JP2003330167A - Heat resistant photosensitive resin composition, method for producing pattern and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat resistant photosensitive resin composition ensuring little impairment of sensitivity and the rate of a residual film, excellent in elongation percentage, excellent in workability of a relief pattern and excellent also in mechanical properties after curing by using a photosensitive polymer which is a relatively low molecular weight body in a fabrication process to improve suitability to a fabrication process and becomes a high molecular weight body during curing. <P>SOLUTION: The heat resistant photosensitive resin composition comprises (A) a photosensitive polymer, (B) a chain extender capable of increasing the molecular weight of the polymer during heat curing, (C) a compound capable of generating an acid under light and (D) a solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat-resistant photosensitive resin composition, a pattern manufacturing method, and a semiconductor device. In particular, as an alkaline aqueous solution development positive type heat-resistant photosensitive material,
The present invention relates to a buffer coat film of a semiconductor device, a heat-resistant photosensitive resin composition suitable for an interlayer insulating film, a pattern manufacturing method, and a semiconductor device.

[0002]

2. Description of the Related Art Polyimide resins and polybenzoxazole resins are widely used because of their excellent heat resistance and their properties. Particularly as a semiconductor material, it is used as a protective film (buffer coat) between a sealant and a chip. Recently, in order to shorten the semiconductor manufacturing process, photosensitivity is imparted to the resin itself so that a relief pattern can be easily formed by coating, exposing and developing.
Polybenzoxazole is becoming mainstream. The conventional photosensitive polyimide is mainly of a negative type, which uses an organic solvent as a developing solution and insolubilizes an exposed portion. The organic solvent waste liquid is usually incinerated, but the demand for alkaline aqueous solution development is increasing from the viewpoint of environmental protection. Further, in general, an organic aqueous solution is effective in developing an alkaline aqueous solution in terms of material cost and waste liquid processing cost. Conventional technologies include naphthoquinonediazide compounds as photosensitizers, polybenzoxazole precursors as base polymers, polyamic acid esters with alkali-soluble groups as base polymers, and copolymers of these. It is on the market. However, both polymer systems have a problem that the dissolution rate ratio of the exposed area and the unexposed area at the time of development, that is, the so-called contrast is not sufficient, and particularly the system of the polybenzoxazole precursor has a problem that the adhesiveness to the semiconductor substrate is poor.

As a heat-resistant resin having a sufficient adhesive strength with a semiconductor substrate, and as one candidate technique capable of improving contrast by developing with an alkaline aqueous solution, a polyamic acid ester as a base polymer is used as a chemically amplified photosensitive resin. Have been devised (JP-A-10-171120, JP-A-4-120171, JP-A-11-20).
2489). However, in the alkaline aqueous solution development photosensitive resin, it is the solubility of the polymer in the alkaline developer that influences the performance, and it is extremely difficult to accurately control the solubility with these devised ones. . In order to control the solubility of the polymer in an alkaline developing solution, various properties such as the molecular weight of the polymer are difficult to be limited to an extremely narrow range. Usually, it is necessary to make a polymer with a low molecular weight in order to improve processability and solubility. A polymer having such a low molecular weight cannot obtain sufficient mechanical properties even when cured, and the original properties of polyimide are lost. In the positive type, the polymer has a low molecular weight, and unlike the negative type, the molecular weight does not increase due to cross-linking during the processing process, so the relief pattern obtained by exposure and development can be heated by heating during the curing process. It may melt. In order to compensate for these problems, it has been proposed to introduce a cross-linking group having a C = C double bond at the end of the polymer (JP-A-11-143070). However, it may polymerize with naphthoquinonediazide, which is a positive-type photosensitizer, and has poor stability.

[0004]

The present invention improves the processability by a relatively low molecular weight material during the processing process and increases the molecular weight during the curing process, so that the sensitivity and the residual film rate are hardly impaired. The present invention provides a photosensitive resin composition having excellent elongation and the like, excellent workability of a relief pattern, and excellent mechanical properties after curing, and its use. The present invention also provides a positive photosensitive resin composition that can be developed with an aqueous alkali solution, and its use.

[0005]

The present invention comprises (A) a photosensitive polymer, (B) a chain extender capable of increasing the molecular weight of the polymer during the heat curing process, and (C) an acid generated by light. And a (D) solvent are contained in the heat-resistant photosensitive resin composition.

