JP5110145B2 - Positive photosensitive resin composition, pattern forming method, and electronic component - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a pattern forming method, and an electronic component, in particular, a positive photosensitive resin composition that is not brittle and has a heat-resistant cured film even by a curing process at a low temperature. The present invention relates to an object, a pattern forming method using the same, and an electronic component.

  Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. 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.

This polyimide resin film is generally made by reacting a tetracarboxylic dianhydride and a diamine in a polar solvent at room temperature and normal pressure to form a polyimide precursor (polyamide acid) solution. It is formed by dehydration ring closure (so-called curing) (see, for example, Non-Patent Document 1).
In recent years, a photosensitive polyimide having a photosensitive property imparted to a polyimide resin itself has been used. However, if this is used, the pattern creation process can be simplified and complicated manufacturing processes can be shortened (for example, patents). References 1-3).

  For the development of the photosensitive polyimide, an organic solvent such as N-methylpyrrolidone has been used. Recently, a positive photosensitive resin that can be developed with an aqueous alkaline solution has been proposed from the viewpoint of environment and cost. Yes. As such a positive photosensitive resin, a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (for example, see Non-Patent Document 2), a soluble hydroxylimide or a polybenzoxazole precursor with naphtho There is a method of mixing a quinonediazide compound (for example, see Patent Documents 4 and 5), and photosensitive polybenzoxazole is attracting attention together with photosensitive polyimide from the viewpoint of expecting low dielectric constant. In addition, as photosensitive polybenzoxazole, there is also a report of a negative photosensitive resin that can be developed with an alkaline aqueous solution in which a photoacid generator and a methylol compound are combined (Non-patent Document 3).

Japanese Patent Laid-Open No. 49-11541 JP 59-108031 A JP 59-219330 A Japanese Examined Patent Publication No. 64-60630 US Pat. No. 4,395,482

Japan Polyimide Study Group “Latest Polyimide: Basics and Applications”, pp. 328-338 (2002) J. et al. Macromol. Sci. , Chem. , A24 (12), pp. 1407-1422 (1987) Polym. J. et al. , Vol. 37, pp. 74-81 (2005)

  When a polyimide precursor or polybenzoxazole precursor is thermally dehydrated and closed to form a polyimide thin film or polybenzoxazole thin film, a high temperature of about 350 ° C. is usually required. However, MRAM (Magnetic Resistive RAM), which has recently appeared and is promising as a next-generation memory, is vulnerable to a high temperature process, and a low temperature process is desired. Accordingly, the surface protective film can be dehydrated and closed at a low temperature of about 250 ° C. or lower, more preferably 200 ° C. or lower, rather than the conventional high temperature of about 350 ° C., and the physical properties of the film after dehydration and ring closure are high. Polyimide materials and polybenzoxazole materials that can obtain performances comparable to those obtained have become indispensable. However, when the curing temperature is lowered, the generally formed film becomes brittle and the physical properties of the film are lowered.

  The present invention has been made in order to solve the conventional problems as described above, and relates to a photosensitive polybenzoxazole precursor that can be alkali-developed, by using a specific compound, and by a curing process at a low temperature. Another object of the present invention is to provide a positive photosensitive resin composition that is not brittle and forms a cured film having high heat resistance. In addition, the present invention can be developed with an alkaline aqueous solution by using the positive photosensitive resin composition, has excellent sensitivity, resolution, and adhesion at the time of development, and is not brittle and heat resistant by a low temperature curing process. It is an object of the present invention to provide a pattern forming method capable of obtaining an excellent pattern having a good shape. Furthermore, the present invention provides a highly reliable electronic component with a high yield by avoiding damage to the device by having a pattern having a good shape and characteristics and being cured by a low temperature process.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, a positive photosensitive resin in which a compound having a specific phenolic hydroxyl group is added to a photosensitive resin containing polyamide soluble in an alkaline aqueous solution. It has been found that a film coated with the composition and cured at a relatively low temperature of 200 ° C. or lower exhibits a high elongation at break. Furthermore, surprisingly, it has been found that the positive photosensitive resin composition used here has high sensitivity, high resolution, excellent adhesion during development, and a pattern that is not brittle can be obtained in the subsequent low-temperature process. It has come to be completed.

  That is, the positive photosensitive resin composition of the present invention comprises (a) an aqueous alkali-soluble polyamide and (b) a compound having a phenolic hydroxyl group represented by the general formula (I), which will be described later. And (c) an o-quinonediazide compound, and (d) a solvent.

（式中、Ｒ¹〜Ｒ⁴は各々独立に水素原子又は一価の有機基を示し、ｍ及びｎは各々独立に１〜３の整数であり、ｐ及びｑは各々独立に０〜４の整数である。Ｘは一般式（ＩＩ）、（ＩＩＩ）又は（ＩＶ）で示される有機基又は原子である。）

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent organic group, m and n are each independently an integer of 1 to 3, and p and q are each independently 0 to 4) X is an organic group or atom represented by the general formula (II), (III) or (IV).

（式中、ｔは１〜１２の整数である。）

(In the formula, t is an integer of 1 to 12.)

  In the positive photosensitive resin composition of the present invention, as described above, the compound (b) having a phenolic hydroxyl group is a compound represented by the general formula (V).

  The compound (b) having a phenolic hydroxyl group may be a compound represented by the general formula (VI), but in the present invention, a compound represented by the general formula (V) is used. .

  In the positive photosensitive resin composition of the present invention, the (a) polyamide soluble in an aqueous alkali solution may be a compound represented by the general formula (VII).

