JP2006227063A - Positive photosensitive resin composition, method for manufacturing pattern, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having excellent sensitivity and resolution, high adhesiveness and heat resistance and solving problems of a conventional photoresist by using a resin composition having excellent heat resistance and other various characteristics and showing a high transmittance in a UV and visible ray region and low residual stress, and by using a photosensitive agent and an additive. <P>SOLUTION: The positive photosensitive resin composition comprises: (a) a polybenzoxazole precursor having an amide unit soluble in alkali aqueous solution and having a repeating unit expressed by general formula (I), wherein j and k in formula (I) satisfy 0.01≤k/(j+k)<1 (in formula (I), U represents a tetravalent organic group, and each of V and W represents a divalent organic group); (b) a compound which generates an acid by light; and (c) a solvent. The invention also provides a method for manufacturing a pattern, and an electronic component using the above composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat-resistant positive photosensitive resin composition containing a photosensitive polyoxazole precursor, a pattern production method using the same, and an electronic component.

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. However, in recent years, as semiconductor devices have been highly integrated and increased in size, there has been a demand for thinner and smaller sealing resin packages, and LOC (lead-on-chip) and surface mounting methods such as solder reflow have been adopted. Therefore, a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.

On the other hand, photosensitive polyimide having a photosensitive property imparted to the polyimide resin itself has been used. However, when this is used, the pattern creation process can be simplified and complicated manufacturing processes can be shortened. A heat-resistant photoresist using a conventional photosensitive polyimide or its precursor and its application are well known. In the negative type, a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, see Patent Documents 1 to 4), a soluble polyimide having a photopolymerizable olefin (for example, see Patent Documents 5 to 10) ), A self-sensitized polyimide having a benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (see, for example, Patent Documents 11 and 12).

  Since the above negative type requires an organic solvent such as N-methylpyrrolidone for development, a positive photosensitive resin that can be developed with an aqueous alkaline solution has recently been proposed. In the positive type, a method in which an o-nitrobenzyl group is introduced into a polyimide precursor via an ester bond (for example, see Non-Patent Document 1), a method in which a naphthoquinonediazide compound is mixed in a soluble hydroxylimide or polyoxazole precursor (for example, Patent Documents 13 and 14), a method of introducing naphthoquinone diazide into a soluble polyimide via an ester bond (for example, see Non-Patent Document 2), and a method in which naphthoquinone diazide is mixed into a polyimide precursor (for example, see Patent Document 15) and so on.

  However, the negative type has a problem in resolution due to its function, and in some applications, there is a problem in that the yield in manufacturing is reduced. In addition, since the structure of the polymer to be used is limited in the above, the physical properties of the finally obtained film are limited, which is not suitable for multipurpose use. On the other hand, the positive type also has the same problems because the sensitivity and resolution are low and the structure is limited due to the problem with the absorption wavelength of the photosensitive agent as described above.

  Also, carboxylic acids such as polybenzoxazole precursor mixed with a diazonaphthoquinone compound (see, for example, Patent Document 16), or polyamic acid having a phenol moiety introduced via an ester bond (for example, see Patent Document 17). Instead of these, phenolic hydroxyl groups have been introduced, but these have insufficient developability, resulting in film loss at unexposed areas and peeling of the resin from the substrate. For the purpose of improving developability and adhesion, a mixture of polyamic acids having a siloxane moiety in the polymer skeleton has been proposed (for example, see Patent Documents 18 and 19). Storage stability deteriorates due to use. In addition, for the purpose of improving storage stability and adhesion, amine end groups sealed with a polymerizable group (see, for example, Patent Documents 20 to 22) have also been proposed. Since a diazoquinone compound containing a large number of aromatic rings is used as a low-sensitivity, it is necessary to increase the addition amount of the diazoquinone compound, and there is a problem that the mechanical properties after thermosetting are remarkably lowered, and it is difficult to say that the material is at a practical level. Is.

  In order to improve the problems of the diazoquinone compound, those using various chemical amplification systems have been proposed. Chemically amplified polyimides (for example, see Patent Document 23), chemically amplified polyimides or polybenzoxazole precursors (for example, see Patent Documents 24 to 30) are mentioned. The deterioration of the induced film characteristics, which are excellent in the film characteristics, show a decrease in sensitivity due to insufficient solubility due to the high molecular weight, and it is difficult to say that both are materials at a practical level. Therefore, in reality, none of them is sufficient for practical use.

