JP2007293075A - Radiation-sensitive resin composition and use thereof - Google Patents

Abstract

Disclosed is a radiation-sensitive resin composition capable of easily processing a thick film wiring pattern and having extremely low pattern defects such as bubbles and deformation in the wiring pattern. Moreover, the wiring formation material which uses the composition of this invention is provided.
[1] Sensitivity containing 0.5% by mass or less of a compound containing the following (A), (B) and (C) and having a boiling point of 250 ° C. or less at 1 atm in the total amount of the composition. Radiation resin composition. (A) An alkali-soluble resin represented by (a) below (a) A novolak resin obtained by condensing a phenol compound and an aldehyde compound. (B) Epoxy-containing silicon compound. (C) A compound that generates an acid upon irradiation with radiation. [2] A wiring forming material comprising the radiation sensitive resin composition. [3] A semiconductor device having a metal wiring pattern obtained using the wiring forming material.
[Selection figure] None

Description

  The present invention relates to a radiation sensitive resin composition suitable for forming a thick film metal wiring in a semiconductor device. More specifically, the present invention relates to a radiation sensitive resin composition suitable for forming a wiring pattern in which the occurrence of deformation caused by bubbles or the like is extremely low.

In recent years, along with downsizing of electronic devices, LSI high-density mounting technology has been improved by multi-pin thin film mounting, flip chip method (CSP), and the like. Among such mounting techniques, a technique called WL-CSP, in which dicing is performed after mounting directly on a wafer on which a semiconductor circuit is formed, has attracted attention. In the mounting, bump electrodes and metal posts called bump electrodes having a height of 20 μm or more need to be arranged on the substrate with high accuracy, and improvement of the rewiring pattern processing technique related to the processing accuracy of these bump electrodes. Is desired. As a rewiring pattern processing technique, photofabrication using a thick film resist capable of further miniaturization is being considered instead of the conventional hole plate printing method or the like (for example, see Patent Document 1). However, pattern processing using the thick film resist has a tendency to generate bubbles in the film or cause the pattern to be deformed. In the metal wiring pattern obtained using such a pattern having a defect, a defective portion is transferred, and as a result, a desired metal wiring pattern may not be obtained.
JP 2000-39709 A

  An object of the present invention is to provide a radiation-sensitive resin composition capable of easily processing a thick film wiring pattern and having extremely low pattern defects such as bubbles and deformation in the wiring pattern. Furthermore, it is providing the semiconductor device which has the wiring formation material which uses the radiation sensitive resin composition of this invention, and the metal wiring formed using this wiring formation material.

（式中、ｎは０，１，２のいずれかを表わす。Ｒ₁は炭素数１〜２０の一価の有機基を表し、Ｒ₁が複数個存在する場合は、それぞれ同一でも異なっていてもよい。）

（式中、Ｒ₂は、水素原子または炭素数１〜２０の一価の有機基を表す）
（ｂ）上記ノボラック樹脂（ａ）のフェノール性水酸基の一部をＯＲ₃基に置換した樹脂（ここで、Ｒ₃は炭素数１〜２０の一価の有機基を表す。）
（Ｂ）式（３）で示される含エポキシ基ケイ素化合物

（式中、Ｑ₂、Ｑ₃は、それぞれ独立に式（４）で表される基であり、Ｑ₁は、式（５）で示される基または式（６）で示される基から選ばれる。）

（式中、Ｔ₁は炭素数１〜６のアルキレン基、炭素数２〜６のアルキレンオキシアルキレン基又はフェニレン基を表す。ｍは０又は１である。）

（式中、Ｔ₂〜Ｔ₇は、それぞれ独立にメチル基又はフェニル基を表す。Ｔ₈は酸素原子、メチレン基、エテニレン基、エチニレン基、フェニレン基、ナフタレンジイル基又はビフェニルジイル基から選ばれる。）
（Ｃ）放射線の照射により酸を発生する化合物 As a result of intensive studies to find a radiation-sensitive composition that can solve the above-mentioned problems, the present inventors have completed the present invention.
That is, this invention provides the radiation sensitive resin composition shown to following [1].
[1] A radiation sensitive resin composition containing the following (A), (B) and (C), and containing 0.5% by mass or less of a compound having a boiling point of 250 ° C. or less at 1 atm in the total amount of the composition. Product (A) An alkali-soluble resin represented by the following (a) and / or (b) (a) A novolak obtained by condensing a phenol compound represented by the formula (1) and an aldehyde compound represented by the formula (2) resin

(In the formula, n represents 0, 1, or 2. R ₁ represents a monovalent organic group having 1 to 20 carbon atoms, and when a plurality of R ₁ are present, they may be the same or different. May be.)