In the present invention, the polymer of the above (A) is represented by the general formula (1)

[Chemical 3] (In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R 1
₁ is hydrogen or a monovalent organic group, and n1 is 2 to 500
Represents the number of repeating units of the polymer), a polyimide precursor having a structure represented by the general formula (2)

[Chemical 4] (In the formula, X ₂ is a divalent organic group, Y ₂ is a tetravalent organic group, n 2
Is a polybenzoxazole precursor having a structure represented by 2 to 500 representing the number of repeating units of the polymer), a copolymer thereof, or a mixture thereof, and the above heat-resistant photosensitive resin composition.

The present invention also relates to the above heat-resistant photosensitive resin composition which is an alkaline aqueous solution development positive type. In the present invention, the polymer (A) has a group represented by -NR'R "(R 'and R" independently represent a hydrogen atom or a monovalent organic group) at the terminal, The chain extender of (B) is
Two or more -COOR '(R' is a hydrogen atom or 1 at the terminal
The present invention relates to the above-mentioned photosensitive resin composition, which is a compound or polymer having a group represented by a valent organic group).

In the present invention, the polymer of (A) has a group represented by -COOR '(R' represents a hydrogen atom or a monovalent organic group) at the terminal, and the polymer of (B) The above photosensitivity, wherein the chain extender is a compound or polymer having two or more -NR'R "groups (R 'and R" independently represent a hydrogen atom or a monovalent organic group) at the terminal. It relates to a resin composition.

The present invention also provides -NR'R "at both ends.
(R ′ and R ″ independently represent a hydrogen atom or a monovalent organic group), a polymer (A) having a group represented by the formula (A), two or more —COOR ′ at the end (R ′ is a hydrogen atom or a monovalent organic group) The present invention relates to a heat-resistant photosensitive resin composition containing a compound having a group represented by (representing an organic group) or a polymer (B), (C) a compound capable of generating an acid by light, and (D) a solvent.

The present invention also provides -COOR 'at both ends.
(R ′ represents a hydrogen atom or a monovalent organic group), a polymer (A) having a group represented by two or more —NR ′ at a terminal.
R ″ (R ′ and R ″ independently represent a hydrogen atom or a monovalent organic group) or a compound or polymer (B), (C) a compound capable of generating an acid by light, and (D) ) A heat-resistant photosensitive resin composition containing a solvent.

The present invention also relates to a pattern manufacturing method including the steps of coating and drying the photosensitive resin composition according to any one of the above on a supporting substrate, exposing, and developing with an aqueous alkaline solution. The present invention also relates to a semiconductor device having a film formed using the photosensitive resin composition according to any one of the above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION One of the present inventions is (A) a heat-resistant photosensitive resin polymer, (B) a chain extender capable of increasing the molecular weight of the polymer in the course of heating and curing the polymer, (C ) A photosensitive resin composition containing a compound capable of generating an acid by light and a solvent (D) as an essential component. (A) in the present invention, from the viewpoint of heat resistance and the like, a polyimide precursor having a structure represented by the general formula (1), which generally has a repeating unit obtained from tetracarboxylic dianhydride and diamine in the main chain, Generally, a polybenzoxazole precursor having a structure represented by the general formula (2) having a repeating unit obtained from a dicarboxylic acid and bisaminophenol in the main chain, a copolymer of these repeating units, or a precursor thereof. It is preferably a mixture of In addition, as n1 and n2 in the said General formula (1) and (2), 6-500 are preferable, 8-500 are more preferable, 8-200 are still more preferable.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4 '.
-Biphenyltetracarboxylic dianhydride, 2,2 ',
3,3'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydrous, 2,2-bis (2,3-
Dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride,
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl)
Sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 1,2,
5,6-naphthalenetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
2,3,5,6-pyridinetetracarboxylic dianhydride,
3,4,9,10-Perylene tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Known tetracarboxylic acid dianhydrides such as hexafluoropropane dianhydride can be mentioned. These are used alone or in combination of two or more. In addition, it is not necessarily limited to those listed here.

