JP5514336B2 - Heat resistant resin composition - Google Patents

Description

  The present invention relates to a resin composition that is a precursor of a polybenzoxazole resin used as a surface protective film or an interlayer insulating film of a semiconductor device, a method for producing a heat-resistant cured film using the resin composition, and The present invention relates to a semiconductor device having the cured film.

Conventionally, polybenzoxazole (hereinafter also referred to as PBO) 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 device. Since this PBO resin has low solubility in various solvents, it is generally used as a composition dissolved in a solvent in the form of a precursor hydroxypolyamide. Therefore, in use, a curing step is required in which the PBO precursor is closed (closed to an oxazole ring) and converted into a PBO resin. This ring closing process is usually performed by thermosetting which is heated to 300 ° C. or higher.
However, in recent years, semiconductor devices that are inferior in heat resistance compared to conventional products have been developed, and a reduction in the thermosetting temperature as a surface protective film or an interlayer insulating film is required, and in particular, thermosetting at 280 ° C. or lower is required. There are many things that can be done. However, in the conventional PBO precursor resin composition, the ring closure reaction from the PBO precursor to PBO does not proceed sufficiently in the region of 280 ° C. or lower, and thus the film obtained by curing at a temperature of 280 ° C. or lower. Did not have the excellent heat resistance, electrical properties, mechanical properties, etc. expected of PBO.

Conventionally, it has been known that the use of a dehydrating agent such as concentrated sulfuric acid, phosphorus oxychloride, polyphosphoric acid or the like is effective for proceeding the ring-closing reaction to the oxazole ring at a low temperature (for example, see Non-Patent Document 1). . However, it is not appropriate to add these dehydrating agents to the PBO precursor resin composition in view of the stability of the composition, and no satisfactory one has been proposed yet.
Furthermore, the PBO precursor resin composition is often used as a positive photosensitive resin composition that can be developed with an alkaline aqueous solution (see, for example, Patent Document 1). The development mechanism of this positive photosensitive resin is that the photosensitive diazoquinone compound in the unexposed area is insoluble in the alkaline aqueous solution, but the photosensitive diazoquinone compound undergoes a chemical change upon exposure to become an indenecarboxylic acid compound. It makes use of being soluble in an alkaline aqueous solution. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, it becomes possible to produce a relief pattern of only the unexposed portion.

  When the PBO precursor resin composition is used for a positive photosensitive resin composition containing a photosensitive diazoquinone compound, it is more difficult to select a method for promoting the ring closure to the oxazole ring from the viewpoint of stability and lithography performance. It is. On the other hand, Patent Document 2 proposes a photosensitive resin composition containing an amine imide compound that generates a base by heating in addition to a polyoxazole precursor and a compound that generates an acid upon irradiation with actinic rays. Further, Patent Document 3 proposes a positive photosensitive resin composition comprising an alkali-soluble resin, a diazoquinone compound, and an aliphatic sulfonic acid compound as a positive photosensitive resin composition having excellent low-temperature curability. Patent Document 4 includes a hydroxypolyamide, an ester compound, and a photosensitive diazoquinone compound as a positive photosensitive resin composition in which the ring closure reaction of PBO proceeds sufficiently even when used at a low thermosetting temperature. A characteristic positive photosensitive resin composition has been proposed.

However, the amine imide compound described in Patent Document 2 that generates a base by heating is insufficient in ring closure, and the expected performance cannot be obtained. In Patent Document 3, it is clear that the sulfonic acid compound used is hydrolyzed during storage of the composition to produce sulfonic acid, and there is a problem in storage stability as described later in Comparative Examples. Further, in Patent Documents 3 and 4, there is a concern that the copper wiring, which is expected to be used in future semiconductor devices due to the generation of acid, is corroded.
Compared with these techniques, the heat-resistant resin composition of the present invention satisfies the cyclization reaction to the oxazole ring at 280 ° C. or less and the storage stability of the composition in a higher dimension.