  In addition, the diameter of the silicon wafer, which is the substrate, increases year by year, and the warpage of the silicon wafer after forming the surface protective film becomes larger than before due to the difference in thermal expansion coefficient between the polyimide or polybenzoxazole precursor and silicon. It has occurred. Therefore, there is a strong demand for a photosensitive polyimide or polybenzoxazole precursor that reduces the warpage of the silicon wafer further than the conventional polyimide or polybenzoxazole precursor. Generally, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, the i-line is hardly transmitted, so that the photosensitive property is lowered.

Japanese Patent Laid-Open No. 49-11541 Japanese Patent Laid-Open No. 50-40922 JP 54-145794 A JP-A-56-38038, etc. JP 59-108031 A JP 59-220730 A JP 59-232122 A Japanese Unexamined Patent Publication No. 60-6729 JP-A-60-72925 JP 61-57620 A, etc. JP 59-219330 A JP-A-231533 Japanese Examined Patent Publication No. 64-60630 US Pat. No. 4,395,482 JP 52-13315 A JP-A-1-46862 JP-A-10-307393 JP-A-4-31861 Japanese Patent Laid-Open No. 4-46345 JP-A-5-197153 JP-A-9-183846 JP 2001-183835 A Japanese Patent Laid-Open No. 3-763 JP 7-219228 A Japanese Patent Laid-Open No. 10-186664 Japanese Patent Laid-Open No. 11-202489 JP 2000-56559 A JP 2001-194791 A JP 2002-526793 A US Pat. No. 6,143,467

J. et al. Macromol. Sci. Chem. , A24, 10, 1407, 1987 Macromolecules, 23, 4796, 1990

  The present invention has excellent heat resistance and other characteristics, exhibits high transmittance in the ultraviolet and visible light range, and uses a photosensitizer and an additive with a resin composition that exhibits low residual stress. The present invention provides a positive photosensitive resin composition that is excellent in resolution, solves the above-mentioned problems of conventional photoresists, and is excellent in adhesion and heat resistance.

  The present invention also provides a method for producing a pattern that can be developed with an alkaline aqueous solution by using the above composition and that has a good sensitivity, resolution, and heat resistance, and that has a good shape. Furthermore, the present invention provides a highly reliable electronic component having a low residual stress surface protective film or interlayer insulating film.

（式中、Ｕは４価の有機基を示し、Ｖ、Wは２価の有機基を示す）で表される一般式(I)のjとkが0.01≦k/(j+k)< 1を満たす繰り返し単位を有するアルカリ水溶液可溶性のアミドユニットを持つポリベンゾオキサゾール前駆体、（ｂ）光により酸を発生する化合物、並びに、（ｃ）溶剤を含有してなるポジ型感光性樹脂組成物。
[2] （a）成分のWが一般式(II)で表される[1]に記載のポジ型感光性樹脂組成物。

(式中、Mは単結合又は２価の有機基を示し、R₁及びR₂は各々独立に一価の有機基で、ｒ及びsは各々独立に0〜4の整数であり、Ｗの二つの結合手はそれぞれ、式中の異なるベンゼン環上に存在する。)
[3] （a）成分のWが一般式(III)で表される

(式中、Xは２価の有機基を示し、R₁及びR₂は各々独立に一価の有機基で、ｒ及びsは各々独立に0〜4の整数であり、Ｗの二つの結合手はそれぞれ、式中の異なるベンゼン環上に存在する。)[1]に記載のポジ型感光性樹脂組成物。
[4] （a）成分のWが一般式(IV)で表され、nが1〜100の整数である[1]に記載のポジ型感光性樹脂組成物。