Examples of diamines are 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3
-Aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-
Aminophenoxy) benzene, 2,2'-dimethyl-
4,4'-diaminobiphenyl, 2,2'-diethyl-
4,4'-diaminobiphenyl, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 3,3'-diethyl-
4,4'-diaminobiphenyl, 2,2 ', 3,3'-
Tetramethyl-4,4'-diaminobiphenyl, 2,
2 ', 3,3'-tetraethyl-4,4'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2, 2'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4 '
Examples thereof include known aromatic diamine compounds such as -diaminobiphenyl and 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl. These are used alone or in combination of two or more. In addition, it is not necessarily limited to those listed here.

As a method for introducing an alkali-soluble group,
At least part of the diamine component is 2,4-diaminobenzoic acid, 3,3′-diaminobiphenyl-5,5′-dicarboxylic acid, 4,4′-diaminodiphenyl ether-
5,5'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-5,5'-dicarboxylic acid, 4,4'-diaminodiphenylsulfone-5,5'-dicarboxylic acid, 4,
4'-diaminodiphenyl sulfide-5,5'-dicarboxylic acid or isomers thereof having one or more carboxyl groups, or 4,4'-diamino-3,
3'-dihydroxybiphenyl, 2,2'-bis (3-
The solubility can also be controlled by polymerizing a compound having a phenolic hydroxyl group such as amino-4-hydroxyphenyl) hexafluoropropane.

By reacting the tetracarboxylic dianhydride and the diamine in this manner, a polyamic acid as a polyimide precursor can be obtained. However, as in the case where R _{1 in the} general formula (1) is a monovalent organic group. In addition, by introducing an ester group, it becomes possible to control the solubility or perform light processing based on the principle of chemical amplification. The ester group of R ₁ is methyl,
There are alkyl groups such as ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, methyl ethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethoxymethyl, 2-trimethylsilylethoxymethyl, 3-oxocyclohexyl and the like. . Also,
It is not necessarily limited to those listed here.

As the dicarboxylic acid for obtaining the polybenzoxazole precursor, 3-fluoroisophthalic acid,
2-fluoroisophthalic acid, 3-fluorophthalic acid, 2
-Fluorophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 3,4,5,6-tetrafluorophthalic acid, 4,4'-hexafluoroisopropylidenediphenyl-1,1'-dicarboxylic acid, Perfluorosuberic acid, 2,2'-bis (trifluoromethyl) -4,4 '
Examples thereof include known dicarboxylic acids such as biphenylenedicarboxylic acid, terephthalic acid, isophthalic acid, and 4,4′-oxydiphenyl-1,1′-dicarboxylic acid. These are used alone or in combination of two or more. Also,
It is not necessarily limited to those listed here.

Examples of bisaminophenol for obtaining the polybenzoxazole precursor include 4,4'-diamino-3,3'-dihydroxybiphenyl and 2,2'-bis (3-amino-4-hydroxyphenyl) propane. ,
Known bisaminophenols such as 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane are used alone or in combination of two or more kinds. In addition, it is not necessarily limited to those listed here.

More generally, the tetracarboxylic dianhydride is represented by the following general formula (3).

[Chemical 5]

More generally, the diamine is represented by the following general formula (4).

[Chemical 6]

More generally, the dicarboxylic acid is represented by the following general formula (5).

[Chemical 7]

More generally, bisaminophenol is represented by the following general formula (6).

[Chemical 8]

In the above formulas, n is the number of repetitions and the symbols R and Z are monovalent and divalent organic groups in common, and examples of each are represented by the following formulas. Examples of monovalent organic groups:

[Chemical 9]

The example of the monovalent organic group is also applied as an example of R ^{1 in} the general formula (1). Examples of divalent organic groups:

[Chemical 10]

In the polymer (A) of the present invention, the chain extender (B) exerts its effect, so that the polymer to be used in combination with the component (B) is determined. For example, the polymer (A) has a group represented by -NR'R "(R 'and R" independently represent a hydrogen atom or a monovalent organic group) at the terminal, preferably both terminals. In this case, the chain extender (B) is a compound or polymer having at least two groups represented by -COOR '(R' represents a hydrogen atom or a monovalent organic group) at the terminal. On the other hand, when the polymer (A) has a group represented by -COOR '(R' represents a hydrogen atom or a monovalent organic group) at the terminal, preferably both terminals, (B) Chain extender has two or more -NR 'at the end.
A compound or polymer having a group represented by R "(R 'and R" independently represent a hydrogen atom or a monovalent organic group). Here, as the examples of the monovalent organic groups of R ′ and R ″, those exemplified as R in the general formulas (3) to (6) can be applied.