JP 63-096162 A JP 2004-077551 A JP 2006-010781 A JP 2006-126809 A

The Chemical Society of Japan "Experimental Chemistry Course 4th Edition Vol. 24 Organic Synthesis VI" published by Maruzen Co., Ltd., p525

  INDUSTRIAL APPLICABILITY The present invention provides a heat-resistant resin composition in which the ring-closing reaction of PBO proceeds sufficiently even when used at a low thermosetting temperature of 280 ° C. or less, and a method for producing a cured film-coated substrate using the composition Another object is to provide a semiconductor device having the cured film. Further, when it contains a photosensitive diazoquinone compound, in addition to the above, a highly sensitive heat-resistant resin composition, a method for producing a substrate with a cured film using the composition, and a semiconductor having the cured film An object is to provide an apparatus.

  As a result of intensive studies to solve the above problems, the present inventor has found that a hydroxypolyamide having a specific structure has a polyester compound having a number average molecular weight of 300 or more and a polyalkylene glycol compound having a number average molecular weight of 200 or more. It has been found that a heat-resistant resin composition that solves the above problems can be obtained by combining at least one compound selected from the group consisting of the present invention, and has led to the present invention.

That is, the present invention is as follows.
1. (A) Hydroxy polyamide having a repeating unit represented by the following general formula (1): 100 parts by mass, (B) a polyester compound having a number average molecular weight of 300 or more, and a polyalkylene glycol compound having a number average molecular weight of 200 or more. A heat-resistant resin composition comprising at least one compound selected from the group consisting of: 1 to 50 parts by mass.
Wherein X ₁ is a tetravalent organic group having 2 or more carbon atoms, X ₂ , Y ₁ and Y ₂ are divalent organic groups having 2 or more carbon atoms, and m is 2 to 1000. An integer, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ and n including X ₂ and Y ₂ (The order of arrangement of the individual diamide units does not matter.)

2. Furthermore, (C) 1-50 mass parts of photosensitive diazoquinone compounds are contained, The heat resistant resin composition of said 1 characterized by the above-mentioned.
3. 3. The heat-resistant resin composition as described in 1 or 2 above, wherein the (B) polyester compound having a number average molecular weight of 300 or more is a polyester compound obtained using fatty acid as one of raw materials.
4). 3. The heat-resistant resin composition as described in 1 or 2 above, wherein the (B) polyalkylene glycol compound having a number average molecular weight of 200 or more is a polyalkylene glycol compound having a repeating unit of ethylene glycol.

5. A method for producing a substrate with a cured film of a heat-resistant resin layer, comprising: laminating a heat-resistant resin layer comprising the heat-resistant resin composition described in 1 above on a substrate and heat-treating the heat-resistant resin layer.
6). (1) A heat-resistant resin layer comprising the heat-resistant resin composition according to any one of 2 to 4 above is laminated on a substrate, and (2) actinic radiation is applied to the heat-resistant resin layer through a mask. Curing of a heat-resistant resin layer, characterized by exposure or irradiation with light, electron beam or ion beam, (3) elution removal of the exposed portion or irradiated portion, and (4) heat treatment of the resulting pattern A method for manufacturing a substrate with a film. 7). A semiconductor device comprising a cured film obtained by the production method according to 5 or 6 above.

  According to the present invention, even when used at a heat curing temperature as low as 280 ° C. or less, the ring closure reaction of PBO proceeds sufficiently, and the heat-resistant resin composition having high storage stability and the substrate with a cured film using the composition A manufacturing method and a semiconductor device having the cured film can be provided. Further, when it contains a photosensitive diazoquinone compound, in addition to the above, a highly sensitive heat-resistant resin composition, a method for producing a substrate with a cured film using the composition, and a semiconductor having the cured film An apparatus can be provided.

<Heat resistant resin composition>
Each component which comprises the heat resistant resin composition of this invention is demonstrated concretely below.
(A) Hydroxypolyamide Hydroxypolyamide, which is the base polymer of the heat resistant resin composition, has a repeating unit represented by the following general formula (1).
Wherein X ₁ is a tetravalent organic group having 2 or more carbon atoms, X ₂ , Y ₁ and Y ₂ are divalent organic groups having 2 or more carbon atoms, and m is 2 to 1000. An integer, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ and n including X ₂ and Y ₂ (The order of arrangement of the individual diamide units does not matter.)

