JPH06181264A - Interconnection structure and manufacturing method - Google Patents

Abstract

PURPOSE:To provide a structure of interconnection capable of being developed at high speed and having reliability in adhesiveness with a sealing resin, by improving permeability of a developer into a film to enhance solubility of an unexposed part to be removed with regard to a photosensitive heat-resistant material for a semiconductor integrated circuit device. CONSTITUTION:A conductive metallic layer 8 in a given pattern is formed on a substrate 7. The substrate 7 is coated with a solution of photosensitive polymerized material, represented by the following formula (R<1> is a quadrivalent organic radical containing at least four carbons, R<2> is a divalent organic radical containing an aromatic group ring or a silicon), and is dried so that a photosensitive film 9 is formed. After a through hole 10 is formed with a given photomask through exposure, development and rinse, the photosensitive film 9 is converted into a hard material layer 11 to complete a protective film. An upper conductive layer 12 is deposited and connected electrically to a lower conductive layer 8 through the through hole 10 in the polyimide layer 11 to complete a two- layered interconnection in a given pattern.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wiring structure having a thin film wiring layer on a substrate, and more particularly to a wiring structure using a heat resistant organic insulating film as an insulating layer or a protective layer and a method for manufacturing the same.

[0002]

2. Description of the Related Art A wiring structure using a heat-resistant organic insulating film as an insulating layer or a protective layer of a thin film wiring layer is conventionally manufactured by a method shown in FIG. 2 using a polyimide resin. That is, the wiring layer 2 having a predetermined pattern is formed on the substrate 1 by a known photoetching technique. Next, a polyamic acid (polyimide precursor) varnish is applied and cured to form a polyimide resin layer 3 (Fig. 2a). Next, a photoresist 4 is applied on the polyimide resin layer 3 and dried (FIG. 2b). The photoresist 4 is exposed using a predetermined photomask, and then developed, rinsed and dried to obtain a predetermined pattern (FIG. 2c). After that, the polyimide resin layer 3
Is a through-hole 5 by selectively removing a predetermined portion by etching using the photoresist pattern as a mask.
The conductor layer 2 in this portion is exposed (FIG. 2d). By removing the unnecessary photoresist 4, a pattern of the polyimide resin layer 3 is formed (FIG. 2e). When the polyimide resin layer 3 is used as a surface protective film or an α-ray shielding film, this opening is used to obtain electrical conduction with the outside of the substrate. For example, it is used as a bonding pad portion or a solder connection portion for gold wiring. When forming a multilayer wiring structure, the conductor layer 2 is used as a lower conductor layer, and an upper conductor layer is further formed on the wiring layer formed as described above. That is, the upper conductor layer 6 is deposited on the entire surface of the substrate by a method such as a vacuum evaporation method or a sputtering method, and a predetermined electrical connection between the lower conductor layer 2 and the through hole 5 of the polyimide resin layer 3 is performed by a photoetching technique. Formed in a pattern, 2
A layer wiring structure is formed (FIG. 2f). Further, by repeating this operation several times, a multilayer wiring structure having three or more layers is formed. In such a conventional technique, since the polyimide resin layer has to be indirectly patterned using a photoresist, the number of steps is large as described above,
Therefore, there are problems that the manufacturing cost is high, the manufacturing period is long, and the yield is reduced.

In order to solve the above problems, various multilayer wiring structures using a photosensitive heat resistant material and various photosensitive heat resistant materials used as an insulating layer of the wiring structure have been proposed. For example, Japanese Patent Publication No. 63-31939 proposes a multilayer wiring structure using, as an insulating layer, a cured product of a photosensitive heat-resistant material comprising a polyamic acid, a bisazide photocrosslinking agent, and an amine compound having an unsaturated bond. In this multilayer wiring structure, a solution of the above-mentioned photosensitive heat-resistant material is applied on a substrate on which a lower conductor layer is formed, dried, and then a film of the above-mentioned material is exposed and developed using a predetermined mask to form a through hole. Is formed, and then a cured film of polyimide is formed by heat curing treatment, and finally, an upper conductor layer electrically connected at the through hole portion is formed. Compared with the above method, this method can omit the steps of applying and removing the photoresist and etching the polyimide film, so that the number of insulating layer forming steps can be reduced to about 1/2. On the other hand, with the recent sophistication of the thin film manufacturing process, from the viewpoint of automating the process and homogenizing the quality, in particular, the development process is changed from the conventional batch manual development of many sheets to the single-wafer automatic development method for processing one by one. Is desired. However, although the above materials have high photosensitivity, they have a slow developing speed and cannot be developed by a single-wafer automatic developing device with a relatively thick film thickness of about 7 to 10 μm. In addition, when used as a surface protection film or α-ray shielding film for LSI, the adhesiveness with the encapsulant resin is poor, and peeling after solder reflow easily occurs, and when used as an interlayer insulating film of a thin-film multilayer wiring board, between polyimide films. In that case, the adhesiveness was poor, and a highly reliable wiring structure could not be obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned problems, to provide a method for producing a wiring structure having a high development rate and a high productivity, and to improve the adhesion reliability with a sealing material resin or the like. It is to provide an excellent wiring structure.