(R₃, R₈は二価の有機基、R₄〜R₇は各々独立に一価の有機基である。)
[5] （a）成分のWが一般式(IV)で表され、nが1〜30の整数である[4]に記載のポジ型感光性樹脂組成物。
[6] （a）一般式（Ｉ）で表される一般式(I)のjとkが0.03≦k/(j+k)< 0.6を満たす繰り返し単位を有するアルカリ水溶液可溶性の芳香族ポリアミドである[１]〜[4]のいずれかに記載のポジ型感光性樹脂組成物。
[7]上記、ポジ型感光性樹脂組成物がさらに(d)フェノール性水酸基を有する化合物、(e)アルカリ水溶液に対する(a)成分の溶解を抑制する化合物を含むことを特徴とする[１]〜[６]のいずれかに記載のポジ型感光性樹脂組成物。
[8]（ａ）成分１００重量部に対して、（ｂ）成分５〜１００重量部、（d）成分１〜３０重量部、（e）成分０．０１〜１５重量部を配合する[１]〜[７]のいずれかに記載のポジ型感光性樹脂組成物。
[9][１]〜[８]のいずれかに記載のポリアミドを脱水閉環して形成されるポリベンゾオキサゾール。
[10][１]〜[８] のいずれかに記載のポジ型感光性樹脂組成物を支持基板上に塗布し乾燥する工程、前記乾燥工程により得られた感光性樹脂膜を露光する工程、前記露光後の感光性樹脂膜を加熱する工程、前記加熱後の感光性樹脂膜をアルカリ水溶液を用いて現像する工程、及び前記現像後の感光性樹脂膜を加熱処理する工程を含むパターンの製造法。
[11][10] に記載の製造方法により得られるパターンの層を有してなる電子デバイスを有する電子部品であって、前記電子デバイス中に前記パターンの層が層間絶縁膜層又は表面保護膜として設けられることを特徴とする電子部品。 The present invention relates to the following.
[1] (a) General formula (I)

(Wherein U represents a tetravalent organic group, and V and W represent a divalent organic group) j and k in the general formula (I) represented by 0.01 ≦ k / (j + k) < A positive-type photosensitive resin composition comprising a polybenzoxazole precursor having an amide unit soluble in an alkaline aqueous solution having a repeating unit satisfying 1, a compound that generates an acid by light, and (c) a solvent. .
[2] The positive photosensitive resin composition according to [1], wherein W of component (a) is represented by general formula (II).

(In the formula, M represents a single bond or a divalent organic group, R ₁ and R ₂ are each independently a monovalent organic group, r and s are each independently an integer of 0 to 4, Each of the two bonds is on a different benzene ring in the formula.)
[3] W of component (a) is represented by general formula (III)

(Wherein X represents a divalent organic group, R ₁ and R ₂ are each independently a monovalent organic group, r and s are each independently an integer of 0 to 4, and two bonds of W Each hand is present on a different benzene ring in the formula.) The positive photosensitive resin composition according to [1].
[4] The positive photosensitive resin composition according to [1], wherein W of component (a) is represented by general formula (IV), and n is an integer of 1 to 100.

(R ₃ and R ₈ are divalent organic groups, and R _{4 to} R ₇ are each independently a monovalent organic group.)
[5] The positive photosensitive resin composition according to [4], wherein W of component (a) is represented by general formula (IV), and n is an integer of 1 to 30.
[6] (a) an aromatic aqueous solution-soluble aromatic polyamide having a repeating unit in which j and k in the general formula (I) represented by the general formula (I) satisfy 0.03 ≦ k / (j + k) <0.6 The positive photosensitive resin composition according to any one of [1] to [4].
[7] The positive photosensitive resin composition further includes (d) a compound having a phenolic hydroxyl group, and (e) a compound that suppresses dissolution of the component (a) in an alkaline aqueous solution [1] -Positive photosensitive resin composition in any one of-[6].
[8] (b) component 5 to 100 parts by weight, (d) component 1 to 30 parts by weight, and (e) component 0.01 to 15 parts by weight per 100 parts by weight of component (a) [1 ] The positive photosensitive resin composition in any one of [7]-[7].
[9] Polybenzoxazole formed by dehydrating and ring-closing the polyamide according to any one of [1] to [8].
[10] A step of applying and drying the positive photosensitive resin composition according to any one of [1] to [8] on a support substrate, a step of exposing the photosensitive resin film obtained by the drying step, Production of a pattern including a step of heating the photosensitive resin film after the exposure, a step of developing the photosensitive resin film after the heating using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development Law.
[11] An electronic component having an electronic device having a pattern layer obtained by the manufacturing method according to [10], wherein the layer of the pattern is an interlayer insulating film layer or a surface protective film in the electronic device An electronic component characterized by being provided as

  The positive photosensitive resin composition of the present invention uses a resin, a photosensitive agent, and an additive having excellent heat resistance and other characteristics, high transmittance in the ultraviolet and visible light range, and low residual stress. It is excellent in sensitivity and resolution. Moreover, according to the method for producing a pattern of the present invention, by using the composition, a pattern having a good shape and excellent sensitivity, resolution, adhesiveness and heat resistance can be obtained. In addition, the electronic component of the present invention is highly reliable because it has a good shape and a pattern with excellent adhesion and heat resistance.