In the general formula (1), the dihydroxydiamide unit is composed of a bisaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ and a dicarboxylic acid having a structure of Y ₁ (COOH) ₂ . Here, the two groups of amino group and hydroxy group of the bisaminophenol are each in the ortho position, and the hydroxypolyamide is closed to change into polybenzoxazole which is a heat resistant resin.
X ₁ is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms. X ₂ , Y ₁ , and Y ₂ are preferably each independently a divalent organic group having 2 to 30 carbon atoms.
m is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20. The hydroxy polyamide may have the following general formula (
N diamide units of 1) may be condensed. The diamide unit is composed of a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of Y ₂ (COOH) ₂ . n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10. If the ratio of the diamide unit in the hydroxy polyamide is too high, the solubility in an alkaline aqueous solution used as a developer is lowered. Therefore, the value of m / (m + n) is preferably 0.5 or more, 0.7 More preferably, it is more preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- ( -Amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3 '-Dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3- And diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Particularly preferred among these bisaminophenols is when X ₁ is an aromatic group selected from the following.

As the diamine having a structure of X ₂ (NH _{2) 2,} an aromatic diamine, such as silicon diamine.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diamino Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9′-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, 4, 4′-diaminobenzanilide and at least one group selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group, as the hydrogen atom of the aromatic nucleus of these aromatic diamines Or the compound substituted by the atom is mentioned.

  Further, silicon diamine can be selected in order to enhance the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4 -Aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis ( γ-aminopropyl) tetraphenyldisiloxane and the like.

Moreover, as a preferable dicarboxylic acid having a structure of Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ , a case where Y ₁ and Y ₂ are aromatic groups selected from the following can be mentioned.
Wherein A is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Means a group of
Among these, preferred examples of dicarboxylic acids include 4,4′-diphenyl ether dicarboxylic acid and isophthalic acid, and 4,4′-diphenyl ether dicarbonyl chloride or isophthaloyl chloride obtained by chlorinating the dicarboxylic acid is a PBO precursor. Used in the synthesis of natural hydroxypolyamides.

(A) The end group of hydroxypolyamide can be sealed with a specific organic group.
Examples of such a blocking group include a group having an unsaturated bond as described in JP-A No. 05-197153, or 4-methylcyclohexyl-1,2-dicarboxylic anhydride. When sealed with these, it is expected that the mechanical properties (particularly elongation) of the coating film after heat curing and the cured relief pattern shape will be good. Preferable examples of such a sealing group include the following groups.

(A) The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of hydroxypolyamide is preferably 3,000 to 50,000, and preferably 6,000 to 30,000. More preferred. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured film of the heat resistant resin composition. Moreover, from a viewpoint of resolution, 50,000 or less is preferable. Tetrahydrofuran (hereinafter also referred to as “THF”) and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are recommended as developing solvents for GPC. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
(B) At least one compound selected from the group consisting of a polyester compound having a number average molecular weight of 300 or more and a polyalkylene glycol compound having a number average molecular weight of 200 or more (hereinafter also simply referred to as “component (B)”).
In the heat resistant resin composition, it is important to contain at least one compound selected from the group consisting of a polyester compound having a number average molecular weight of 300 or more and a polyalkylene glycol compound having a number average molecular weight of 200 or more. The polyester compound is a compound containing a plurality of repeating units having an ester group, and the polyalkylene glycol is a compound obtained by polymerizing a plurality of alkylene glycols.