(Wherein R ₂ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)
(B) A resin obtained by substituting a part of the phenolic hydroxyl group of the novolak resin (a) with an OR ₃ group (where R ₃ represents a monovalent organic group having 1 to 20 carbon atoms).
(B) Epoxy-containing silicon compound represented by formula (3)

(In the formula, Q ₂ and Q ₃ are each independently a group represented by the formula (4), and Q ₁ is selected from a group represented by the formula (5) or a group represented by the formula (6)). .)

(Wherein, T ₁ is .m representing an alkylene group, an alkylene oxyalkylene group or a phenylene group having 2 to 6 carbon atoms having 1 to 6 carbon atoms is 0 or 1.)

(Wherein T _{2 to} T ₇ each independently represents a methyl group or a phenyl group. T ₈ is selected from an oxygen atom, a methylene group, an ethenylene group, an ethynylene group, a phenylene group, a naphthalenediyl group or a biphenyldiyl group. .)
(C) Compound that generates acid upon irradiation

Moreover, the radiation sensitive resin composition of this invention has more preferable that said (A), (B), (C) and a highly volatile component are following [2] and [3].
[2] The radiation sensitive resin composition of [1] above, comprising (A) 39.9 to 90% by mass, (B) 9.9 to 60% by mass, and (C) 0.1 to 20% by mass. The radiation-sensitive resin composition according to the above [1] or [2], wherein the 0.5% weight loss temperature in thermogravimetric analysis is 100 to 250 ° C.

Moreover, from the viewpoint of improving the sensitivity to radiation of the radiation-sensitive resin composition of the present invention, the following [4] is more preferable.
[4] The radiation-sensitive resin composition according to any one of [1] to [3], further comprising (D) a photosensitizer.

Furthermore, the present invention provides the following [5] and [6].
[5] Wiring forming material using the radiation sensitive resin composition according to any one of the above [6] Semiconductor device having a metal wiring formed using the wiring forming material according to the above [5]

  When the radiation-sensitive resin composition of the present invention is used, a wiring pattern having almost no pattern defects such as bubbles or deformation can be obtained even when a thick film wiring pattern is processed. The radiation-sensitive resin composition can also be applied to a vacuum coating method suitable for forming a thick film wiring. The wiring forming material using the radiation-sensitive resin composition can form a metal wiring which is thick and hardly causes pattern defects, and can provide a suitable semiconductor device.

<Radiation sensitive resin composition>
The photosensitive composition of the present invention comprises:
(A) Alkali-soluble resin of (a) and / or (b) above (B) Epoxy-containing silicon compound represented by the above formula (3) (C) Contains a compound that generates an acid upon irradiation with radiation. A compound having a boiling point at 1 atm of 250 ° C. or less (hereinafter sometimes referred to as “highly volatile component”) is 0.5% by mass or less.

The (A) alkali-soluble resin applied to the radiation-sensitive resin composition of the present invention will be described.
Here, the notation of “alkali-soluble” indicates that it can be dissolved in either an alkaline aqueous solution, an alkaline organic solvent, or an alkaline organic solvent-water mixed solution. In the present invention, the above (a), One type or two or more types of resins selected from (b) are shown.

(A) is a novolak resin obtained by condensing the phenol compound represented by the above formula (1) and the aldehyde compound represented by the formula (2), wherein R ₁ in the formula (1) is ₁ carbon atom. Represents a monovalent organic group of ˜20. The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and examples thereof include a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms and 3 to 20 carbon atoms. A branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like. The aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted with an alkyl group or alkenyl group having about 1 to 4 carbon atoms, and may be a group having 6 to 20 carbon atoms in total.

  Among these, a straight hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic carbon atom having 6 to 20 carbon atoms. A hydrogen group is preferred.

  Examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl. Group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and the like, in particular, methyl group, ethyl group, propyl group, butyl group, pentyl group, A hexyl group is preferred.

  Examples of the branched aliphatic hydrocarbon group having 3 to 20 carbon atoms include isopropyl group, isobutyl group, tertiary butyl group, tertiary octyl group, and the like, and isopropyl group and isobutyl group are particularly preferable.

  Examples of the cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. In particular, a cyclopentyl group and a cyclohexyl group are exemplified. preferable.

  The aromatic hydrocarbon group having 6 to 20 carbon atoms represents a group having an aromatic ring constituting the group or a group having a group in which a hydrocarbon group is substituted on the aromatic ring, and the number of carbon atoms constituting the group The sum is 6-20. Here, examples of the substituent of the aromatic ring include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, alkenyl groups such as allyl group and vinyl group, alkenyloxy groups such as allyloxy group, and ethynyl group. Examples include alkynyloxy groups such as alkynyl group and ethynyloxy group.