  The polybenzoxazole precursor of the present invention can be obtained by reacting a diamine with a dicarboxylic acid derivative and a hydroxy group-containing diamine as a raw material to obtain an alkali-soluble polymer, which is compatible with both photosensitive properties and high cured film properties. Is possible. Moreover, since the amide unit produced | generated by reaction of diamine and dicarboxylic acid derivative has high light transmittance in i line | wire area | region, it is preferable at the point which can expect a big improvement in light transmittance by introduce | transducing the amide unit. Diamines are easier to produce and obtain monomers as raw materials than hydroxy group-containing diamines, and a wide variety of alkali-soluble polybenzoxazole precursors can be obtained by copolymerizing diamines.

（式中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。ｊとｋは、モル分率を示し、ｊとｋの和は１００モル％であり、ｊが1〜９９モル％、ｋが1〜９９モル％である）で表されるポリアミドである。ここで、式中のｊとｋのモル分率は、ｊ＝４０〜９７モル％、ｋ＝６０〜３モル％であることがアルカリ溶解性の点でより好ましい。 A polybenzoxazole precursor having an amide unit having a repeating unit having a repeating unit represented by the general formula (I) used in the present invention,
That is, the following formula

(In the formula, U represents a tetravalent organic group, V and W represent a divalent organic group, j and k represent a mole fraction, and the sum of j and k is 100 mol%, j Is 1 to 99 mol%, and k is 1 to 99 mol%). Here, the molar fraction of j and k in the formula is more preferably j = 40 to 97 mol% and k = 60 to 3 mol% from the viewpoint of alkali solubility.

  The component (a) having a repeating unit represented by the general formula (I) in the present invention is a polybenzoxazole precursor having an amide unit soluble in an alkaline aqueous solution. In addition, alkaline aqueous solution is alkaline solutions, such as tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution. The amide unit containing a hydroxy group represented by the general formula (I) is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure at the time of curing.

  The molecular weight of the component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. Here, the molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  In the present invention, a polybenzoxazole precursor having an amide unit having a repeating unit represented by formula (I) can be synthesized from a dicarboxylic acid derivative, a hydroxy group-containing diamine and a diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the two kinds of diamines. As the dihalide derivative, a dichloride derivative is preferable.

  The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorination reaction of carboxylic acid can be used.

  As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

  The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol relative to the dicarboxylic acid derivative. When making it react in an agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction of the dichloride derivative with hydroxy group-containing diamines and diamines is preferably carried out in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

  In the present invention, the divalent organic group represented by W in formula (I) generally reacts with a dicarboxylic acid to form a polyamide structure. It is preferable to have a structure represented by the general formula (II) as a diamine that has heat resistance and improves i-line permeability.

(式中、Mは単結合又は２価の有機基を示し、R₁及びR₂は各々独立に一価の有機基で、ｒ及びsは各々独立に0〜4の整数であり、Ｗの二つの結合手はそれぞれ、式中の異なるベンゼン環上に存在する。)
ここで、Mで示される２価の有機基としては−ＣＨ_２−，−Ｃ（ＣＨ_３）_２−，−Ｏ−，−Ｓ−，−ＳＯ_２−，−ＣＯ−，−（ＣＦ_３）_２−等が好ましいものとして挙げられる。
また、Ｒ_１及びＲ_２で示される一価の有機基としては、炭素数１〜１０の、アルキル基、アルキルエーテル基、フルオロアルキル基、フルオロアルキルエーテル基等が好ましいものとして挙げられる。ｒ及びｓの数としては、各々0〜4であることが好ましい。

(In the formula, M represents a single bond or a divalent organic group, R ₁ and R ₂ are each independently a monovalent organic group, r and s are each independently an integer of 0 to 4, Each of the two bonds is on a different benzene ring in the formula.)
Here, the divalent organic group represented by M is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, — (CF ₃ ). _2- and the like are preferable.
Moreover, as a monovalent organic group shown by R < ₁ > and R < ₂ >, a C1-C10 alkyl group, an alkyl ether group, a fluoroalkyl group, a fluoroalkyl ether group etc. are mentioned as a preferable thing. The number of r and s is preferably 0-4.

  As a divalent organic group represented by W in the general formula (I) in addition to the diamines, the diamine represented by the general formula (III) exhibits not only heat resistance and i-line permeability but also low residual stress. More preferable.