Examples of the polyester compound having a number average molecular weight of 300 or more include, for example, Polysizer (registered trademark, manufactured by Dainippon Ink & Chemicals, Inc., the same shall apply hereinafter) W-4000 (adipic acid type, number average molecular weight 4000), Polycizer W-2610 (Adipin). Acid system, number average molecular weight 2600), polysizer W-2310 (adipic acid system, number average molecular weight 2300), polysizer W-2050 (adipic acid system, number average molecular weight 2000), polysizer W-1000 (adipic acid system, number average) Molecular weight 1000), polysizer W-320 (adipic acid type, number average molecular weight 1000), polysizer W-83 (adipic acid type, number average molecular weight 500), polysizer P-29 (phthalic acid type, number average molecular weight 1500), polysizer W-23-S (phthalic acid type, number average molecular weight 650) Polycizer W-20 (phthalic acid-based, number-average molecular weight 1000) and the like. The number average molecular weight of the polyester compound is preferably 10,000 or less. Among them, the polyester compound having a number average molecular weight of 300 or more is preferably a polyester obtained using fatty acid as one of the raw materials from the viewpoint of promoting the ring-closing reaction from the PBO precursor to PBO. Specific examples include polysizer W-4000 (adipic acid type, number average molecular weight 4000), polysizer W-2610 (adipic acid type, number average molecular weight 2600), polysizer W-2310 (adipic acid type, number average molecular weight 2300), Polysizer W-2050 (Adipic acid type, number average molecular weight 2000), Polycizer W-1000 (Adipic acid type, number average molecular weight 1000), Polysizer W-320 (Adipic acid type, number average molecular weight 1000), Polycizer W-83 ( Adipic acid type, number average molecular weight 500).

Furthermore, as a polyester compound having a number average molecular weight of 300 or more, fatty acid is obtained as one of the raw materials from the viewpoint of promoting the ring-closure reaction from the PBO precursor to PBO and the storage stability of the composition. A polyester compound of 500 to 3000 is preferred. Specific examples include polysizer W-2610 (adipic acid type, number average molecular weight 2600), polysizer W-2310 (adipic acid type, number average molecular weight 2300), polysizer W-2050 (adipic acid type, number average molecular weight 2000), Examples include Polysizer W-1000 (adipic acid type, number average molecular weight 1000), Polycizer W-320 (adipic acid type, number average molecular weight 1000), and Polycizer W-83 (adipic acid type, number average molecular weight 500).
Examples of the polyalkylene glycol compound having a number average molecular weight of 200 or more include pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, dodecaethylene glycol, polyethylene glycol 200 (pure chemistry Company, number average molecular weight 200), polyethylene glycol 300 (manufactured by Junsei Chemical, number average molecular weight 300), polyethylene glycol 400 (manufactured by Junsei Chemical, number average molecular weight 400), polyethylene glycol 600 (manufactured by Junsei Chemical, number average) Molecular weight 600), polyethylene glycol 1000 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 1000), polyethylene glycol 2000 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 2000), polyethylene Glycol 4000 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 3000), polyethylene glycol 6000 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 8500), polyethylene glycol 20000 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 20000), polypropylene glycol 400 (Junsei Chemical Company, number average molecular weight 400), polypropylene glycol 700 (manufactured by Junsei, number average molecular weight 700), polypropylene glycol 1000 (manufactured by Junsei, number average molecular weight 1000), polypropylene glycol 2000 (manufactured by Junsei Chemical, number average) Molecular weight 2000).

  Among these, as the polyalkylene glycol compound having a number average molecular weight of 200 or more, a polyalkylene glycol compound having a repeating unit of ethylene glycol is preferable from the viewpoint of promoting the ring-closing reaction from the PBO precursor to PBO. Specific examples include pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, dodecaethylene glycol, polyethylene glycol 200 (manufactured by Junsei Co., Ltd., number average molecular weight 200), polyethylene glycol 300 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 300), polyethylene glycol 400 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 400), polyethylene glycol 600 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 600), polyethylene glycol 1000 (Junsei Chemical Co., Ltd.) Manufactured, number average molecular weight 1000), polyethylene glycol 2000 (manufactured by Junsei Co., Ltd., number average molecular weight 2000), polyethylene glycol 4000 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 3000) Polyethylene glycol 6000 (Junsei Chemical Co., Ltd., number average molecular weight 8500), polyethylene glycol 20000 (Junsei Chemical Co., Ltd., number-average molecular weight 20000) and the like.