  Specific examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propyl A phenyl group, a butylphenyl group, a methyl naphthyl group, a dimethyl naphthyl group, a trimethyl naphthyl group, a vinyl naphthyl group, a methyl anthryl group, an ethyl anthryl group and the like can be mentioned, and a phenyl group, a tolyl group and a xylyl group are particularly preferable.

The substitution position of R ₁ in the formula (1) is preferably _one in which at least two positions are not substituted among the 2-position, 4-position and 6-position from the phenol hydroxyl group. Specifically, phenol (hydroxybenzene), o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p -Propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-tertiarybutylphenol, m-tertiarybutylphenol, o-hexylphenol, m-hexylphenol, o-decylphenol, m-decylphenol O-dodecylphenol, m-dodecylphenol, o-hexadecylphenol, m-hexadecylphenol, o-icosylphenol, m-icosylphenol, o-cyclopentylphenol, -Cyclopentylphenol, o-cyclohexylphenol, m-cyclohexylphenol, o-cycloheptylphenol, m-cycloheptylphenol, o-phenylphenol, m-phenylphenol, o-toluylphenol, m-toluylphenol, o-naphthylphenol , M-naphthylphenol,
2,5-xylenol, 2,3-xylenol, 3,5-xylenol, 2-ethyl-5-methylphenol, 2-ethyl-3-methylphenol, 3-ethyl-5-methylphenol, 2-isopropyl-5 -Methylphenol, 2-isopropyl-3-methylphenol, 3-isopropyl-5-methylphenol, 2-tertiarybutyl-5-methylphenol, 2-tertiarybutyl-3-methylphenol, 3-tertiarybutyl- 5-methylphenol, 2-hexyl-5-methylphenol, 2-hexyl-3-methylphenol, 3-hexyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-cyclohexyl-3-methylphenol, 3-cyclohexyl-5-methylphenol, 2-phenyl Nyl-5-methylphenol, 2-phenyl-3-methylphenol, 3-phenyl-5-methylphenol, 2-naphthyl-5-methylphenol, 2-naphthyl-3-methylphenol, 3-naphthyl-5-methyl Phenol, 2,5-diethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,5-dipropylphenol, 2,3-dipropylphenol, 3,5-dipropylphenol, 2,5 -Biscyclohexylphenol, 2,3-biscyclohexylphenol, 3,5-biscyclohexylphenol, 2,5-diphenylphenol, 2,3-diphenylphenol, 3,5-diphenylphenol and the like.
In particular, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3-xylenol, 2-butylphenol, 2-isobutylphenol, 2-cyclohexylphenol or 2- Phenylphenol is preferred, especially phenol, o-cresol, m-cresol or p-cresol.

The R ₂ group in the formula (2) is selected from a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and examples of the monovalent organic group include those equivalent to the R ₁ group. Specific examples of the aldehyde compound represented by the formula (2) include formaldehyde, acetaldehyde, propanal, butanal, hexanal, octanal, decanal, dodecanal, hexadecanal, icosanal, 2-methylpropanal, 2-methylbutanal. 2-ethylbutanal, 2,2-dimethylpropanal, acrolein, 2-butenal, 2-hexenal, 2-octenal, acetylenic aldehyde, 2-butynal, 2-hexinal, 2-octynal, cycloheptylcarbalaldehyde, Examples include cyclohexyl carbaldehyde, benzaldehyde, 1-naphthyl aldehyde, 2-naphthyl aldehyde, styryl aldehyde, and the like. As the aldehyde compound, a depolymerizable polymer precursor can be used, and the aldehyde group may be protected with an acetal group or a hemiacetal group.

  Among the aldehyde compounds represented by the formula (2), formaldehyde and acetaldehyde are particularly preferable, and formaldehyde is particularly preferable. As formaldehyde, paraformaldehyde which is a depolymerizable polymer or formalin which is an aqueous solution can also be used.

  Although the condensation method of the compound represented by Formula (1) and the aldehyde compound represented by Formula (2) is not specifically limited, For example, by using an acid catalyst or an alkali catalyst in the presence or absence of a reaction solvent. Can be achieved. The reaction temperature is 0 to 200 ° C., preferably 50 to 150 ° C., and the reaction time is 0.1 to 30 hours, preferably 1 to 20 hours. Examples of the acid catalyst include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, malonic acid, and toluenesulfonic acid. Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, and carbonate. Examples thereof include sodium hydrogen, ammonia, tetramethylammonium hydroxide, triethylamine, morpholine, pyridine and the like.