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)

  Moreover, in the positive photosensitive resin composition of this invention, the said positive photosensitive resin composition may further contain the thermal latent acid generator which generate | occur | produces an acid by (e) heating.

  In the positive photosensitive resin composition of the present invention, 1 to 30 parts by weight of the component (b) and 5 to 100 parts by weight of the component (c) with respect to 100 parts by weight of the component (a). Parts may be blended.

  Moreover, in the positive photosensitive resin composition of the present invention, 1 to 30 parts by weight of the component (b) and 5 to 100 parts by weight of the component (c) with respect to 100 parts by weight of the component (a). And 0.1 to 30 parts by weight of the component (e) may be blended.

  Moreover, in the pattern formation method of this invention, it exposes the photosensitive resin film obtained by the process of apply | coating one of the said positive photosensitive resin compositions on a support substrate, and drying, and the said drying process. A step of developing the photosensitive resin film after the exposure using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development.

  In the pattern forming method of the present invention, in the step of heat-treating the photosensitive resin film after development, the heat treatment is a treatment of irradiating microwaves in a pulsed manner while changing the frequency. Also good.

  Moreover, in the pattern formation method of this invention, a heating temperature can be 200 degrees C or less in the process of heat-processing the photosensitive resin film after image development.

  The electronic component of the present invention is characterized in that a layer of a pattern obtained by the pattern forming method is provided as an interlayer insulating film layer or a surface protective film layer.

  In the electronic component of the present invention, the electronic component may be an MRAM.

  In the positive photosensitive resin composition according to the present invention, a specific compound having a phenolic hydroxyl group reacts with the polyamide, that is, crosslinks, in the step of heat-treating the photosensitive resin film after exposure and development. This enables curing at a relatively low temperature, for example, 200 ° C. or lower. Moreover, the brittleness of the film | membrane which is anxious about hardening at the temperature of 200 degrees C or less can be prevented. The specific compound having a phenolic hydroxyl group used in the present invention does not adversely affect the difference in dissolution rate (dissolution contrast) between the exposed portion and the unexposed portion of the developer, and is excellent in sensitivity and resolution.

  Moreover, according to the pattern formation method of this invention, it is excellent in a sensitivity, resolution, and adhesiveness by use of the said composition. Furthermore, since the bridging reaction proceeds sufficiently even in the low temperature curing process, a pattern having a good shape with excellent physical properties such as heat resistance can be obtained.

  In addition, the electronic component of the present invention has a good shape, adhesion and heat resistance, and can be cured by a low-temperature process. is there. In addition, since the damage to the device is small, the yield is high.

FIG. 1-1 is a schematic cross-sectional view illustrating a manufacturing process of a semiconductor device having a multilayer wiring structure in an embodiment of the present invention. FIG. 1-2 is a schematic cross-sectional view illustrating a manufacturing process of a semiconductor device having a multilayer wiring structure in an embodiment of the present invention. 1-3 is a schematic cross-sectional view illustrating a manufacturing process of a semiconductor device having a multilayer wiring structure according to an embodiment of the present invention. 1-4 is a schematic cross-sectional view illustrating a manufacturing process of a semiconductor device having a multilayer wiring structure according to an embodiment of the present invention. FIGS. 1-5 is schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. FIGS. FIG. 2 is a schematic cross-sectional view showing the electronic components produced in Example 5, Reference Example 4 and Comparative Example 3.

  Embodiments of a positive photosensitive resin composition, a pattern forming method, and an electronic component according to the present invention will be described below in detail with reference to the drawings. In addition, this invention is not limited by this embodiment.

[Positive photosensitive resin composition]
First, the positive photosensitive resin composition according to the present invention will be described.
The positive photosensitive resin composition according to the present invention is represented by the following general formula (V) among the compounds having (a) an aqueous alkali-soluble polyamide and (b) a phenolic hydroxyl group represented by the general formula (I). And a positive photosensitive resin composition comprising (c) an o-quinonediazide compound, and (d) a solvent.

（式中、Ｒ¹〜Ｒ⁴は各々独立に水素原子又は一価の有機基を示し、ｍ及びｎは各々独立に１〜３の整数であり、ｐ及びｑは各々独立に０〜４の整数である。Ｘは一般式（ＩＩ）、（ＩＩＩ）又は（ＩＶ）で示される有機基又は原子である。）

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent organic group, m and n are each independently an integer of 1 to 3, and p and q are each independently 0 to 4) X is an organic group or atom represented by the general formula (II), (III) or (IV).

（式中、ｔは１〜１２の整数である。）

(In the formula, t is an integer of 1 to 12.)

[(A) Alkaline aqueous solution-soluble polyamide (polybenzoxazole precursor)]
The (a) aqueous alkali-soluble polyamide is a phenolic hydroxyl group-containing polyamide soluble in an aqueous alkaline solution, which generally functions as a precursor of polyoxazole, preferably polybenzoxazole. Specifically, it is a compound represented by the general formula (VII).

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)

  The amide unit containing a hydroxy group represented by the general formula (VII) 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 polyamide having the repeating unit represented by the general formula (VII) may have the repeating unit. However, the solubility of the polyamide in an alkaline aqueous solution is an OH group (generally a phenolic hydroxyl group) bonded to U. ), The amide unit containing the OH group is preferably contained in a certain proportion or more.
That is, it is preferably a polyamide represented by the following formula (VIII).

（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、モル分率を示す。）

(In the formula, U represents a tetravalent organic group, V and W represent a divalent organic group, and j and k represent molar fractions.)