Furthermore, the polyalkylene glycol compound having a number average molecular weight of 200 or more has a repeating unit of ethylene glycol and a number average molecular weight of 300 from the viewpoint of promoting the ring closure reaction from the PBO precursor to PBO and the storage stability of the composition. To 1000 polyalkylene glycol compounds are preferred. Specific examples include heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, dodecaethylene glycol, polyethylene glycol 300 (manufactured by Junsei Co., Ltd., number average molecular weight 300), polyethylene glycol 400 (manufactured by Junsei Chemical Co., Ltd., several Average molecular weight 400), polyethylene glycol 600 (manufactured by Pure Chemical Co., Ltd., number average molecular weight 600), and polyethylene glycol 1000 (manufactured by Junsei Chemical Co., Ltd., number average molecular weight 1000).
As the component (B), the group consisting of a polyester compound having a number average molecular weight of 300 or more is more heat-sensitive resin composition having photosensitivity than the group consisting of a polyalkylene glycol compound having a number average molecular weight of 200 or more. It is preferable because the composition has good adhesion to a silicon wafer when applied, pre-baked, exposed and developed on the silicon wafer.

When component (B) is added to the above-mentioned (A) hydroxypolyamide, the cyclization reaction of PBO sufficiently proceeds even at a heat treatment at a low temperature of 280 ° C. or less, and excellent heat resistance, electrical properties, mechanical properties, etc. To express.
(B) As addition amount of a component, 1-50 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide, 2-40 mass parts is more preferable, and 3-30 mass parts is further more preferable. If the addition amount of the polyester compound having a number average molecular weight of 300 or more and the polyalkylene glycol compound having a number average molecular weight of 200 or more is 1 part by mass or more, an effect of promoting cyclization of PBO can be obtained by heat treatment at a low temperature of 280 ° C. or less. If it is 50 parts by mass or less, the properties of the obtained cured film are not impaired.

(C) Photosensitive diazoquinone compound It is a preferred embodiment of the present invention that the heat-resistant resin composition contains (C) a photosensitive diazoquinone compound and has lithographic performance.
The photosensitive diazoquinone compound is a compound having a 1,2-naphthoquinonediazide structure, and U.S. Pat. Nos. 2,772,972, 2,797,213, and 3,669,658. Is a known substance. As an example of a preferable thing, the following are mentioned, for example.
(In the formula, Q is a hydrogen atom or a naphthoquinonediazide sulfonic acid ester group shown below, and all Qs are not hydrogen atoms at the same time.)

Among these, the following are particularly preferable.
In the case where the heat-resistant resin composition contains a photosensitive diazoquinone compound, the content is preferably 1 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the (A) hydroxypolyamide. If the blending amount of the photosensitive diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good. Conversely, if it is 50 parts by mass or less, the tensile elongation of the cured film is maintained, and the development residue ( Scum) is suppressed.

(D) Other components It is also possible to add a dye, a surfactant, an adhesion aid for improving adhesion to the substrate, and a crosslinking agent to the heat-resistant resin composition as necessary.
The additives will be described more specifically. Examples of the dye include methyl violet, crystal violet, and malachite green.
As addition amount of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide.
In addition, as the surfactant, for example, nonionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, such as Florard (registered trademark, trade name, manufactured by Sumitomo 3M), Fluorosurfactants such as MegaFac (registered trademark, trade name, manufactured by Dainippon Ink and Chemicals) or Lumiflon (registered trademark, trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) And organosiloxane surfactants such as DBE (trade name, manufactured by Chisso Corporation) and Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

When the surfactant is contained in the heat resistant resin composition, the content is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of (A) hydroxypolyamide.
Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.
Specific preferred examples of the silane coupling agent include, for example, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, and 3-methacryloxypropyl. Trialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkyl Silane and acid anhydride or acid dianhydride reactant, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino group converted to urethane group or urea group And the like of. In this case, methyl group, ethyl group, butyl group, etc. as the alkyl group, maleic anhydride, phthalic anhydride, etc. as the acid anhydride, pyromellitic dianhydride as the acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, etc., t-butoxycarbonylamino group as a urethane group, phenylamino as a urea group Examples thereof include a carbonylamino group.