Examples of the component (A) having -NR'R "at both ends include the following: General formula (7):

[Chemical 11] (In the formula, X ₃ is a tetravalent organic group, Y ₃ is a divalent organic group, and R and R ₃ are hydrogen or a monovalent organic group. N3 is 2 to 5).
00 represents the number of repeating units of the polymer. )

General formula (8):

[Chemical 12] (In the formula, X ₄ is a divalent organic group, Y ₄ is a tetravalent organic group, and R and R ₄ are hydrogen or a monovalent organic group. N4 is 2 to 5
00 represents the number of repeating units of the polymer. )

In these cases, the chain extender of (B) is a compound or polymer having a group represented by two or more --COOR '(R' represents a hydrogen atom or a monovalent organic group) at the terminal. Examples include: General formula (9):

[Chemical 13] (In the formula, X ₅ is a (n5) -valent organic group, R ₅ is a monovalent organic group, and n 5 is an integer of 1 to 10.)

General formula (10):

[Chemical 14] (In the formula, X ₆ is a tetravalent organic group, Y ₆ is a divalent organic group, R ₆
Are independently hydrogen or a monovalent organic group. n6 is 0-2
0 (preferably 0 to 7, more preferably 0 to 5) represents the number of repeating units of the polymer. )

General formula (11):

[Chemical 15] (In the formula, X ₇ is a divalent organic group, Y ₇ is a tetravalent organic group, and R ₇ is independently hydrogen or a monovalent organic group. N7
Is 0 to 20 (preferably 0 to 7, more preferably 0 to
5) represents the number of repeating units of the polymer. )

On the other hand, examples of the component (A) having -COOR 'at both ends include the following. General formula (12):

[Chemical 16] (In the formula, X ₈ is a tetravalent organic group, Y ₈ is a divalent organic group, R ₈
Is hydrogen or a monovalent organic group. n8 is 2 to 500 and represents the number of repeating units of the polymer. )

General formula (13):

[Chemical 17] (In the formula, X ₉ is a divalent organic group, Y ₉ is a tetravalent organic group, R ₉
Is hydrogen or a monovalent organic group. n9 is 2 to 500 and represents the number of repeating units of the polymer. )

A group represented by two or more --NR'R "(R 'and R" independently represent a hydrogen atom or a monovalent organic group) at the terminal which is the chain extender of (B) in these cases. Examples of the compound or polymer having: General formula (14):

[Chemical 18] (In the formula, Y ₁₀ is a (n10) -valent organic group and R ₁₀ is a monovalent organic group. N10 is an integer of 1 to 10.)

General formula (15):

[Chemical 19] (In the formula, X ₁₁ is a tetravalent organic group, Y ₁₁ is a divalent organic group,
R is hydrogen or a monovalent organic group. n ₁₁ is 0 to 20
(Preferably 0 to 7, more preferably 0 to 5) represents the number of repeating units of the polymer. )

General formula (16):

[Chemical 20] (In the formula, X ₁₂ is a divalent organic group, Y ₁₂ is a tetravalent organic group, R is hydrogen or a monovalent organic group. N12 is 0.
-20 (preferably 0-7, more preferably 0-5) represents the number of repeating units of the polymer. ) Here, as an example of the monovalent organic group of R and R _{3 to} R ₁₀ described in the above general formulas (7) to (16), R of the above general formulas (3) to (6) is used. What is illustrated can be applied.

The chain extender capable of increasing the molecular weight of the polymer (B) in the present invention in the process of heat curing is a component different from the component (A), and is basically the above general formula ( 9), (10), (11), (14), (1
5), low molecular weight substances such as diamine, dicarboxylic acid, tetracarboxylic acid, and tetracarboxylic acid dianhydride exemplified in (16), low molecular weight polyimide precursor obtained from tetracarboxylic acid dianhydride and diamine, or Polymers of low molecular weight polybenzoxazole precursors obtained from dicarboxylic acids and bisaminophenol are preferred. However, when the polymer component (A) is acid-terminated, it must be amine-terminated, and when the polymer component is amine-terminated, it must be acid-terminated. When the chain extender (B) is a polymer,
It is preferable that the number of repeating units is 0 to 20 and the molecular weight is low, from the viewpoints of processability and physical properties, more preferably 0 to 10, further preferably 0 to 7, and particularly 0 to 5. preferable.