  Examples of the reaction solvent used for the condensation include alcohols such as methanol, ethanol, isopropanol, and tertiary butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, and cyclohexyl ketone; propyl acetate, butyl acetate, Esters such as isobutyl acetate, methyl propionate, ethyl lactate, and propylene glycol acetate; ethers such as dibutyl ether, tetrahydrofuran, tetrahydropyran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, chloroform, and four Halogenated hydrocarbons such as carbon chloride and bromoform; hydrocarbons such as hexane, heptane, decane, and petroleum ether can be used. It can be mixed with use. In addition, water may coexist in the reaction system, and in the case of a solvent that is incompatible with water, a reaction solvent separated into two layers may be used. Water may be removed by distillation dehydration or the like.

  In the above examples of the condensation method, ketones, esters, aromatic hydrocarbons are used as reaction solvents, organic acids such as acetic acid, oxalic acid, malonic acid, toluenesulfonic acid, or ammonia, tetramethylammonium hydroxide, triethylamine It is preferable to use an alkali such as a catalyst. The catalyst may or may not dissolve in the reaction solvent used.

(B) is obtained by converting a part of the phenolic hydroxyl group of the novolak resin (a) obtained as described above into an OR ₃ group. Here, the R ₃ group is a monovalent organic group having 1 to 20 carbon atoms, and examples equivalent to R ₁ or R ₂ can be given.

（式中、Ｒ₃は前記と同等の定義である。Ｔはフッ素原子、塩素原子、臭素原子、ヨウ素原子、メシル基及びトシル基からなる群から選ばれる。）
式（６）で示される化合物は、使用するノボラック樹脂（ａ）のフェノール性水酸基１モル当量に対して、０．９９モル当量以下、好ましくは０．８モル当量以下、最も好ましくは０．５モル当量以下を使用する。
ここで、使用するノボラック樹脂（ａ）中のフェノール性水酸基のモル当量は、アルカリ滴定法を用いて求めることができる。 Examples of the reaction for replacing the phenolic hydroxyl group with an OR ₃ group include strong alkalis such as sodium hydroxide, potassium hydroxide, metallic sodium, metallic lithium, metallic potassium, n-butyllithium, sodium naphthalate, and sodium methoxide. It can be used by converting the phenolic hydroxyl group into a metal phenolate group and reacting the compound represented by the formula (6).

(In the formula, R ₃ has the same definition as above. T is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyl group, and a tosyl group.)
The compound represented by the formula (6) is 0.99 molar equivalents or less, preferably 0.8 molar equivalents or less, most preferably 0.5 molar equivalents with respect to 1 molar equivalent of the phenolic hydroxyl group of the novolak resin (a) used. Use molar equivalents or less.
Here, the molar equivalent of the phenolic hydroxyl group in the novolak resin (a) to be used can be determined using an alkali titration method.

  Specific examples of the compound represented by the formula (6) are methyl fluoride, ethyl fluoride, decyl fluoride, hexyl fluoride, octyl fluoride, dodecyl fluoride, hexadecyl fluoride, icosyl fluoride, methyl chloride, ethyl chloride. Decyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, hexadecyl chloride, icosyl chloride, methyl bromide, ethyl bromide, decyl bromide, hexyl bromide, octyl bromide, dodecyl bromide, hexadecyl bromide, icosyl bromide , Benzyl bromide, methyl iodide, ethyl iodide, decyl iodide, hexyl iodide, octyl iodide, dodecyl iodide, hexadecyl iodide, icosyl iodide, benzyl iodide, methyl ethyl sulfonate, methyl butyl sulfonate , Methyl octyl sulfonate, methyl decyl sulfonate, toluyl ethyl sulfonate, buty Acid toluyl, octyl sulfonic acid toluyl, cited toluic decyl sulfonate and the like, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide are preferred.

  Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, and tertiary butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, and cyclohexyl ketone; dibutyl ether, tetrahydrofuran, tetrahydropyran, and dioxane. Ethers such as benzene, toluene, xylene, etc .; hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, bromoform, etc .; hydrocarbons such as hexane, heptane, decane, petroleum ether, etc. These may be used alone or in combination of two or more. In particular, ethers, aromatic hydrocarbons or halogenated hydrocarbons are preferred. In the reaction, water may coexist as long as the reactant used is not deactivated, but a dehydrated solvent having a water content of 100 ppm or less is preferred. The reaction temperature is 0.1 to 20 hours, preferably 1 to 10 hours, and the reaction temperature is −60 to 100 ° C., preferably −20 to 50 ° C.

In particular, (A) of the present invention is particularly preferably a phenol novolak resin or a cresol novolak resin obtained by polymerizing formaldehyde with a compound in which R ₁ in formula (1) is a hydrogen atom or a methyl group. Phenol novolac resins or cresol novolac resins can be preferably used because of high dissolution contrast. Moreover, the addition ratio of (A) used for the photosensitive composition of this invention becomes like this. Preferably it is 39.9-90 mass% with respect to the photosensitive composition whole quantity, More preferably, it is 50-80 mass%. is there.