As content in the case where an adhesive aid is contained in the heat resistant resin composition, 0.1 to 30 parts by mass is preferable with respect to 100 parts by mass of (A) hydroxypolyamide.
Examples of the crosslinking agent include 1,1,2,2-tetra (p-hydroxyphenyl) ethane, tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy ) Epoxy compounds such as naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone magnesium (II) ) Salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, Metal chelating agents such as fluoroacetylacetone magnesium (II) salt and trifluoroacetylacetone nickel (II) salt, Nicalak MW-30MH, MW-100LH (trade name, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, Cymel 303 (trade name, And alkylated melamine resins such as Mitsui Cytec).
As addition amount of a crosslinking agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide.

(E) Solvent The heat resistant resin composition may be dissolved in a solvent to form a varnish and used as a solution of the heat resistant resin composition. Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. , Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3- Methoxypropionate or the like can be used alone or in combination. Of these solvents, non-amide solvents are preferable from the viewpoint of little influence on photoresists, and specific more preferable examples include γ-butyrolactone, cyclopentanone, cyclohexanone, isophorone and the like.
As content when a solvent is contained in a heat resistant resin composition, 50-1000 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, a method for producing a cured film by applying a heat resistant resin composition to a substrate will be specifically described below.
(1) The process of laminating | stacking the heat resistant resin layer which consists of a heat resistant resin composition on a board | substrate.
As a first step, the heat-resistant resin composition is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spinner or a roll coater. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent.
(2) A step of exposing the heat-resistant resin layer to actinic radiation or irradiating with a light beam, an electron beam or an ion beam through a mask.
As a second step, the heat-resistant resin layer is exposed to actinic radiation through a mask using a contact aligner or a stepper, or directly irradiated with a light beam, an electron beam or an ion beam.
(3) A step of eluting and removing the exposed portion or irradiated portion.
As a third step, the irradiated part is dissolved and removed with a developing solution, and preferably, a desired pattern is obtained by subsequently rinsing with a rinsing solution. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.

The developer used for developing the resin film formed from the heat-resistant resin composition dissolves and removes the alkali-soluble polymer and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.
Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia and the like.

Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.
Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

(4) The process of heat-processing the obtained pattern.
As a fourth step, the obtained pattern can be heat-treated to form a heat-resistant cured film having a polybenzoxazole structure. In this heat treatment, a temperature of 180 ° C. or higher is applied for 5 minutes or more, and a certain constant temperature may be maintained, or the temperature may be continuously increased. Preferred heat treatment conditions are such that the maximum temperature is 200 ° C. or higher and the time of 200 ° C. or higher is 30 minutes or longer.
Specifically, when the composition of the present invention is used for the production of a semiconductor device having inferior heat resistance, such as MRAM, organic semiconductor, and CMOS having copper wiring, which cannot be heated at 300 ° C. or higher, the heat treatment temperature is set to 180 to It is preferable to set it as 280 degreeC, and it is more preferable to set it as 220-250 degreeC. On the other hand, when used for the manufacture of a semiconductor device which does not have a problem in heating to 300 ° C. or higher, it is more preferably 300 to 350 ° C.

When the heat resistant resin composition does not contain (C) a photosensitive diazoquinone compound and does not have photosensitivity, the second step and the third step may not be performed.
The cured film prepared by the above-described manufacturing method is a known method for manufacturing a semiconductor device as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a device having a bump structure. By combining with, a semiconductor device can be manufactured. It is also useful as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like.

The present invention will be described more specifically based on reference examples, examples and comparative examples.
<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a separable flask having a volume of 2 liters, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine, N, 692 g of N-dimethylacetamide (hereinafter referred to as “DMAc”) was mixed and stirred at room temperature (25 ° C.) to dissolve. A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of diethylene glycol dimethyl ether (hereinafter referred to as “DMDG”) separately was added dropwise to the dropping funnel. . The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared.