  The sum of these j and k is 100 mol%, j is preferably 60 to 100 mol%, and k is preferably 40 to 0 mol%. Moreover, it is more preferable that the molar fraction of j and k is j = 80-100 mol% and k = 20-0 mol%.

  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, the polyamide having a repeating unit represented by the general formula (VII) can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the 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 ordinary acid chlorination reactions of carboxylic acids 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 between the dichloride derivative and the diamine is preferably performed 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.

(Aminophenol)
Here, in the general formula (VII), the tetravalent organic group represented by U is generally a residue derived from dihydroxydiamine that reacts with a dicarboxylic acid to form a polyamide structure, and is a tetravalent aromatic group. A group having 6 to 40 carbon atoms is preferable, and a tetravalent aromatic group having 6 to 40 carbon atoms is more preferable. As the tetravalent aromatic group, a residue of diamine having a structure in which all four bonding sites are present on the aromatic ring and each of the two hydroxy groups is located at the ortho position of the amine is preferable.

  Such diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,2-bis (3-amino-4- Hydroxyphenyl) propane, 2,2-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, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 9,9-bis {4- (3-amino-4-hydro) Ciphenoxy) phenyl} fluorene, 1,3-bis (3-amino-4-hydroxyphenyl) adamantane, 1,3-bis {4- (3-amino-4-hydroxyphenoxy) phenyl} adamantane, 2,2- Examples include bis (3-amino-4-hydroxyphenyl) adamantane, 2,2-bis {4- (3-amino-4-hydroxyphenoxy) phenyl} adamantane, but are not limited thereto. These compounds can be used alone or in combination of two or more.

Among the above diamines, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-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, Like 2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (aromatic orthohydroxylamine) is sp ³ carbon atom, sulfur atom, Diamines bonded to atoms such as oxygen atoms are molecules with moderate flexibility, and are characterized by dehydration and ring closure at relatively low temperatures, and are also resistant to heat from aromatic groups. More preferable in that it combines.

(Diamine (copolymerization component))
In the general formula (VIII) of the polyamide, the divalent organic group represented by W is generally derived from a diamine that forms a polyamide structure by reacting with a dicarboxylic acid (however, dihydroxydiamine that forms the U). A divalent aromatic group or aliphatic group, preferably having 4 to 40 carbon atoms, more preferably a 4 to 40 carbon atom divalent aromatic group. .

  Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 As an aromatic diamine compound such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene, and other diamines containing a siloxane skeleton, LP-7100, X-22- 161AS, X-22-161A, X-2 -161B, X-22-161C, and X-22-161E (both Shin-Etsu Chemical Co., Ltd., trade name), but like, but is not limited thereto. These compounds can be used alone or in combination of two or more.

(Dicarboxylic acid)
In the general formula (VII), the divalent organic group represented by V is a dicarboxylic acid-derived residue that reacts with diamine to form a polyamide structure, and is preferably 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 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis {4- (3 Or 4-carboxyphenoxy) phenyl} fluorene, 1,3-bis (4-carboxyphenyl) adaman 1,3-bis {4- (3 or 4-carboxyphenoxy) phenyl} adamantane, 2,2-bis (4-carboxyphenyl) adamantane, 2,2-bis {4- (3 or 4-carboxyphenoxy) ) Aromatic dicarboxylic acids such as phenyl} adamantane, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, and other aliphatic systems Examples thereof include, but are not limited to, dicarboxylic acids. These compounds can be used alone or in combination of two or more.

Among the above dicarboxylic acids, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxy As in tetraphenylsilane, bis (4-carboxyphenyl) sulfone, and 2,2-bis (p-carboxyphenyl) propane, bis (aromatic carboxylic acid) is an atom such as sp ³ carbon atom, sulfur atom, oxygen atom, etc. The dicarboxylic acids bonded to are more preferable because they are molecules having moderate flexibility and are characterized in that dehydration ring closure occurs at a relatively low temperature and also have heat resistance derived from an aromatic group.

  In addition, although the dicarboxylic acids shown in (IX) and (X) below are not aromatic, they can be cited as preferred examples in that dehydration ring closure occurs at a relatively low temperature because they are molecules having moderate flexibility.

（式中、Ｚは炭素数１〜６の炭化水素基を表す。）

(In the formula, Z represents a hydrocarbon group having 1 to 6 carbon atoms.)

  Furthermore, dicarboxylic acids shown in the following (XI) and (XIII) can also be exemplified.

（式中、Ｚは炭素数１〜６の炭化水素基であり、Ｍは単結合又は２価の基又は原子、例えば−ＣＨ₂−，−Ｃ（ＣＨ₃）₂−，−Ｏ−，−Ｓ−，−ＳＯ₂−，−ＣＯ−，−（ＣＦ₃）₂−等であり、Ｘは下記の（ＸＩＩ）に示されるいずれかの式で表される。）

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, M is a single bond or a divalent group or atom, for example, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, — S—, —SO ₂ —, —CO—, — (CF ₃ ) ₂ — and the like, and X is represented by any formula shown in the following (XII).)

（式中、ｎは１〜６の整数を表す。）

(In the formula, n represents an integer of 1 to 6.)

In general formula (XIII), R ⁵ and R ¹⁰ are each independently a divalent organic group, R ^{6 to} R ⁹ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and r is 1 to 100. Represents an integer. Examples of divalent organic groups of R ⁵ and R ¹⁰ and monovalent organic groups of R ^{6 to} R ⁹ include hydrocarbon groups having 1 to 10 carbon atoms (alkyl groups, alkylene groups, etc.), alkyl ether groups, and fluoroalkyls. Group, fluoroalkyl ether group, phenyl group and the like, and the number of repeating units r is 1-100.