The alkali-soluble resin obtained as described above contains the catalyst or catalyst residue used in the condensation reaction or conversion reaction, the unreacted phenol compound represented by the formula (1), and the unreacted aldehyde represented by the formula (2). It is preferable to remove the compound or the unreacted compound represented by the formula (6) by a known method.
In particular, in order to apply to the radiation-sensitive resin of the present invention, it is preferable to remove the highly volatile component contained in (A) after producing (A). Preferably, the highly volatile component contained in (A) is preferably 0.4% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.2% by mass. 0.1 mass% is particularly preferable.

  The polystyrene-converted weight average molecular weight of the alkali-soluble resin (A) by gel permeation (GPC) method is preferably 350 to 30,000, more preferably 350 to 10,000. When the weight average molecular weight is in the above range, the curability of the exposed area tends to be high, the solubility of the unexposed area tends to be high, and the pattern formation characteristics tend to be favorable, which is preferable.

Next, the epoxy-containing silicon compound (B) will be described.
Here, Q ₂ and Q ₃ each independently represent a group having an epoxy group or an oxetane group represented by the formula (4). Here, Q ₂ and Q ₃ are glycidyl group, 1,2-epoxybutyl group, 1,2-epoxyhexyl group and the like when T ₁ is an alkylene group, and when T ₁ is an alkyleneoxyalkylene group. , Glycidyloxyethyl group, glycidyloxypropyl group, glycidyloxybutyl group, 1,3-epoxybutyl group, 1,3-epoxyhexyl group. When T ₁ is a phenylene group, examples of Q ₂ and Q ₃ include a 1,2-epoxyethylphenyl group and a 1,3-epoxypropylphenyl group. In particular, the case where T ₁ is an alkyleneoxyalkylene group is preferable since it is simple in production, and a glycidyloxypropyl group is particularly preferable.
Q ₁ is a divalent group having one or two silicon atoms represented by the formula (5), and is a dimethylsilanediyl group, diphenylsilanediyl group, 1,1,3,3-tetramethyldisiloxanediyl. Group, 1,1,3,3-tetraphenyldisiloxanediyl group, 1,1,3,3-tetramethyldisilamethylenediyl group, phenylenebis (dimethylsilylene) group and the like.

（式中、Ｔ₁、ｍは上記一般式（４）と同等の定義である。Ｔ₁₀、Ｔ₂₀はそれぞれ独立にメチル基又はフェニル基を表す。Ｒ₁₀は水素原子であるか、１価の有機基である。） Specific examples of the method for producing the compound represented by the general formula (3) include a method in which the silanol group or the alkoxysilyl group of the compound represented by the general formula (7) is hydrolyzed and condensed.

(In the formula, T ₁ and m have the same definitions as in the general formula (4). T ₁₀ and T ₂₀ each independently represent a methyl group or a phenyl group. R ₁₀ is a hydrogen atom or a monovalent group. Organic group.)

（式中、Ｔ₂〜Ｔ₇は上記の一般式（５）又は一般式（６）と同等の定義である。）

（式中、ｍは一般式（４）と同等の定義であり、Ｔ１０は直接結合、炭素数１〜４のアルキレン基、炭素数２〜４のアルキレンオキシアルキレン基を表す。） Further, the compound represented by the general formula (5a) or the compound represented by the general formula (6a) and the compound represented by the general formula (8) are subjected to an addition reaction using chloroplatinic acid or the like as a catalyst. However, the epoxy-containing silicon compound (B) can be easily produced.

(In the formula, T _{2 to} T ₇ have the same definition as the above general formula (5) or general formula (6).)

(In the formula, m is the same definition as in the general formula (4), and T10 represents a direct bond, an alkylene group having 1 to 4 carbon atoms, and an alkyleneoxyalkylene group having 2 to 4 carbon atoms.)

  In order to apply to the radiation sensitive resin of the present invention, it is preferable to remove the highly volatile component contained in (B) after producing (B). Preferably, the highly volatile component contained in (B) is preferably 0.4% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.2% by mass. 0.1 mass% is particularly preferable.

Among the above examples, 1,3-di (3′-glycidyloxypropyl) -1,1,3,3, -tetramethyldisiloxane is particularly preferable as (B). 1,3-di (3′-glycidyloxypropyl) -1,1,3,3, -tetramethyldisiloxane is readily available from the market for use as an epoxy resin modifier, such as Rhodel PC-606PEX made from PC etc. can be mentioned.
In addition, 1,3-di (3′-glycidyloxypropyl) -1,1,3,3, -tetramethyldisiloxane, which can be easily obtained from the market, is usually purified by distillation under reduced pressure. There is almost no volatile component. From such a viewpoint, it is suitable for application to the radiation-sensitive resin composition of the present invention.