(式中、Xは２価の有機基を示し、R₁及びR₂は各々独立に一価の有機基で、ｒ及びsは各々独立に0〜4の整数であり、Ｗの二つの結合手はそれぞれ、式中の異なるベンゼン環上に存在する。)
ここで、Xで示される２価の有機基としては炭素数１〜１０の、アルキル基、フルオロアルキル基および

(Wherein X represents a divalent organic group, R ₁ and R ₂ are each independently a monovalent organic group, r and s are each independently an integer of 0 to 4, and two bonds of W Each hand is on a different benzene ring in the formula.)
Here, as the divalent organic group represented by X, an alkyl group, a fluoroalkyl group having 1 to 10 carbon atoms, and

等が好ましいものとして挙げられる。
また、Ｒ_１及びＲ_２で示される一価の有機基としては、炭素数１〜１０の、アルキル基、アルキルエーテル基、フルオロアルキル基、フルオロアルキルエーテル基等が好ましいものとして挙げられる。ｒ及びｓの数としては、各々0〜4であることが好ましい。

And the like are preferable.
Moreover, as a monovalent organic group shown by R < ₁ > and R < ₂ >, a C1-C10 alkyl group, an alkyl ether group, a fluoroalkyl group, a fluoroalkyl ether group etc. are mentioned as a preferable thing. The number of r and s is preferably 0-4.

  In the present invention, the divalent organic group represented by W in the general formula (I) and the structure represented by the general formula (IV) are preferable because they exhibit heat resistance, i-line permeability and low residual stress.

(R₃, R₈は二価の有機基、R₄〜R₇は各々独立に一価の有機基である。)
R₃, R₈の二価の有機基、R₄〜R₇の一価の有機基としては、炭素数１〜１０の、アルキル基、アルキルエーテル基、フルオロアルキル基、フルオロアルキルエーテル基およびフェニル基等が好ましいものとして挙げられる。
繰返し単位数nとしては1〜100が好ましく、膜質や高Tg性の点からnは1〜30がより好ましい。

(R ₃ and R ₈ are divalent organic groups, and R _{4 to} R ₇ are each independently a monovalent organic group.)
Examples of the divalent organic group represented by R ₃ and R _{8 and} the monovalent organic group represented by R _{4 to} R ₇ include an alkyl group, an alkyl ether group, a fluoroalkyl group, a fluoroalkyl ether group, and phenyl having 1 to 10 carbon atoms. Group etc. are mentioned as a preferable thing.
The number of repeating units n is preferably 1 to 100, and n is more preferably 1 to 30 from the viewpoint of film quality and high Tg property.

  The tetravalent organic group represented by U is generally a diamine having a structure in which two hydroxy groups, each reacting with a dicarboxylic acid to form a polybenzoxazole precursor structure, are located at the ortho positions of the amine. It is a residue and is preferably a tetravalent aromatic group. The number of carbon atoms is preferably 6 to 40, and more preferably a tetravalent aromatic group having 6 to 40 carbon atoms. As the tetravalent aromatic group, those in which all four bonding sites are present on the aromatic ring are preferable.

  Such hydroxy group-containing diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxy Phenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3 -Amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3 , 3-hexafluoropropane and the like, but are not limited thereto. These compounds can be used alone or in combination of two or more.

  In general formula (I), the divalent organic group represented by V is a dicarboxylic acid residue that reacts with diamine to form a polybenzoxazole precursor structure, and is a divalent aromatic group. The number of carbon atoms is preferably 6 to 40, and more preferably a divalent aromatic group having 6 to 40 carbon atoms. As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred.

  Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, Aliphatic systems such as 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid and succinic acid Although such a carboxylic acid is not limited thereto. These compounds can be used alone or in combination of two or more.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound may be blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. preferable. A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.

  In the positive photosensitive resin composition of the present invention, the blending amount of the component (b) is based on the difference in dissolution rate between the exposed and unexposed areas and the allowable range of sensitivity with respect to 100 parts by weight of the component (a). 5 to 100 parts by weight is preferable, and 8 to 40 parts by weight is more preferable.

  Examples of the solvent (c) used in the present invention include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide. Aprotic polar solvents such as tetramethylene sulfone and γ-butyrolactone are preferred, and these are used alone or in combination of two or more.

  The compound having a phenolic hydroxyl group, which is the component (d) used in the present invention, increases the dissolution rate of the exposed area when developing with an alkaline aqueous solution, thereby increasing the sensitivity. When the film is cured, the film can be prevented from melting. Although there is no restriction | limiting in particular in the compound which has a phenolic hydroxyl group which can be used for this invention, Since the melt | dissolution promotion effect of an exposure part will become small when molecular weight becomes large, a compound with a molecular weight of 1,500 or less is generally preferable. For example, the compounds represented by the following general formula (V) are particularly preferred because they are excellent in the balance between the effect of promoting dissolution of the exposed portion and the effect of preventing melting during curing of the film.