[(B) Compound having phenolic hydroxyl group]
Next, the compound which has the phenolic hydroxyl group which is (b) component used by this invention is demonstrated. The compound having this phenolic hydroxyl group increases the sensitivity by increasing the dissolution rate of the exposed area when developing with an alkaline aqueous solution by adding this compound, and reacts with the polyamide when the film after pattern formation is cured. That is, it is bridged. Accordingly, the brittleness of the film and the melting of the film which are concerned can be prevented at a relatively low temperature, for example, a curing temperature of 200 ° C. or lower. Such a compound having a phenolic hydroxyl group can be represented by the following general formula (I). In the present invention, a compound represented by the general formula (V) is used.

（式中、Ｒ¹〜Ｒ⁴は各々独立に水素原子又は一価の有機基を示し、ｍ及びｎは各々独立に１〜３の整数であり、ｐ及びｑは各々独立に０〜４の整数である。Ｘは一般式（ＩＩ）又は（ＩＩＩ）又は（ＩＶ）で示される有機基又は原子である。）

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent organic group, m and n are each independently an integer of 1 to 3, and p and q are each independently 0 to 4) X is an organic group or atom represented by the general formula (II) or (III) or (IV).

（式中、ｔは１〜１２の整数である。）

(In the formula, t is an integer of 1 to 12.)

  Examples of such a compound having a phenolic hydroxyl group include those represented by the following (XIV). In the present invention, a compound represented by the general formula (V) is used. In addition, you may use it individually by the compound shown by general formula (V), and can use it combining the other compound shown below.

（ＸＩＶ）

(XIV)

  Among the compounds having a phenolic hydroxyl group, a positive photosensitive resin composition containing the following formula (V) or (VI) is preferable in that it exhibits a high elongation at break when cured at 200 ° C. or lower.

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

[(C) o-quinonediazide compound]
Next, the o-quinonediazide compound which is the component (c) used in the present invention will be described. This o-quinonediazide compound is a photosensitizer and has a function of generating carboxylic acid upon irradiation with light and increasing the solubility of the irradiated portion in an alkaline aqueous solution. Such an o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane, and bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  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 dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the positive photosensitive resin composition of the present invention, the blending amount of component (c) is based on 100 parts by weight of component (a) in terms of the difference in dissolution rate between exposed and unexposed areas and the allowable sensitivity range. 5 to 100 parts by weight is preferable, and 8 to 40 parts by weight is more preferable. Moreover, when (b) component is considered, it is preferable to mix | blend (b) component 1-30 weight part and (c) component 5-100 weight part with respect to (a) component 100 weight part.

[(D) Solvent]
Next, the solvent which is the component (d) used in the present invention will be described. Examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol mono Examples include butyl ether and dipropylene glycol monomethyl ether.
These solvents can be used alone or in combination of two or more. The amount of the solvent (d) is not particularly limited, but it is generally preferable to adjust the solvent so that the proportion of the solvent in the photosensitive resin composition is 20 to 90% by weight.

[(E) Thermal latent acid generator]
In the positive photosensitive resin composition of the present invention, in addition to the components (a) to (d), (e) a thermal latent acid generator that generates an acid by heating may be blended. Examples of the acid generated from the thermal latent acid generator include p-toluenesulfonic acid, aryl sulfonic acid such as benzene sulfonic acid, camphor sulfonic acid, trifluoromethane sulfonic acid, and perafluorosulfonic acid such as nonafluorobutane sulfonic acid. Alkyl sulfonic acids such as fluoroalkyl sulfonic acids, methane sulfonic acids, ethane sulfonic acids, butane sulfonic acids are desirable. These acids are efficient when the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and cyclizes, and as a catalyst for the reaction between the phenolic hydroxyl group-containing compound and the phenolic hydroxyl group-containing polyamide. Even if the curing temperature is lowered, a decrease in the cyclization rate can be prevented. In contrast, acid generators that generate hydrochloric acid, bromic acid, iodic acid, and nitric acid have weak acidity and are likely to volatilize when heated. Since it is not involved in the dehydration reaction, no effect is obtained.

  These acids are added to the photosensitive composition of the present invention in the form of a salt such as an onium salt or a covalent bond such as an imide sulfonate as a heat latent acid generator. Specifically, as an onium salt, a diphenyliodonium salt, a di (alkylphenyl) iodonium salt such as di (t-butylphenyl) iodonium salt, a trialkylsulfonium salt such as trimethylsulfonium salt, or a dimethylphenylsulfonium salt is used. Diaryl monoalkyl iodonium such as dialkyl monoaryl sulfonium salt and diphenylmethyl sulfonium salt are desirable. These have a decomposition initiation temperature of about 150 ° C. or higher, and effectively act in the cyclization dehydration reaction of the polybenzoxazole precursor at 200 ° C. or lower. In contrast, triphenylsulfonium salts are not desirable as the thermal latent acid generator of the present invention. Triphenylsulfonium salts have high thermal stability and generally have a decomposition temperature exceeding 300 ° C. Accordingly, since no decomposition occurs during the cyclization dehydration reaction of the polybenzoxazole precursor at 200 ° C. or lower, it does not work as a catalyst for cyclization dehydration.

As the imide sulfonate, naphthoyl imide sulfonate is desirable. On the other hand, phthalimide sulfonate is not desirable because it has poor thermal stability, so that acid is generated before the curing reaction and storage stability is deteriorated.
In addition, as shown in the following (XV), a compound having a structure of ═N—O—SO ₂ —R can also be used.