[0005]

The above object is to find a material having a high development rate and a good adhesiveness with a sealing resin or the like as a photosensitive heat-resistant material used for a wiring structure. The wiring structure referred to here is a semiconductor integrated circuit element, an individual transistor element, a thin film multilayer wiring board used for a computer, or the like.

In order to increase the developing speed, it is necessary to improve the film solubility of the unexposed portion removed by the developing solution. For this purpose, the penetrability of the developing solution into the film should be improved. it is conceivable that. Since the developer used in this system contains an aprotic polar solvent as the main component, in order to improve the penetrability of the developer into the film, the polyamic acid, which is the base polymer, has a polar substitution with good miscibility with the developer. It was thought that it would be good to add an additive having a group. On the other hand, in order to secure the heat resistance and mechanical properties of the final film, it is necessary to sufficiently volatilize the polyamic acid in the heating step for converting the polyamic acid into polyimide having high heat resistance. As a result of various studies on a developing rate improver satisfying such requirements, it was found that the sulfonamide compound exhibits a remarkable effect. It was also found that when the sulfonamide compound is decomposed and volatilized in the heating step, fine irregularities are generated on the surface of the polyimide film, so that the adhesiveness with the encapsulant resin and the like is also improved.

Therefore, as a result of intensive investigations by the present inventors based on the above idea, the surface protective film, the α-ray shielding film or the wiring interlayer insulating film is a photosensitive heat-resistant polymer composition represented by the following [A]. It has been found that in the case of being composed of (1), the development speed is high, the material has excellent adhesiveness to the encapsulant resin, and the wiring structure and the manufacturing method thereof have excellent productivity and reliability.

[A] General formula 1

[0009]

[Chemical 1]

(Wherein R ¹ represents a tetravalent organic group containing at least 4 or more carbon atoms, and R ² represents an aromatic ring or a silicon-containing divalent organic group). 0.1 to 100 parts by weight of an aromatic bisazide photocrosslinking agent, 1 to 400 parts by weight of an amine compound having an unsaturated bond, and 100 to 100 parts by weight of a polymer as a main component.
Alternatively, the sulfonamide compound represented by Chemical formula 4 0.5 to 50
A heat-resistant, heat-resistant polymer composition comprising 1 part by weight.

[0011]

Embedded image R ³ SO ₂ NHR ⁴

[0012]

Embedded image R ³ SO ₂ NR ⁴ ₂

[0013]

Embedded image R ³ SO ₂ NHR ⁵ NHSO ₂ R ⁴ (wherein R ³ is an aromatic group or an alkyl group, R ⁴ is a group selected from hydrogen, an aromatic group and an alkyl group, and R ⁵ is an alkylene Or represents a divalent organic group having an aromatic ring) Hereinafter, a method for producing a wiring structure of the present invention will be described with reference to FIG.

A conductor metal is deposited on the substrate or a substrate 7 on which a necessary element structure is formed by a vacuum deposition method or a sputtering method, and a conductor layer 8 having a predetermined pattern is formed by a well-known photoetching method. . Next, the solution of Photosensitive Polymer Composition 1 is applied and dried at 50 ° C. or higher and 120 ° C. or lower to form a photosensitive coating 9 (FIG. 1a). next,
A predetermined photomask is exposed, then developed and rinsed to form the through hole 10. The photosensitive polymer composition gives a negative image in which the exposed area is insoluble in the developer. Then, the photosensitive film 9 is converted into a cured product layer (polyimide) 11 at a temperature of 150 ° C. or higher and 500 ° C. or lower (FIG. 1b). The manufacturing process of the protective film or the α-ray shielding film is completed by the steps so far. To use as a wiring interlayer insulating film, the following steps are further continued. An upper conductor layer 12 is deposited on the entire surface of the substrate by a vacuum evaporation method or a sputtering method, and a lower conductor layer 8 and a polyimide resin layer 11 are formed by a photoetching technique.
A predetermined pattern electrically connected at the through hole 10 of the
To form a two-layer wiring (FIG. 1c). The above operation is repeated to form a multi-layered wiring having three or more layers.