The chain extender capable of increasing the molecular weight of the polymer (B) during the heat curing process is the polymer component 1 of (A).
The amount is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 00 parts by weight.

The compound (C) used in the present invention, which generates an acid by light, is a photosensitizer, and has a function of generating an acid and increasing the solubility of the light-irradiated part in the alkaline aqueous solution. It is a thing. Examples thereof include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Not limited to the compounds listed here, any compound that generates an acid by light can be used.

The o-quinonediazide compound is, for example, o
It is obtained by subjecting a quinonediazidesulfonyl chloride compound to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazidesulfonyl chlorides include benzoquinone-
1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride and the like can be used.

Examples of the hydroxy compound include:
Hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Benzophenone, 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 (2,1-a) indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

(C) The compound capable of generating an acid by light is
0.1 to 5 relative to 100 parts by weight of the polymer component (A)
It is preferable to add 0 part by weight, and more preferably 1 to 20 parts by weight.

As the solvent (D) in the present invention, gamma butyrolactone, N-methyl-2-pyrrolidone, N
-Acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylsulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone, N-
Acetyl-ε-caprolactam and the like can be mentioned, and the kind thereof is particularly limited as long as it dissolves (A) a heat-resistant photosensitive polymer, (B) a chain extender, and (C) a compound capable of generating an acid by light. Not a thing. The amount is not particularly limited,
The amount is preferably 50 to 500 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the polymer (A).

In addition to the above essential components, the photosensitive resin composition of the present invention contains
The base polymer can be modified by adding a silane coupling agent or using diaminosiloxane as a material of the polymer (A). Further, in the present invention, the photosensitive characteristics,
A compound having a phenolic hydroxyl group may be added as a dissolution accelerator in order to improve the developing characteristics. Examples of the compound having a phenolic hydroxyl group include methylene bisphenol, 4,4′-ethylidene bisphenol, 2,2 ′
-Methylenebis (4-methylphenol), 4,4'-
Methylidene bis (2,6-dimethylphenol), 4,
4 '-(1-methyl-ethylidene) bis (2-methylphenol), 4,4'-cyclohexylidenebisphenol, 4,4'-(1,3-dimethylbutylidene) bisphenol, 4,4 '-( 1-methylethylidene) bis (2,6-di-methylphenol), 4,4 '-(1-
Phenylethylidene) bisphenol, 4,4'-oxybisphenol, binuclear such as bis (4-hydroxyphenyl) methanone, 4,4 ', 4 ",-methylidenetrisphenol, 2,6-bis [(2- Hydroxy-5
-Methylphenyl) methyl] -4-methylphenol,
Trinuclear bodies such as 4,4 ', 4 "-ethylidene tris (2-methylphenol), 4,4', 4", 4 "'-
(1,2-ethanediylidene) tetrakis (2-methylphenol), 4,4 ', 4 ", 4'"-(1,2-
Ethanediylidene) tetrakisphenol, 2,2'-
Examples thereof include tetranuclear compounds such as methylenebis [6-[(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol], but are not limited thereto. These are preferably added in an amount of 1 to 50 parts by weight, based on 100 parts by weight of the polymer component (A).
It is more preferable to blend in parts by weight. Further, a dissolution inhibitor, a dissolution accelerator, a stabilizer and the like may be added depending on the purpose.

The photosensitive resin composition of the present invention described above can be used as a material for forming a buffer coat film, an α-ray shielding film, and an interlayer insulating film of a semiconductor device such as a VLSI. . Here, in the process of obtaining a relief pattern, a usual photolithography process is followed.
First, the resin composition of the present invention is applied by a spin coater,
The solvent is volatilized on a hot plate to obtain a semi-cured film.
After that, exposure is performed through a required photomask by an exposure device such as an i-line stepper. Thereafter, if necessary, post-exposure heating (PEB; post exposure bak) is performed.
e) Process and develop. As the developer, an alkaline aqueous solution is preferably used, typically, caustic potash, an aqueous solution of an alkali metal hydroxide such as caustic soda, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium hydroxide such as choline, ethanol. An aqueous amine solution of amine, propylamine, ethylenediamine, etc. is used. As the rinse liquid, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, water or the like is used. After obtaining the relief pattern, the polymer film is cured by heating, and at this time, the ring-closing dehydration reaction of the polyimide precursor and the polybenzoxazole precursor occurs. The heating temperature at this time is preferably in the range of 150 to 450 ° C.