  The addition ratio of (B) used for the radiation sensitive resin composition of this invention becomes like this. Preferably it is 9.9-60 mass% with respect to the photosensitive composition whole quantity, More preferably, it is 20-50 mass%. is there.

Next, (C) a compound that generates an acid upon irradiation with radiation will be described.
Here, the definition of “radiation” is the definition of “electromagnetic wave or particle beam” as described in the Dictionary of Chemistry (edited by Michinori Ohki et al., Page 2205, Tokyo Kagaku Dojin, Vol. 7, published on July 1, 2005). It is a generic name. Examples of the electromagnetic wave include microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, and γ rays. Examples of the particle beam include an α particle beam, an electron beam, and a neutron beam. (C) applied to the present invention is a compound capable of generating an acid by the action of electromagnetic rays or particle rays selected from these. Among these radiations, ultraviolet rays, visible rays, electron beams, and the like used for general-purpose semiconductor processing exposure apparatuses used in an exposure process described later are preferable. Specific examples include a photo acid generator and a photo cationic polymerization initiator.

  Examples of the photoacid generator include [cyclohexyl- (2-cyclohexanonyl) -methyl] sulfonium trifluoromethanesulfonate, bis (p-tolylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and tertiary butylcarbonylmethyl. -Tetrahydrothiophenium trifluoromethanesulfonate etc. are mentioned. As the photoacid generator, in addition to the above, compounds described in JP-A-11-202495 can also be used.

  Examples of the photocationic polymerization initiator include iodonium salts, sulfonium salts, phosphate salts, and antimonate salts. Specifically, Rhodesyl Photoinitiator 2074 (manufactured by Rodel), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172 (all Asahi Denka Kogyo Co., Ltd.) Etc.). In addition, compounds described in JP-A-9-118663 can also be used.

  Content of (C) with respect to the photosensitive composition of this invention becomes like this. Preferably it is 0.1-20 mass% with respect to the said composition whole quantity, More preferably, it is 1-15 mass%. When the content of (C) is in the above range, there is a tendency that a pattern can be formed with good productivity, which is preferable.

Moreover, it is suitable to reduce the highly volatile component contained in (C) like (A) and (B). Here, since any of the compounds suitable for (C) exemplified above is a compound that is easily denatured by heating, a highly volatile component contained in (C) can be obtained using a technique such as freeze drying or reduced pressure drying. Is preferably reduced. The highly volatile component contained in (C) is preferably 0.4% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.2% by mass, 0.1% by mass is particularly preferable.

The radiation sensitive resin composition of this invention contains said (A), (B) and (C), and a highly volatile component is 0.5 mass% or less. As described above, in order to reduce the highly volatile component to 0.5% by mass or less, the components (A), (B) and (C) are each reduced in the highly volatile component as described above. This can be achieved by controlling the ratio.
Moreover, after mixing (A), (B) and (C) to make a composition, the highly volatile component contained in the total amount of the composition is reduced to 0.5 by removing the highly volatile component from the composition. It is also possible to control the mass% or less. Thus, in order to remove highly volatile components from the composition, a technique such as freeze drying or reduced pressure drying exemplified in the case of (C) may be used.
The radiation-sensitive resin composition may contain 0.5% by mass or less of highly volatile components contained in the total amount thereof, but is preferably 0.3% by mass or less, and more preferably 0.2% by mass. More preferably, it is 0.1 mass% or less, Most preferably, it is 0.05 mass% or less. In particular, it is preferable that substantially no highly volatile components are contained in the total amount of the radiation-sensitive resin composition.

  Thus, it is preferable that the radiation sensitive resin composition which made the highly volatile component 0.5 mass% or less has the 0.5% weight reduction temperature which concerns on a thermogravimetric analysis in the range of 100-250 degreeC. According to the thermogravimetric analysis, even if the content of highly volatile components in the composition is increased by absorbing moisture in the atmosphere, the wiring pattern formation described later is controlled to 0.5% by mass or less. Can be used for

Furthermore, additives such as a light absorber, a photosensitizer, a plasticizer, and a leveling agent may be added to the radiation-sensitive resin composition of the present invention as necessary. If it is a range hold | maintained at 5 mass% or less, it will not specifically limit.
Even such an additive is more preferable when (D) a photosensitizer is included. Examples of the photosensitizer include aromatic compounds such as perylene, pyrene, anthracene, benzanthracene, and phenothiazine, aromatic carbonyl compounds such as thioxanthone, benzophenone, fluorene, and anthraquinone, or the aromatic compound and the aromatic carbonyl compound. Examples thereof include compounds in which an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms are substituted. The photosensitizer is preferably a compound that can be easily obtained from the market. Examples thereof include DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.). Moreover, it is preferable to manage the highly volatile component contained in the photosensitizer illustrated by these to 0.4 mass% or less.