Next, this was cooled to 8 ° C. with a water bath, and a solution obtained by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropwise addition, the reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water and dehydrated appropriately, followed by vacuum drying. Got. The weight average molecular weight of the hydroxypolyamide thus synthesized by gel permeation chromatography (hereinafter also referred to as “GPC”) was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: manufactured by Showa Denko KK, trade name: Shodex, KF-807 / KF-806M / KF-806M / KF-802.5; serial eluent: tetrahydrofuran, 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, trade name: Shodex RI-101
Further, when further purification of hydroxypolyamide is required, it can be carried out by the following method. That is, after re-dissolving the hydroxypolyamide obtained above in DMDG, this was treated with a cation exchange resin and an anion exchange resin, and the resulting solution was poured into ion exchange water and then precipitated hydroxy By purifying the polyamide by filtration, washing with water and vacuum drying, a purified hydroxypolyamide can be obtained.

[Reference Example 2]
In a 2 liter separable flask, 171.4 g (0.47 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 71.2 g (0.90 mol) of pyridine, N, 600 g of N-dimethylacetamide (hereinafter referred to as “DMAc”) was mixed and stirred at room temperature (25 ° C.) for dissolution. Separately, 6.1 g (0.04 mol) of 4-methylcyclohexyl-1,2-dicarboxylic anhydride was dissolved in 30 g of γ-butyrolactone (hereinafter referred to as “GBL”) from a dropping funnel. It was dripped. The time required for the dropwise addition was 10 minutes, and the maximum reaction solution temperature was 27 ° C.
After stirring for 5 hours, the reaction solution was analyzed by GPC (for low molecular weight measurement) and it was confirmed that 4-methylcyclohexyl-1,2-dicarboxylic anhydride had disappeared. GP
The analysis conditions for C (for low molecular weight measurement) are described below.
Column: manufactured by Showa Denko KK, trade name: Shodex, KF-802 / KF-801 / KF-801; serial eluent: tetrahydrofuran, 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, trade name: Shodex RI-930
Next, this was cooled to −10 ° C. with a dry ice bath, and separately, 99.6 g (0.34 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride and 22.8 g (0.12 mol) of isophthaloyl chloride were added to 612 g of GBL. ) Was dissolved from the dropping funnel. The time required for the dropwise addition was 120 minutes, and the maximum reaction solution temperature was 2 ° C. Three hours after the completion of dropping, hydroxypolyamide P-2 having a weight average molecular weight of 25000 (polystyrene conversion) measured by GPC method was obtained.

<Synthesis of photosensitive diazoquinone compound>
[Reference Example 3]
In a 1-liter separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g of pyridine (0.6 mol) ), And 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added in powder form at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected and the product was detected as a single peak with a purity of 99%. This reaction solution was dropped as it was into 1 liter of ion-exchanged water with stirring, and the precipitate was filtered off, and then 500 ml of THF was added and dissolved by stirring. This homogeneous solution was dissolved in a cation exchange resin: Amberlyst 15 (organo) Residual pyridine was removed through a glass column packed with 100 g. Next, this solution was dropped into 3 liters of ion-exchanged water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.
The product is imidized, it is not characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1 appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum is present, and NMR spectrum This was confirmed by the absence of amide and carboxylic acid proton peaks.

Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for an additional 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. . The filtrate obtained at this time was added dropwise to 5 liters of a 0.5 wt% aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 liters of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like material obtained was vacuum-dried at 40 ° C. for 24 hours to obtain photosensitive diazoquinone compound Q-1.

<Preparation of heat resistant resin composition>
[Examples 1 to 11 and Comparative Examples 1 to 3]
Table 1 shows the photosensitive diazoquinone compound (Q-1) obtained in Reference Example 3 with respect to 100 parts by mass of the hydroxypolyamide (P-1 or P-2) obtained in Reference Examples 1 and 2 above. After adding the stated amount and further adding the component (B) shown below and other additives Z (PAG108, manufactured by Ciba Specialty Chemicals) in the amount shown in Table 1 and dissolving in 170 parts by weight of GBL, It filtered with a 0.2 micrometer filter, and the heat resistant resin composition of Examples 1-11 described in Table 1 and Comparative Examples 1-3 was prepared.