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

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

Further, by using a known photo-etching technique, the second
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is completed (step (d)). When forming a multi-layer wiring structure having three or more layers, each layer can be formed by repeating the above steps.

Next, the surface protective film 8 is formed. In the example of this figure, the surface protective film is applied with the photosensitive resin composition by a spin coating method, dried, and irradiated with light from above a mask on which a pattern for forming a window 6C is drawn on a predetermined portion, and then an alkaline aqueous solution. To develop a pattern, and heat to form a resin film. This resin film allows the conductor layer to be stressed from the outside,
Since it protects against α rays and the like, the obtained semiconductor device has excellent reliability. In the above example, it is also possible to form the interlayer insulating film using the photosensitive resin composition of the present invention.

[0049]

EXAMPLES The present invention will be described below with reference to examples. Production Example 1 1 in a 0.5 liter pressure vessel equipped with stirrer and thermometer
50 g of N-methylpyrrolidone and 0.2 mol of n-butyl alcohol are added, 0.1 mol of bis (3,4-dicarboxyphenyl) ether dianhydride (DDE) is added, and the mixture is sealed and stirred. The mixture was stirred at 70 ° C for 24 hours to obtain an ester. This solution was cooled to 0 ° C., and 0.2 mol of thionyl chloride was added dropwise while maintaining the reaction temperature at 10 ° C. or lower, and after the addition, the solution was stirred at about 10 ° C. for 30 minutes to obtain a solution of dichloride. Then, 100 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with another stirrer and a thermometer, and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1, 0.03 mol of 3,3,3-hexafluoropropane (bis-AP-AF) was added, dissolved with stirring, and then 0.2 mol of pyridine was added. The solution was cooled, and the solution of dichloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 10 ° C, and then 1
The mixture was stirred at around 0 ° C for 30 minutes. The reaction solution was poured into 4 liters of water, the precipitate was collected and washed, and then dried under reduced pressure at 40 ° C. for 2 days to obtain acid-terminated polyhydroxyamide (about 9 repeating units) P-1.

Production Example 2 In the same manner as in Production Example 1, n-butyl alcohol, bis (3,4-dicarboxyphenyl) ether dianhydride (DDE), 2,2-bis (3-amino-4-). The molar ratio of hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bis-AP-AF) is 0.1.
Amine-terminated polyhydroxyamide P-2 having 8, 0.09, and 0.1 (the number of repeating units was about 9) was obtained.

Preparation Example 3 In a 0.5 liter flask equipped with a stirrer and a thermometer, 4,4'-dicarboxydiphenyl ether (OB
(BA) 0.1 mol and N-methylpyrrolidone 150 g were charged, the flask was cooled to 0 ° C., and thionyl chloride 0.2
Mol was added dropwise while maintaining the reaction temperature at 10 ° C or lower, and after the addition, the mixture was stirred at about 10 ° C for 30 minutes to obtain a solution of 4,4-dicarboxydiphenyl ether dichloride. Then, 100 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer,
2-bis (3-amino-4-hydroxyphenyl)-
1,1,1,3,3,3-hexafluoropropane (b
0.09 mol of is-AP-AF) was added, and the mixture was stirred and dissolved, and then 0.2 mol of pyridine was added. The solution was cooled, and while maintaining the temperature at 0 to 10 ° C, a solution of 4,4'-dicarboxydiphenyl ether dichloride was added dropwise over 30 minutes, and then the mixture was stirred at about 10 ° C for 30 minutes. The reaction solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure at 40 ° C. for 2 days to obtain acid-terminated polyhydroxyamide P-3 (repeating unit number: about 9).