  Next, an example is given and demonstrated about the method of patterning using the radiation sensitive resin composition of this invention, However, This invention is not limited to these methods.

First, a radiation-sensitive resin composition is applied over the entire surface or partially under normal pressure (about 1 atm) or reduced pressure on a substrate. Here, “applying under reduced pressure” applies, for example, a vacuum coating apparatus described in Japanese Patent Application Laid-Open No. 2001-267339, and the vacuum degree of the vacuum coating apparatus is usually 25000 Pa or more. is there.
As a coating method, for example, a coating method such as a spin coater, a bar coater, a roll coater, a die coater, or screen printing, or a coating apparatus according to these coating methods is mounted in a chamber set at the above-described vacuum degree. A placed vacuum coating device can be used. The coating thickness can be adjusted by selecting the number of coatings and the viscosity of the radiation sensitive resin composition. The radiation-sensitive resin composition of the present invention can form a coating film having a thickness of up to 250 μm, but usually about 5 to 50 μm is sufficient.

  Here, the vacuum coating apparatus is an apparatus that has been attracting attention as an apparatus that can be applied while removing bubbles from the film obtained from the liquid sealing material as a packaging technique using a thick liquid sealing material. It is. However, since the thick film resists disclosed so far usually use a low-boiling organic solvent as a coating aid, it is extremely difficult to maintain the coating property under reduced pressure. There was no example where the film resist was applied. Although the radiation-sensitive resin composition of the present invention has a thixotropy capable of being spin-coated, the highly volatile component that impairs the coating property by the vacuum coating method is extremely low. Even if it is used, it is possible to apply a radiation-sensitive resin film.

Moreover, when apply | coating a radiation sensitive resin composition on a board | substrate, in order to improve the adhesiveness of a board | substrate and a coating film, the board | substrate surface can be processed with a surface treatment liquid.
Examples of the surface treatment liquid include silane coupling agents such as glycidyloxypropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, and oxetanyloxypropyltriethoxysilane. As the silane coupling agent, it is preferable to use a silane coupling agent diluted to a concentration of 0.1 to 5% with an organic solvent such as ethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol.

  Examples of the surface treatment method include a method in which a surface treatment liquid is uniformly applied on a substrate with a spinner or the like and then dried at 80 to 140 ° C. for 5 to 60 minutes. As a drying method, a hot plate, a far-infrared oven, or the like is preferable.

  Thus, a coating film (radiation sensitive resin film) obtained from the radiation sensitive resin composition is obtained on the substrate. The radiation-sensitive resin film is suitable as a wiring forming material in which a wiring pattern is formed on the surface by irradiation with radiation, which will be described later, and the wiring pattern functions as a sacrificial film to form a metal wiring on the substrate .

Next, a method for forming a wiring pattern on the radiation sensitive resin film will be described.
As described above, a radiation-sensitive resin film is obtained on the substrate, and the film is exposed (radiation irradiation) using an exposure apparatus. Examples of the exposure apparatus include a proximity exposure machine.

  When performing exposure of a large area, a radiation-sensitive resin composition is applied onto a substrate to obtain a radiation-sensitive resin film, and then exposure is performed while moving the substrate. With an exposure machine, a large area can be exposed. Further, at the time of exposure, the wiring pattern of the mask pattern is transferred to the radiation-sensitive resin film by irradiating the radiation-sensitive resin film with radiation through a mask pattern having a desired wiring pattern. Further, the mass pattern can be reduced and projected using a lens.

  The exposure dose in the exposure can be optimized as appropriate depending on the type of exposure source used or the type of (C) used in the radiation-sensitive resin composition. As long as the effect is not disturbed, it does not matter.

Particularly preferably, using the wavelength 365nm of light source using a high pressure mercury lamp as an exposure source, the temperature is achieved at room temperature (25 ± 5 ℃) under exposure amount ^{10mJ / cm 2 ~2000mJ / cm 2} .

  Development is performed after exposure. By this development, unexposed portions are dissolved and removed, and a pattern obtained from the radiation-sensitive resin composition is formed on the substrate. The developing method is usually performed by a dipping method, a spray method, a brush method or the like.

  Examples of the developer include aqueous alkali solutions such as tetramethylammonium hydroxide, monoethanolamine, diethanolamine, sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.

  The alkali concentration in the aqueous solution is preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass. When the alkali concentration is within the above range, the removability of the portion to be developed and removed is good, and the pattern to be left is less likely to be peeled off or eroded.

  The temperature during development is preferably 15 to 50 ° C. in terms of process control. Moreover, you may perform water washing, drying, etc. after image development as needed.