式中、Ｘは単結合又は２価の有機基を示し、Ｒはアルキル基又はアルケニル基を示し、Ｒ1及びＲ2は各々独立にアルキル基又はアルケニル基を示し、ｍ及びｎは各々独立に１又は２であり、ｐ及びｑは各々独立に０〜３の整数である）

In the formula, X represents a single bond or a divalent organic group, R represents an alkyl group or an alkenyl group, R 1 and R 2 each independently represents an alkyl group or an alkenyl group, and m and n each independently represents 1 or 2 and p and q are each independently an integer of 0 to 3)

  In the positive photosensitive resin composition of the present invention, the blending amount of the component (d) is 1 to 100 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of the development time and the allowable width of the unexposed part remaining film ratio. 30 parts by weight is preferable, and 3 to 25 parts by weight is more preferable.

  In the present invention, the component (e) used is a compound that inhibits the solubility of the component (a) in an alkaline aqueous solution. As such component (e), onium salts, diaryl compounds and tetraalkylammonium salts are preferred. Examples of the onium salt include iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts and aryldiazonium salts. Examples of the diaryl compound include those in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are bonded via a bonding group. Groups are preferred. Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group or an ethyl group.

  Among these, those showing a good dissolution inhibiting effect include diaryl iodonium salts, diaryl urea compounds, diaryl sulfone compounds, tetramethyl ammonium halide compounds, etc., and diaryl urea compounds include diphenyl urea, dimethyl diphenyl urea and the like. Examples of the tetramethylammonium halide compound include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

  Examples of the diaryliodonium salt include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, and diphenyliodonium. Bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like can be used.

  Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium-8-anilinonanaphthalene-1-sulfonate are preferable because of their high effects.

  The blending amount of the component (e) is preferably 0.01 to 30 parts by weight and more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of sensitivity and an allowable range of development time. Preferably, 0.05 to 3 parts by weight is more preferable.

  The positive photosensitive resin composition of the present invention can contain an organic silane compound, an aluminum chelate compound, or the like in order to enhance the adhesion of the cured film to the substrate. Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol , N-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldi) Droxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxy) And silyl) benzene. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like. When using these adhesion grant agents, 0.1-20 weight part is preferable with respect to 100 weight part of (A) component, and 0.5-10 weight part is more preferable.

  In addition, the positive photosensitive resin composition of the present invention may be added with an appropriate surfactant or leveling agent in order to prevent coating properties such as striation (film thickness unevenness) and improve developability. it can. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Megafax F171 is a commercially available product. , F173, R-08 (Dainippon Ink Chemical Co., Ltd. product name), Florard FC430, FC431 (Sumitomo 3M Co., Ltd. product name), Organosiloxane polymer KP341, KBM303, KBM403, KBM803 (Product made by Shin-Etsu Chemical Co., Ltd.) Name).

The positive photosensitive resin composition of the present invention can be formed into a polybenzoxazole pattern through a step of coating on a support substrate and drying, a step of exposing, a step of developing, and a step of heat treatment. In the step of applying and drying on the support substrate, the photosensitive resin composition is applied to the support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride with a spinner or the like. After spin coating, dry using a hot plate, oven, etc.

  Next, in the exposure step, the photosensitive resin composition formed as a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In the development process, the pattern is obtained by removing the exposed portion with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by weight. Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer.

  Next, in the heat treatment step, the resulting pattern is preferably heat-treated at 150 to 450 ° C. to form a heat-resistant polybenzoxazole pattern having an oxazole ring or other functional group.

  The positive photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, the surface protective film, interlayer insulating film of semiconductor devices, and interlayers of multilayer wiring boards are used. It can be used for forming an insulating film or the like. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

  An example of the manufacturing process of the semiconductor device of the present invention will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of polyimide resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coat method or the like (step (a)).

  Next, a chlorinated rubber-based or phenol novolak-based photosensitive resin layer 5 is formed on the interlayer insulating film 4 by spin coating, and a window is formed so that a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. 6A is provided (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

  Furthermore, the second conductor layer 7 is formed using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (step (d)). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

  Next, the surface protective film 8 is formed. In the example of this figure, this surface protective film is applied with the photosensitive resin composition by a spin coat method, dried, and irradiated with light from a mask on which a pattern for forming a window 6C is formed at a predetermined portion, and then an alkaline aqueous solution. A pattern is formed by developing at, and heated to form a polybenzoxazole film. This polybenzoxazole film protects the conductor layer from external stress, α rays, and the like, and the obtained semiconductor device is excellent in reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

  Hereinafter, the present invention will be described specifically by way of examples.