In addition, a compound having an amide structure —HN—SO ₂ —R can be used as follows.

  As (e) component used by this invention, the salt formed from strong acids and bases other than onium salt can also be used. Examples of the strong acid include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, methanesulfonic acid, and ethane. Alkyl sulfonic acids such as sulfonic acid and butane sulfonic acid are desirable. As the base, pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, halogenated-N-alkylpyridine and the like are desirable. These are also decomposed during the cyclization dehydration reaction of the polybenzoxazole precursor at 200 ° C. or lower and function as a catalyst.

  Component (e) is preferably blended in an amount of 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, and even more preferably 0.5 to 10 parts by weight per 100 parts by weight of component (a). . Further, considering the component (b) and the component (c), the component (b) is 1 to 30 parts by weight, the component (c) is 5 to 100 parts by weight, and the component (e) ) It is preferable to blend 0.1 to 30 parts by weight of the component.

[Other components: (1) Dissolution inhibitor]
In the present invention, in addition to the components (a) to (e) described above, (1) a dissolution inhibitor, (2) a coupling agent, and (3) a surfactant may be blended. First, (1) a dissolution inhibitor is a compound that inhibits the solubility of the component (a) in an alkaline aqueous solution, and can be contained in the photosensitive resin composition.

Specific examples include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide, and the like.
These are useful for controlling the remaining film thickness and development time. The blending amount of the above components is preferably 0.01 to 15 parts by weight, 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. 0.05-3 weight part is further more preferable.

[Other components: (2) Coupling agent]
The positive photosensitive resin composition of the present invention can contain an adhesion-imparting agent that is a coupling agent such as an organic silane compound or an aluminum chelate compound 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, γ-aminopropyltriethoxysilane, bis (2- Hydroxyethyl) -3-aminopropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butyl Phenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n- Tylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenyl Silanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1, 4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyl) Dihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) ) Benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene and the like.

  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.

[Other components: (3) surfactant]
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) or improve developability. Can do. 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).

[Pattern formation method]
Next, the pattern forming method according to the present invention will be described. The pattern forming method of the present invention includes a step of applying the positive photosensitive resin composition described above on a support substrate and drying, a step of exposing the photosensitive resin film obtained by the drying step, and the post-exposure step The step of developing the photosensitive resin film using an alkaline aqueous solution, and the step of heat-treating the photosensitive resin film after the development. Hereinafter, each step will be described.

(Coating / drying (film formation) process)
First, in the step of applying and drying a positive photosensitive resin composition on a support substrate, on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.), silicon nitride, The above-described positive photosensitive resin composition is spin-coated using a spinner or the like, and then the support substrate is dried using a hot plate, an oven, or the like. As a result, a film of the positive photosensitive resin composition is formed on the support substrate.

(Exposure process)
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.
It should be noted that after exposure, post-exposure heating (PEB) may be performed as necessary, and then the development process may be performed. The post-exposure heating temperature is preferably 70 ° C. to 140 ° C., and the post-exposure heating time is preferably 1 minute to 5 minutes.

(Development process)
In the development step, a pattern is obtained by removing the exposed portion of the photosensitive resin composition exposed to actinic rays 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.

(Heat treatment process)
Next, in the heat treatment step, a pattern of heat-resistant polyoxazole having an oxazole ring or other functional group can be formed by heat-treating the pattern obtained after development. The heating temperature in the heat treatment step is desirably 200 ° C. or less, and more desirably in the range of 140 to 200 ° C.

  The heat treatment is performed using a quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace, or the like. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the treatment under nitrogen because the oxidation of the photosensitive resin composition film can be prevented. The cyclization dehydration reaction and the bridge reaction can be sufficiently progressed within the above heating temperature range, and since the temperature is lower than the conventional heating temperature, damage to the support substrate and the device can be suppressed to a low level. Therefore, by using the pattern forming method of the present invention, the device can be obtained with a high yield. It also leads to energy saving in the process.

  The heat treatment time in the heat treatment step of the present invention is the time until the positive photosensitive resin composition is cured, for example, the time until the reaction such as dehydration and ring closure of the polyamide sufficiently proceeds. From the balance, approximately 5 hours or less is preferable.

(Microwave curing)
As the heat treatment in the heat treatment step of the pattern forming method, a microwave curing device or a variable frequency microwave curing device can be used in addition to the above-described curing furnace. By using these, it is possible to effectively heat only the photosensitive resin composition film while keeping the temperature of the substrate or device at, for example, 200 ° C. or lower.

  In the variable frequency microwave curing apparatus, the microwave is irradiated in pulses while changing its frequency, so that standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when a metal wiring is included as an electronic component to be described later as a substrate, the occurrence of discharge (arc) from the metal can be prevented by irradiating microwaves in a pulsed manner while changing the frequency. It is preferable in that it can be protected from destruction. Furthermore, heating using a frequency-variable microwave is preferable because the cured film properties do not deteriorate even when the curing temperature is lowered as compared to an oven (see J. Photopolym. Sci. Technol., 18, 327-332 (2005)). .

  The frequency of the frequency variable microwave is in the range of 0.5 to 20 GHz, but is practically preferably in the range of 1 to 10 GHz, and more preferably in the range of 2 to 9 GHz. In addition, it is desirable to continuously change the frequency of the microwave to be irradiated, but actually the irradiation is performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is that standing waves or metal discharges occur, and the time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  The output of the microwave to be irradiated varies depending on the size of the apparatus and the amount of the object to be heated, but is generally in the range of 10 to 2000 W, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 700 W. 500 W is most preferred. If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, a rapid temperature rise tends to occur.