After the pattern is formed as described above, the wiring pattern can be formed by embedding the wiring material in the concave portion of the pattern. Examples of the burying method include a sputtering method and a plating method.
As the wiring material, copper or copper alloy is usually used.

After embedding the wiring material, the wiring pattern made of the wiring material can be obtained by removing the pattern obtained from the radiation-sensitive resin composition of the present invention. Since the wiring pattern obtained in this way has no wiring defects such as bubbles and loss of shape in the pattern obtained from the radiation-sensitive resin composition that is a sacrificial film, the desired wiring pattern can be defective. You can get without.
Here, as a method for removing the pattern obtained from the radiation-sensitive resin composition, plasma ashing, resist stripper treatment or the like can be usually performed.

  Thus, since the metal wiring pattern obtained on the substrate is a thick film and has almost no pattern defects, it can be suitably used for protruding electrodes, bumps, and the like related to the rewiring process of semiconductor device manufacturing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Example 1
10 g of phenol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4261), 1,3-di (3′-glycidyloxypropyl) -1,1,3,3, -tetramethyl-disiloxane (Rodel) Made of PC-606PEX), 1.5 g of Rhodosyl photoinitiator (Rodel, PI-2074), 0.3 g of sensitizer (manufactured by Kawasaki Kasei Kogyo Co., Ltd., DBA) was placed in a 200 ml eggplant flask. A uniform radiation-sensitive resin composition was prepared by heating and stirring. Here, as a result of measuring moisture in the phenol novolak resin by the Karl Fischer method (KF method), it was 0.06% by mass, and the amount of moisture brought into the composition was 0.04% by mass or less. Met. Since other highly volatile components were not substantially detected, the highly volatile component of the composition is 0.5% by mass or less.

  The prepared radiation sensitive resin composition was applied on a silicon wafer using a spin coater while heating to obtain a radiation sensitive resin film.

Next, the film was exposed with a proximity exposure machine (manufactured by Dainippon Screen Mfg. Co., Ltd .; MAP-1300) using a 50 μm line, 230 μm pitch mask. The irradiation exposure dose was 100 mJ / cm ² . After exposure, after baking at 60 ° C. for 10 minutes and further at 100 ° C. for 30 minutes, development with a 0.3 wt% aqueous sodium hydroxide solution results in a pattern with a pattern upper width of 59 μm, pattern lower width of 66 μm, and height of 35 μm. It was. The appearance of the obtained pattern was observed with a scanning electron microscope (SEM). As a result, defects such as bubbles and loss of shape were not recognized in the pattern.

Claims (6)

A radiation-sensitive resin composition containing the following (A), (B) and (C), and containing 0.5% by mass or less of a compound having a boiling point of 250 ° C. or less at 1 atm in the total amount of the composition.
(A) An alkali-soluble resin represented by the following (a) and / or (b) (a) A novolak resin obtained by condensing a phenol compound represented by formula (1) and an aldehyde compound represented by formula (2)

(Wherein, n .R ₁ representing one of 0, 1, 2 represents a monovalent organic group having 1 to 20 carbon atoms, when R ₁ is present in plurality, each be the same or different May be.)

(Wherein R ₂ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)
(B) A resin obtained by substituting a part of the phenolic hydroxyl group of the novolak resin (a) with an OR ₃ group (where R ₃ represents a monovalent organic group having 1 to 20 carbon atoms).
(B) Epoxy-containing silicon compound represented by formula (3)

(In the formula, Q ₂ and Q ₃ are each independently a group represented by the formula (4), and Q ₁ is selected from a group represented by the formula (5) or a group represented by the formula (6)). .)

(In the formula, T ₁ represents an alkylene group having 1 to 6 carbon atoms, an alkyleneoxyalkylene group having 2 to 6 carbon atoms, or a phenylene group. M is 0 or 1.)

(Wherein, T ₂ through T ₇ are each independently selected from .T ₈ oxygen atoms that represents a methyl group or a phenyl group, a methylene group, ethenylene group, ethynylene group, a phenylene group, a naphthalene-diyl group or a biphenyl-diyl group .)
(C) Compound that generates acid upon irradiation   The radiation sensitive resin composition of Claim 1 containing (A) 39.9-90 mass%, (B) 9.9-60 mass%, and (C) 0.1-20 mass%.   The radiation sensitive resin composition of Claim 1 or 2 whose 0.5% weight reduction | decrease temperature in a thermogravimetric analysis is 100-250 degreeC.   Furthermore, the radiation sensitive resin composition in any one of Claims 1-3 containing a photosensitizer (D).   The wiring formation material which uses the radiation sensitive resin composition in any one of Claims 1-4. A semiconductor device having a metal wiring formed using the wiring forming material according to claim 5.