Synthesis Example 1 Synthesis of polybenzoxazole precursor having diamine unit In a 0.5 liter flask equipped with a stirrer and a thermometer, 19.94 g of isophthalic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C. Thereafter, 28.55 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of isophthalic acid chloride. Next, 110 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 25.64 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1,3-bis ( After adding 8.77 g of 4-aminophenoxy) benzene and dissolving with stirring, 18.98 g of pyridine was added, and the solution of isophthalic acid chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ° C., followed by stirring for 60 minutes. Continued. The solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain a diamine unit-containing polyhydroxyamide (hereinafter referred to as polymer I). The weight average molecular weight calculated | required by standard polystyrene conversion of the polymer I was 19800, and dispersion degree was 1.6.
Synthesis example 2
The same as Synthesis Example 1 except that 1,3-bis (4-aminophenoxy) benzene used in Synthesis Example 1 was replaced with 2,2-bis (4 ′-(4 ″ -aminophenoxy) phenyl) propane. The synthesis was performed under conditions. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 17700 and a dispersity of 1.5 determined by standard polystyrene conversion.
Synthesis example 3
Synthesis was performed under the same conditions as in Synthesis Example 1 except that 1,3-bis (4-aminophenoxy) benzene used in Synthesis Example 1 was replaced with 1,3-bis (3-aminopropyl) tetramethyldisiloxane. went. The obtained polyhydroxyamide (hereinafter referred to as polymer IIII) had a weight average molecular weight of 16,100 and a dispersity of 1.5 determined by standard polystyrene conversion.
Synthesis example 4
The synthesis was performed under the same conditions as in Synthesis Example 1 except that 1,3-bis (4-aminophenoxy) benzene used in Synthesis Example 1 was replaced with a diamine-terminated polysiloxane having a molecular weight of 1630. The resulting polyhydroxyamide (hereinafter referred to as polymer IV) had a weight average molecular weight of 17300 and a dispersity of 1.5 determined by standard polystyrene conversion.

Comparative Example Synthesis Example 5
In a 0.5 liter flask equipped with a stirrer and a thermometer, 19.94 g of isophthalic acid and 90 g of N-methylpyrrolidone were charged, and after the flask was cooled to 5 ° C., 28.55 g of thionyl chloride was added dropwise and reacted for 30 minutes. Thus, a solution of isophthalic acid chloride was obtained. Next, 110 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 36.63 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved by stirring. Thereafter, 18.98 g of pyridine was added, and the solution of isophthalic acid chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ° C., followed by stirring for 60 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain a diamine unit-containing polyhydroxyamide (hereinafter referred to as polymer V). The weight average molecular weight determined by standard polystyrene conversion of the polymer V was 15200, and the degree of dispersion was 1.5.
Synthesis example 6
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the isophthalic acid used in Synthesis Example 5 was replaced with biphenyldicarboxylic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer VI) had a weight average molecular weight of 41400 and a dispersity of 1.7 determined by standard polystyrene conversion.

GPC method for measuring weight average molecular weight: Detector: L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi L6000
Shimadzu C-R4A Chromatopac
Measurement conditions: Column: Gelpack GL-S300MDT-5 x2
Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0ml / min, Detector: UV270nm
Measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

Examples 1 to 4 and Comparative Examples 1 and 2
After coating a polybenzoxazole precursor having a diamine unit obtained in Synthesis Examples 1 to 6 and a polybenzoxazole precursor 10.0 g in N-methylpyrrolidone 15 g on a glass plate using a spin coater Then, it was dried on a hot plate at 120 ° C. for 3 minutes to obtain a coating film having a thickness of 10 μm. The transmittance of this coating film was measured with an ultraviolet-visible spectrophotometer. Next was spin coated on a silicon wafer, coating having a dry film thickness of 10~20μm to form, in a petri dish, immersed in 2.38% TMAH aqueous solution at 23 ^o C, it was calculated alkali dissolution rate from completely dissolved time. Residual stress was measured by heating on a silicon wafer at 350 ° C. for 60 minutes to form a polybenzoxazole film and using a stress measuring device (FLX-2320 type) manufactured by Tencor. Table 1 shows the measurement results of polymer permeability, alkali dissolution rate and stress.