  Moreover, it is preferable to irradiate the microwave by turning it on / off in a pulsed manner. By irradiating the microwaves in a pulsed manner, it is preferable in that the set heating temperature can be maintained and damage to the cured film and the substrate can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is preferably about 10 seconds or less.

[Semiconductor device manufacturing process]
Next, as an example of the pattern forming method according to the present invention, a manufacturing process of a semiconductor device will be described with reference to the drawings. 1A to 1E are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure. 1-1 to 1-5, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element. A first conductor layer 3 is formed on the exposed circuit element. An interlayer insulating film 4 such as a polyimide resin is formed on the semiconductor substrate 1 by a spin coat method or the like (FIG. 1-1).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film 4 as a mask by a spin coating method, and a predetermined portion of the interlayer insulating film 4 is formed by a known photolithography technique. A window 6A is provided so as to be exposed (FIG. 1-2). 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 (FIGS. 1-3). Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (FIGS. 1-4).

  Next, the surface protective film 8 is formed. In the example of FIGS. 1-1 to 1-5, the positive photosensitive resin composition according to the present invention is applied onto the interlayer insulating film 4 and the second conductor layer 7 by a spin coat method and dried. Next, after irradiating light from a mask on which a pattern for forming the window 6C is formed at a predetermined portion, the pattern is formed by developing with an alkaline aqueous solution. Then, it heats (hardens) and forms the polyoxazole film | membrane as the surface protective film 8 (FIGS. 1-5). This polyoxazole film protects the conductor layer from external stress, α rays, and the like, and the obtained semiconductor device is excellent in reliability.

  When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps. That is, it is possible to form a multilayer pattern by repeating each step of forming the interlayer insulating film 4 and each step of forming the surface protective film 8. In the above example, not only the surface protective film 8 but also the interlayer insulating film 4 can be formed using the positive photosensitive resin composition of the present invention.

[Electronic parts]
Next, the electronic component according to the present invention will be described. The electronic component according to the present invention has a pattern formed by the above pattern forming method using a positive photosensitive resin composition. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like. Further, the pattern can be used specifically for forming a surface protective film, an interlayer insulating film of a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. The electronic component according to 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.

  As an electronic component having a surface protective film, an interlayer insulating film, or the like obtained by using the photosensitive resin composition of the present invention, for example, MRAM having low heat resistance is preferable. That is, the photosensitive resin composition of the present invention is suitable for a surface protective film of MRAM.

  In addition to the MRAM, a polymer memory (Polymer RAM: PFRAM) and a phase change memory (Phase RAM: PCRAM, or Ovonics Unified Memory: OUM), which are promising as next-generation memories, are also more heat resistant than conventional memories. The possibility of using new materials with low Therefore, the photosensitive resin composition of the present invention is also suitable for these surface protective films.

  As described above, by using the positive photosensitive resin composition according to the present invention, curing can be performed by using low-temperature heating of 200 ° C. or lower in the above heat treatment step that conventionally required 300 ° C. or higher. is there. In addition, the positive photosensitive resin composition according to the present invention has high film physical properties, particularly elongation at break, even when cured at 200 ° C. or lower, and therefore becomes a surface protective film that is not brittle and excellent in heat resistance. Further, since the process can be performed at a low temperature, defects due to heat of the device can be reduced, and an electronic component such as a semiconductor device having excellent reliability can be obtained with high yield and high yield.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.

(Synthesis Example 1) Synthesis of polyamide In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid (30 mol%) and 90 g of N-methylpyrrolidone were charged. After cooling to 5 ° C., 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether tetracarboxylic acid chloride. Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 87.5 g of N-methylpyrrolidone was charged, and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1, After adding 3.30 g of 3,3,3-hexafluoropropane and stirring and dissolving, 8.53 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride Was added dropwise over 30 minutes, and stirring was continued for 30 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 polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer A1). The weight average molecular weight calculated | required by GPC method standard polystyrene conversion of polymer A1 was 14580, and dispersion degree was 1.6.

(Synthesis Example 2) Synthesis of Polyamide Under the same conditions as in Synthesis Example 1, except that 30 mol% of 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was replaced with cyclohexane-1,4-dicarboxylic acid. Synthesis was performed. The obtained polyhydroxyamide (hereinafter referred to as polymer A2) had a weight average molecular weight determined by standard polystyrene conversion of 18580 and a dispersity of 1.5.

Synthesis Example 3 Synthesis of Polyamide In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C. Then, 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether tetracarboxylic acid chloride. Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 87.5 g of N-methylpyrrolidone was charged, and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1, 18.30 g of 3,3,3-hexafluoropropane and 2.46 g of 4-amino-3-methylphenol were added and dissolved by stirring, then 8.53 g of pyridine was added, and the temperature was maintained at 0 to 5 ° C. The solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and stirring was continued for 30 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 polyhydroxyamide (hereinafter referred to as polymer A3). The polymer A3 had a weight average molecular weight of 16,200 and a dispersity of 1.7 determined by GPC standard polystyrene conversion.

(Examples 1 to 4 and Reference Examples 1 to 3) Preparation and characteristics evaluation of positive photosensitive resin composition
Table 1 shows (b) a compound having a phenolic hydroxyl group, (c) an o-quinonediazide compound, (d) a solvent, and (e) a thermal latent acid generator for 100 parts by weight of the blended polyamide [component (a)]. The prescribed amount shown was blended, and 5 parts by weight of a 50% methanol solution of urea propyltriethoxysilane was blended as an adhesion aid. This solution was subjected to pressure filtration using a 3 μm pore Teflon (registered trademark) filter to obtain a solution (M1 to M7) of a photosensitive resin composition.