<Evaluation of heat resistant resin composition>
(1) Evaluation of Oxazolization Rate The above heat-resistant resin composition was spin-coated on a 6-inch silicon wafer with a spin coater (clean track Mark-8) manufactured by Tokyo Electron, and prebaked at 120 ° C. for 180 seconds on a hot plate. And a coating film was formed. In a vertical curing furnace (manufactured by Koyo Lindberg), curing (heat curing treatment) was performed in a nitrogen atmosphere at 250 ° C. or 350 ° C. for 1 hour. The IR spectrum of the obtained cured film was measured by a microscopic ATR method, and after adjusting the size of each spectrum using the peak at 1490 cm ⁻¹ as a reference, the peak at 1050 cm ⁻¹ , which is the characteristic absorption of the oxazole ring, was measured. Using the size, the oxazolation rate at 250 ° C. when the oxazolation rate at 350 ° C. was taken as 100% was calculated according to the following formula and shown in Table 2.
Oxazole rate (%) = (250 ℃ heat treatment the peak height of the sample 1050cm ^-1) ÷ (350 ℃ heat treatment the peak height of 1050 cm ^-1 of sample) × 100

(2) Viscosity change rate evaluation The change rate of the viscosity of the heat resistant resin composition after being allowed to stand at 23 ° C for 1 week was measured as follows and shown in Table 2. If the rate of change in viscosity was within 5%, the storage stability was good.
Viscosity change rate (%) = (viscosity of heat resistant resin composition after standing for 1 week−viscosity of heat resistant resin composition immediately after preparation) ÷ viscosity of heat resistant resin composition immediately after preparation × 100
(3) Sensitivity evaluation The heat resistant resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3 were spin-coated on a 6-inch silicon wafer with a spin coater (clean track Mark-8) manufactured by Tokyo Electron, Pre-baking was performed at 120 ° C. for 180 seconds on a hot plate to form a coating film having a thickness of 10.7 μm. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg.

The obtained coating film was exposed with a stepper (NSR2005i8A) manufactured by Nikon Corporation having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern while changing the exposure stepwise. This was developed using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) manufactured by AZ Electronic Materials, so that the film thickness after development was 9.1 μm at 23 ° C. Development was carried out by adjusting the time to form a positive relief pattern. The sensitivity of the heat resistant resin composition is shown in Table 2.
The sensitivity of the heat resistant resin composition was evaluated as follows.
[Sensitivity (mJ / cm ² )]
The minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film during the development time.

From the examples, the composition added with the component (B), which is an essential component of the present invention, exhibits a sufficiently high oxazolation rate to obtain various properties expected as a final film, and also exhibits storage stability (viscosity change). Rate) and patterning characteristics (sensitivity) were satisfactory. On the other hand, the composition in which the component (B) was not added has a low oxazolation rate, and the composition in which a compound that generates an acid by heat instead of the component (B) has a high oxazolation rate, Patterning characteristics deteriorated.

  The heat resistant resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a device having a bump structure, and an interlayer insulating film for a multilayer circuit It can be suitably used as a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (2)

(A) Hydroxy polyamide having a repeating unit represented by the following general formula (1): 100 parts by mass, (B) a polyester compound having a number average molecular weight of 500 or more and 4000 or less , and a poly having a number average molecular weight of 600 or more and 2000 or less . at least one compound selected from the group consisting of alkylene glycol compounds: 1 to 50 parts by weight, the heat-resistant resin layer made of a heat resistance resin composition you containing laminated on a substrate, heat treating the heat-resistant resin layer A method for producing a substrate with a cured film of a heat-resistant resin layer, comprising:
(Wherein, X ₁ is have a 2 or more carbon atoms, the tetravalent organic group two pairs amino group and a hydroxy group is derived from bisaminophenols in each ortho position to each other, X _2, Y ₁ and Y ₂ is a divalent organic group having 2 or more carbon atoms, m is an integer of 2 to 1000, n is an integer of 0 to 500, and m / (m + n)> 0.5. (The order of arrangement of m dihydroxydiamide units containing X ₁ and Y ₁ and n diamide units containing X ₂ and Y ₂ is not limited.) A semiconductor device comprising a cured film obtained by the manufacturing method according to claim 1 .