Production Example 4 In the same manner as in Production Example 3, 4,4′-dicarboxydiphenyl ether (OBBA) and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3. 3,3
-Hexafluoropropane (bis-AP-AF) molar ratios of 0.09 and 0.10 were respectively obtained to obtain amine-terminated polyhydroxyamide P-4 (the number of repeating units was about 9).

Production Example 5 Under an atmosphere of nitrogen, 0.1 mol of 4,4'-diaminodiphenyl ether (DDE) is dissolved in 300 g of N-methyl-pyrrolidone to prepare an amine solution. This solution was ice-cooled and kept at about 15 ° C while stirring, 0.2 mol of bis (3,4-dicarboxyphenyl) ether dianhydride (ODPA) was added, and the mixture was heated and stirred in a water bath at 80 ° C for 3 hours for reaction. . N of acid-terminated polyamic acid (1 repeating unit)
MP solution E-1 was obtained.

Production Example 6 In the same manner as in Production Example 5, the molar ratio of 4,4′-diaminodiphenyl ether (DDE) and bis (3,4-dicarboxyphenyl) ether dianhydride (ODPA) was 0.2. , 0.1 mol to obtain NMP solution E-2 of amine-terminated polyamic acid (repeating unit number 1).

Production Example 7 0.1 mol of tris (4-hydroxyphenyl) methane and 0.29 mol of naphthoquinone-1,2-diazide-4-sulfonyl chloride were dissolved in 150 g of dioxane,
0.3 mol of triethylamine was reacted dropwise under cooling. The reaction solution was filtered, the filtrate was dropped into water for precipitation, filtered, and dried to obtain an orthoquinonediazide compound C-1.

Example 1 100 parts by weight of P-1 obtained in Production Example 1, 5 parts by weight of the chain extender E-2 obtained in Production Example 6 in resin, and Photosensitizer C obtained in Production Example 7 -1 was dissolved in 15 parts by weight, 10 parts by weight of a 50% methanol solution of ureapropyltriethoxysilane as an adhesion aid in 150 parts by weight of n-methylpyrrolidone, and this solution was filtered through a Teflon (registered trademark) filter having 3 μm pores. It pressure-filtered using and obtained the photosensitive resin composition. This was applied onto a silicon wafer using a spinner and prebaked for 240 seconds on a hot plate at 120 ° C. to obtain a coating film having a thickness of 17 μm. This wafer was exposed to an exposure dose of 200 to 1000 mJ / cm ² through a mask using an i-line stepper,
Exposed. Using a paddle type developing device, development was performed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide and rinsed with deionized water to obtain a relief pattern. When this wafer is observed with a microscope, it is 50 at an exposure dose of 400 mJ / cm ² .
A resolution of × 50 μm ² was confirmed, and the ratio of the film thickness after development to the film thickness after prebaking, that is, the residual film rate was 80%.

This photosensitive resin composition was applied onto a silicon wafer using a spinner and prebaked for 240 seconds on a hot plate at 120 ° C. to obtain a coating film having a thickness of 17 μm. This wafer was exposed through a mask using a contact aligner. It was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide and rinsed with deionized water using a paddle type developing device to obtain a strip-shaped pattern of 10 mm × 120 mm. The wafer was cured and baked at 350 ° C. for 1 hour in an oven whose atmosphere was replaced with nitrogen to obtain a cured film. The strip-shaped thin film was peeled from the silicon wafer using a hydrofluoric acid aqueous solution and dried, and then the elongation rate was measured using an autograph. As a result, the growth rate was 40%.

Examples 2-8 and Comparative Examples 1-4 As in Example 1, 100 parts by weight of the photosensitive polymer, 5 parts by weight of the chain extender, 15 parts by weight of the photosensitizer obtained in Production Example 7, 50% of urea propyltriethoxysilane as an adhesion aid
10 parts by weight of a methanol solution was dissolved in 150 parts by weight of n-methylpyrrolidone, and this solution was pressure-filtered using a Teflon filter having 3 μm pores to obtain a photosensitive polymer composition. The combination of each photosensitive polymer and chain extender, and the results of photosensitivity and elongation are summarized in the table below. However, no chain extender was added in Comparative Examples. In addition, since the elongation rate of the example is higher than that of the comparative example,
It can be observed that the chain is extended.

