (5).

Wherein R ³ , R ⁴ and R ⁵ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X, Y and Z are a single bond or the following formula (6) In the divalent siloxane structure shown, at least one of X, Y, and Z is a divalent siloxane structure of the following formula (6).

Wherein R ⁶ and R ⁷ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Me is a methyl group, and m and n are each 0 or a positive number. M + n is an integer of 1 or more.]] The modified novolak resin is obtained by a hydrosilylation reaction of an allyl group-containing novolak resin having a structural unit represented by the following formula (7) and an organosiloxane containing one hydrosilyl group in the molecule. The positive resist material of any one of -4.

(In the formula, R ² represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.) i) applying a resist material according to any one of claims 1 to 5 on a substrate;
ii) heating the coated substrate;
iii) a step of irradiating ultraviolet rays having a wavelength of 500 nm or less;
iv) A pattern forming method comprising a step of performing heat treatment as necessary and then developing using an alkali developer.

Images