  In addition, about Examples 1-4 and Reference Examples 1-3, the said (a)-(e) component was mix | blended as shown in Table 1. As the component (a), the polymers A1 to A3 synthesized in Synthesis Examples 1 to 3 were used, and as the component (b), B1 to B3 represented by the following formula (XVII) were used. As the component (c), C1 and C2 represented by the following formula (XVIII) were used. Q in these formulas C1 and C2 is Q: shown in the following formula (XVIII). As the component (d), N-methyl-2-pyrrolidone was used as D1, and γ-butyrolactone / propylene glycol monomethyl ether acetate = 90/10 (weight ratio) was used as D2. As the component (e), E1 and E2 represented by the following formula (XIX) were used.

表１中、括弧内は（ａ）成分ポリマー１００重量部に対する添加量を重量部で示す。

In Table 1, the amount in parentheses indicates the amount added relative to 100 parts by weight of the component (a) polymer in parts by weight.

（ＸＶＩＩ）

(XVII)

（ＸＶＩＩＩ）

(XVIII)

（ＸＩＸ）

(XIX)

（ＸＸ）

(XX)

Photosensitive characteristics A solution (M1 to M7) of the photosensitive resin composition was spin coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 11 to 13 μm. Thereafter, reduction projection exposure was performed with i-line (365 nm) through a mask using an i-line stepper (FPA-3000iW manufactured by Canon). After the exposure, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and development was performed so that the remaining film thickness was about 70 to 90% of the initial film thickness. Thereafter, the film was rinsed with water, and the minimum exposure and resolution required for pattern formation were determined. The results are shown in Table 2.

解像度：開口している最小の正方形ホールパターン
剥がれ：８μｍライン／スペースパターンが剥離しているかどうかを判断

Resolution: smallest open square hole pattern Peeling: Judges whether 8 μm line / space pattern is peeled off

Film physical property sample patterning Further, the solution (M1 to M7) of the photosensitive resin composition was spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of about 15 μm. Then, it exposed with i line | wire (365 nm) through the mask using the proximity exposure machine (PLA-600FA by Canon). After exposure, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to obtain a 10 mm wide rectangular pattern. Thereafter, the coating film was heat-treated (cured) by the following method.

Curing and curing were performed by the following methods to obtain a polyoxazole film having a thickness of about 10 μm.
(I) Using a vertical diffusion furnace (μ-TF manufactured by Koyo Thermo System), the coating film was heat-treated in nitrogen at a temperature of 200 ° C. (heating time: 1.5 hours) for 1 hour.
(Ii) Using a vertical diffusion furnace (μ-TF manufactured by Koyo Thermo System), the coating film was heat-treated in nitrogen at a temperature of 180 ° C. (heating time: 1.5 hours) for 1 hour.
(Iii) Using a frequency-variable microwave curing furnace (Microcure 2100 manufactured by Lambda Technology Co., Ltd.), with a microwave output of 450 W, a microwave frequency of 5.9 to 7.0 GHz, and a temperature of 175 ° C. (heating time of 5 minutes) for 2 hours Heat-treated.

Film Properties The polyoxazole film having a thickness of about 10 μm cured by the above method was peeled from the silicon substrate, and the glass transition temperature (Tg) of the peeled film was measured with TMA / SS600 manufactured by Seiko Instruments Inc. Note that the width of the sample is 2 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 10 mm. The load is 10 g, and the rate of temperature increase is 5 ° C./min. Moreover, the average breaking elongation (El) of the peeling film was measured by Shimadzu Corporation autograph AGS-H100N. The width of the sample is 10 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 20 mm. The pulling speed is 5 mm / min, and the measurement temperature is about room temperature (20 ° C. to 25 ° C.). Here, the average of five or more measured values for the cured film obtained under the same conditions is defined as “average elongation at break (El)”. Table 3 shows the curing conditions, Tg, and El.

(Comparative Examples 1-2)
Β1 and β2, o-quinonediazite compound (c), solvent (d), thermal latent acid generator (as compound (b) having a phenolic hydroxyl group with respect to 100 parts by weight of polyamide [component (a)] in the above synthesis example ( e) was blended, and 5 parts by weight of a 50% methanol solution of urea propyltriethoxysilane was blended as an adhesion assistant. This solution was subjected to pressure filtration using a 3 μm pore Teflon (registered trademark) filter to obtain a solution (M8 to M9) of a photosensitive resin composition. The blending amounts are also shown in Table 1.

  For Comparative Examples 1 and 2, the component (a) used was the polymer A1 synthesized in Synthesis Example 1, and the component (b) used was β1 and β2 represented by the above formula (XX). . As the component (c), C1 and C2 represented by the above formula (XVIII) were used. In addition, Q in these formulas C1 and C2 is Q: shown in the above formula (XVIII). As the component (d), N-methyl-2-pyrrolidone was used as D1, and γ-butyrolactone / propylene glycol monomethyl ether acetate = 90/10 (weight ratio) was used as D2. As the component (e), E1 represented by the above formula (XIX) was used.

  Subsequently, the photosensitive characteristics were examined in the same manner as in Examples 1 to 4 and Reference Examples 1 to 3, and the results are also shown in Table 2. Furthermore, the physical properties of the cured films were measured in the same manner as in Examples 1 to 4 and Reference Examples 1 to 3, and the results are also shown in Table 3.