[0059]

[Table 1]

[0060]

EFFECTS OF THE INVENTION The heat-resistant photosensitive resin composition of the present invention contains a polymer chain extender in the curing process.
The photosensitive polymer as the main component can have a low molecular weight. Therefore, in the pattern manufacturing method, the workability of the relief pattern is excellent, the mechanical properties after curing can be improved, and the sensitivity and the residual film property are hardly impaired. Also,
The semiconductor device of the present invention is highly reliable because it has a pattern of polyimide or polybenzoxazole having a good shape as a surface protective film or an interlayer insulating film.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... First conductor layer, 4 ... Interlayer insulating film layer, 5 ... Photosensitive resin layer, 6
A, 6B, 6C ... Window, 7 ... Second conductor layer, 8 ... Surface protective film layer.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) H01L 21/027 H01L 21/30 502R (72) Inventor Nagatoshi Fujieda 4-13-1 Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Kasei DuPont Micro Systems Co., Ltd. Yamazaki Development Center (72) Inventor Toshinori Tachain 4-13-1 Higashimachi, Hitachi City, Ibaraki Hitachi Kasei DuPont Micro Systems Co., Ltd. Yamazaki Development Center F-term (reference) 2H025 AA04 AA10 AA13 AA14 AC01 AD03 BE00 BJ10 CB25 CB41 CB45 CC03 CC17 CC20 FA17 FA29 2H096 AA25 BA09 EA02 HA01 4J043 PA02 PB07 PB11 QB31 RA05 RA34 UA UB UA UB UB UA 622 UA 221 UA 221 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 122 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 122 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 142 UA 1 UB172 UB301 UB302 ZA34 ZB22

Claims (9)

[Claims] 1. (A) a photosensitive polymer, (B) a chain extender capable of increasing the molecular weight of the polymer in the process of heat curing,
A heat-resistant photosensitive resin composition comprising (C) a compound capable of generating an acid by light and (D) a solvent. 2. The polymer of (A) has the general formula (1): (In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R 1
₁ is hydrogen or a monovalent organic group, and n1 is 2 to 500
Represents the number of repeating units of the polymer), a polyimide precursor having a structure represented by the general formula (2): (In the formula, X ₂ is a divalent organic group, Y ₂ is a tetravalent organic group, n 2
Is a polybenzoxazole precursor having a structure represented by 2 to 500, which represents the number of repeating units of the polymer), a copolymer thereof or a mixture thereof, and the heat-resistant photosensitive resin composition according to claim 1. 3. The heat-resistant photosensitive resin composition according to claim 1, which is an alkaline aqueous solution development positive type. 4. The polymer of (A) is terminated with -NR'R ".
(R 'and R "independently represent a hydrogen atom or a monovalent organic group), and the chain extender of (B) has two or more -COOR' at the terminal (R 'is The photosensitive resin composition according to claim 1, which is a compound or a polymer having a group represented by a hydrogen atom or a monovalent organic group). 5. The polymer of (A) is terminated with -COOR '.
(R 'represents a hydrogen atom or a monovalent organic group), and the chain extender of (B) has 2
The photosensitivity according to claim 1, 2 or 3, which is a compound or polymer having a group represented by -NR'R "(R 'and R" independently represent a hydrogen atom or a monovalent organic group). Resin composition. 6. A polymer (A) having a group represented by —NR′R ″ (R ′ and R ″ independently represent a hydrogen atom or a monovalent organic group) at both ends, and two or more at the ends. -COOR '
(R 'represents a hydrogen atom or a monovalent organic group) or a compound or a polymer having a group (B), (C) a compound capable of generating an acid by light, and (D) a solvent. Heat-resistant photosensitive resin composition. 7. A polymer (A) having a group represented by —COOR ′ (R ′ represents a hydrogen atom or a monovalent organic group) at both ends, and two or more —NR′R ″ (R 'And R "
Is independently a hydrogen atom or a monovalent organic group) or a polymer (B), (C) a compound capable of generating an acid by light, and (D) a heat-resistant solvent containing a solvent. Photosensitive resin composition. 8. A pattern manufacturing method comprising a step of coating the photosensitive resin composition according to claim 1 on a supporting substrate and drying, a step of exposing, and a step of developing with an alkaline aqueous solution. 9. A semiconductor device having a film formed by using the photosensitive resin composition according to claim 1.