以上の結果から、実施例1〜4のポリマは比較例1, 2に比べて透過率が高くかつ応力が低かった。

From the above results, the polymers of Examples 1 to 4 had higher transmittance and lower stress than Comparative Examples 1 and 2.

  Components (b) to (e) were blended in predetermined amounts shown in Table 2 with respect to 100 parts by weight of the polybenzoxazole precursor having a diamine unit and the polybenzoxazole precursor. The evaluation results of the photosensitive characteristics are shown in Table 2.

表中、NMP：N-メチルピロリドンを表す。（）内はポリマー１００重量部に対する添加量を重量部で示した。

In the table, NMP represents N-methylpyrrolidone. The amount in parentheses indicates the amount added relative to 100 parts by weight of the polymer in parts by weight.

  The solution was then exposed to i-line (365 nm) using an ultra-high pressure mercury lamp through an interference filter. After exposure, heat at 120 ° C. for 3 minutes, develop with a 2.38% aqueous solution of tetramethylammonium hydroxide until the exposed silicon wafer is exposed, then rinse with water to obtain the minimum exposure required for pattern formation. The resolution was determined. The results are shown in Table 3.

以上の結果から、実施例5〜8のポリマは比較例3, 4に比べて高感度、高解像度のパターンが形成できた。

From the above results, the polymers of Examples 5 to 8 were able to form a pattern with higher sensitivity and higher resolution than Comparative Examples 3 and 4.

It is a manufacturing process figure of the semiconductor device of a multilayer wiring structure.

Explanation of symbols

1: semiconductor substrate,
2: Protective film,
3: First conductor layer,
4: Interlayer insulating film layer,
5: photosensitive resin layer,
6A, 6B, 6C: window,
7: second conductor layer,
8: Surface protective film layer

Claims (11)

(A) General formula (I)

(Wherein U represents a tetravalent organic group, and V and W represent a divalent organic group) j and k in the general formula (I) represented by 0.01 ≦ k / (j + k) < A positive-type photosensitive resin composition comprising a polybenzoxazole precursor having an amide unit soluble in an alkaline aqueous solution having a repeating unit satisfying 1, a compound that generates an acid by light, and (c) a solvent. . 2. The positive photosensitive resin composition according to claim 1, wherein W of component (a) is represented by general formula (II).

(In the formula, M represents a single bond or a divalent organic group, R ₁ and R ₂ are each independently a monovalent organic group, r and s are each independently an integer of 0 to 4, Each of the two bonds is on a different benzene ring in the formula.) (A) W of component is represented by general formula (III)

(Wherein X represents a divalent organic group, R ₁ and R ₂ are each independently a monovalent organic group, r and s are each independently an integer of 0 to 4, and two bonds of W The hands are present on different benzene rings in the formula.) The positive photosensitive resin composition according to claim 1. 2. The positive photosensitive resin composition according to claim 1, wherein W of component (a) is represented by general formula (IV), and n is an integer of 1 to 100.

(R ₃ and R ₈ are divalent organic groups, and R _{4 to} R ₇ are each independently a monovalent organic group.) 5. The positive photosensitive resin composition according to claim 4, wherein W of component (a) is represented by general formula (IV), and n is an integer of 1 to 30. (A) An alkaline aqueous solution-soluble aromatic polyamide having a repeating unit in which j and k in the general formula (I) represented by the general formula (I) satisfy 0.03 ≦ k / (j + k) <0.6 The positive photosensitive resin composition in any one of 1-4. 7. The positive photosensitive resin composition according to claim 1, further comprising (d) a compound having a phenolic hydroxyl group, and (e) a compound that suppresses dissolution of the component (a) in the alkaline aqueous solution. The positive photosensitive resin composition according to any one of the above. (B) 5-100 parts by weight of component, (d) 1-30 parts by weight of component, and (e) 0.01-15 parts by weight of component are blended with 100 parts by weight of component (a). The positive photosensitive resin composition according to any one of the above. A polybenzoxazole formed by dehydrating and ring-closing the polyamide according to claim 1. The process of apply | coating the positive photosensitive resin composition in any one of Claims 1-8 on a support substrate, and drying, The process of exposing the photosensitive resin film obtained by the said drying process, The photosensitive after the said exposure A method for producing a pattern comprising a step of heating a photosensitive resin film, a step of developing the photosensitive resin film after heating using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after development. 11. An electronic component having an electronic device having a pattern layer obtained by the manufacturing method according to claim 10, wherein the pattern layer is provided as an interlayer insulating film layer or a surface protective film in the electronic device. An electronic component characterized by that.

Images