(Example 5 and Reference Example 4)
The photosensitive resin compositions M1 and M4 prepared in Example 1 and Reference Example 1, respectively, are coated with a protective film 2 such as a silicon oxide film as shown in FIG. After spin coating on the top, it was dried to form a coating film having a thickness of 13 μm. Then, exposure (exposure amount 250 mJ / cm < ² >) was performed by i line | wire (365 nm) through the mask using the proximity exposure machine (PLA-600FA by Canon). After exposure, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to form a window 6D having a 100 μm square. The semiconductor substrate 1 is heat-treated in an inert gas oven (manufactured by Koyo Thermo System) in nitrogen at a temperature of 200 ° C. (temperature raising time: 1.5 hours) for 1 hour to form a surface protective film layer 8. Such test parts (electronic parts) were created.

  The created test parts were subjected to a temperature cycle test (−55 ° C. to 125 ° C., 500 cycles), and observed for defects such as peeling and cracking. The results are shown in Table 4.

(Comparative Example 3)
A test component (electronic component) shown in FIG. 2 was prepared using the photosensitive resin composition M9 of Comparative Example 2 in the same manner as in Example 5 and Reference Example 4. This test component was subjected to a temperature cycle test in the same manner as in Example 5 and Reference Example 4, and the presence or absence of defects such as peeling and cracking was observed. The results are shown in Table 4.

  The measurement results will be examined below. First, the photosensitive properties are summarized in Table 2. As is clear from this, the resin compositions (Examples 1 to 3 and Reference Examples 1 to 3) of the present invention have high sensitivity and resolution. Furthermore, it turned out that the sensitivity of Examples 1-4 becomes higher than Comparative Examples 1-2 using (beta) 1 and (beta) 2 as a compound which has a phenolic hydroxyl group. Moreover, in Comparative Examples 1-2, although a narrow line / space pattern has a tendency to peel at the time of image development, when the resin composition of this invention was used, pattern peeling was not able to be confirmed.

  Table 3 shows the physical properties of the cured resin film. The resin composition of the present invention exhibited Tg of about 250 ° C. even when cured at 200 ° C., and El showed a high value of 30% or more. In Example 1, sufficient Tg and El were exhibited even at 180 ° C. curing (curing condition ii). Further, the 175 ° C. microwave-cured (curing condition iii) film had physical properties comparable to the 200 ° C. heat-cured (curing condition i) film. On the other hand, the cured resin films (Comparative Examples 1 and 2) using β1 and β2 other than the compound having a phenolic hydroxyl group used in the present invention were brittle, and the El was less than 20%. Furthermore, since the film was broken during the measurement, Tg could not be measured by TMA.

  Table 4 shows the results of subjecting a semiconductor component using the photosensitive resin composition to the surface protective film layer to a temperature cycle test. When the photosensitive resin composition of the present invention is used for the surface protective film layer, since the elongation at break of the film cured at 200 ° C. is high, the stress generated in the temperature cycle can be alleviated, and the semiconductor component is peeled off or cracked. Can be prevented. On the other hand, as a comparison, when a photosensitive resin having a low elongation at break of a film cured at 200 ° C. was used, interfacial peeling or cracking occurred due to stress.

  As described above, in the positive photosensitive resin composition, the pattern forming method, and the electronic component according to the present invention, the compound having a phenolic hydroxyl group reacts with the polyamide in the step of heat-treating the photosensitive resin film after exposure and development. To do. As a result, the positive photosensitive resin composition according to the present invention has high film physical properties, in particular, elongation at break even when cured at 200 ° C. or lower, and therefore has a good shape excellent in physical properties including heat resistance without being brittle. A pattern is obtained. Furthermore, since the process can be performed at a low temperature, defects due to heat of the device can be reduced, which is useful for electronic parts such as semiconductor devices having excellent reliability.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulation film layer 5 Photosensitive resin layer 6A, 6B, 6C, 6D Window 7 2nd conductor layer 8 Surface protective film layer 9 Conductor layer

Claims (10)

(A) a polyamide soluble in an aqueous alkali solution; and (b) a general formula (V):

A positive photosensitive resin composition comprising: a compound having a phenolic hydroxyl group shown in (2); (c) an o-quinonediazide compound; and (d) a solvent. The (a) polyamide soluble in an aqueous alkali solution is represented by the general formula (VII):

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)
The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition is represented by the formula:   The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition further comprises (e) a thermal latent acid generator that generates an acid by heating.   The component (a) is formed by blending 1 to 30 parts by weight of the component (b) and 5 to 100 parts by weight of the component (c). The positive photosensitive resin composition according to any one of the above.   (B) Component 1-30 parts by weight, (c) Component 5-100 parts by weight, and (e) Component 0.1-30 parts by weight with respect to 100 parts by weight of component (a). The positive photosensitive resin composition according to claim 3, wherein   Applying the positive photosensitive resin composition according to any one of claims 1 to 5 on a support substrate and drying; exposing the photosensitive resin film obtained by the drying step; The pattern formation method characterized by including the process which develops the photosensitive resin film after the said exposure using alkaline aqueous solution, and the process which heat-processes the photosensitive resin film after the said development.   The pattern forming method according to claim 6, wherein in the step of heat-treating the photosensitive resin film after the development, the heat treatment is a treatment of irradiating microwaves in a pulsed manner while changing a frequency. .   8. The pattern forming method according to claim 6, wherein the heating temperature is 200 ° C. or lower in the step of heat-treating the photosensitive resin film after development.   An electronic component comprising a layer of a pattern obtained by the pattern forming method according to claim 6 as an interlayer insulating film layer or a surface protective film layer.   The electronic component according to claim 9, wherein the electronic component is an MRAM.

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