The substrate used in the present invention is a silicon wafer, glass, ceramic or the like, and is made of SiO ₂ ,
A metal oxide film such as Ta ₂ O ₅ or In ₂ O ₃ can be provided. Al is mainly used as a metal for the conductor layer, but Cu, Au, Pt, Cr, Ti, Mo, W, M
It may be a metal such as n or an alloy film or a multilayer film of two or more kinds of these.

In the photosensitive heat-resistant polymer composition used in the present invention, preferred examples of R ¹ of the polymer represented by the repeating unit of the general formula ¹ are:

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

Examples include, but are not limited to: In addition, R ¹ is different from that in the above-mentioned specific examples.
It may be used as a copolymer containing at least one species.

Examples of preferable R ² of the polymer represented by the repeating unit of the general formula 1 are:

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

Examples thereof include, but are not limited to: Further, R ² is different from that in the above-mentioned specific examples.
It may be used as a copolymer containing at least one species.

Examples of aromatic bisazide photocrosslinking agents include:
Examples thereof include compounds represented by the general formulas 19 and 20.

[0035]

[Chemical 19]

(However, X is> CH-R ⁶ ,> CH-OR ⁶
,> CH-CO ₂ R ⁶ ,> CH-COR ⁷ ,> CH-N
^{HCOR 7,> CH-NR 6} 2, -O -, - S -,> N-
R ⁶ , a group selected from> N-CO-R ⁷ ,> N-CO-OR ⁷ , R ⁶ represents hydrogen or a lower alkyl group, R ⁷ represents a lower alkyl group, and n is 1 or 0)

[0037]

[Chemical 20]

(However, Y is -CO-, -CH = CH-,
-COCH = CH-, a group selected from -CH = CHCOCH = CH-) Specific preferred examples include 2,6-di (paraazidobenzal) -cyclohexanone and 2,6-di (paraazidobene). Monkey) -4-methylcyclohexanone, 2,6-di (paraazidobenzal) -4-hydroxycyclohexanone, 2,6-di (paraazidobenzal) -4-carboxycyclohexanone, 2,6-di (paraazide) Benzal) -4-methoxycyclohexanone, 2,6-di (paraazidobenzal) -4-aminocyclohexanone,
2,6-di (paraazidobenzal) -4-dimethylaminocyclohexanone, 2,6-di (paraazidobenzal) -4-hydroxymethylcyclohexanone, 2,6
-Di (paraazidobenzal) -4-methoxycarbonylcyclohexanone, 2,6-di (paraazidobenzal)
-4-Acetylaminocyclohexanone, 3,5-di (paraazidobenzal) -N-methyl-4-piperidone, 3,5-di (paraazidobenzal) -4-piperidone, 3,5-di (para Azidobenzal) -N-acetyl-4-piperidone, 3,5-di (paraazidobenzal)
-N-methoxycarbonyl-4-piperidone, 3,5-
Di (paraazidobenzal) -tetrahydro-4H-pyran-4-one, 2,6-di (metaazidobenzal) -cyclohexanone, 2,6-di (metaazidobenzal)-
4-methylcyclohexanone, 2,6-di (metaazidobenzal) -4-methylcyclohexanone, 2,6-di (metaazidobenzal) -4-hydroxycyclohexanone, 2,6-di (metaazidobenzal) -4-carboxycyclohexanone, 2,6-di (metaazidobenzal) -4-methoxycyclohexanone, 2,6-di (metaazidobenzal) -4-aminocyclohexanone,
2,6-di (paraazidobenzal) -4-dimethylaminocyclohexanone, 2,6-di (methazidobenzal) -4-hydroxymethylcyclohexanone, 2,6
-Di (metaazidobenzal) -4-methoxycarbonylcyclohexanone, 3,5-di (metaazidobenzal)
-N-methyl-4-piperidone, 3,5-di (methazidobenzal) -4-piperidone, 3,5-di (methazidobenzal) -N-acetyl-4-piperidone, 3,5
-Di (metaazidobenzal) -N-methoxycarbonyl-4-piperidone, 3,5-di (metaazidobenzal)
-Tetrahydro-4H-pyran-4-one, 2,6-di (paraazidocinnamylidene) -4-hydroxycyclohexanone, 2,6-di (paraazidocinnamylidene)
-4-Carboxycyclohexanone, 2,6-di (paraazidocinnamylidene) -4-methoxycyclohexanone, 2,6-di (paraazidocinnamylidene) -4-aminocyclohexanone, 2,6-di (paraazide) Cinnamylidene) -4-dimethylaminocyclohexanone,
2,6-di (paraazidocinnamylidene) -4-hydroxymethylcyclohexanone, 2,6-di (paraazidocinnamylidene) -4-methoxycarbonylcyclohexanone, 3,5-di (paraazidocinnamylidene) -N
-Methyl-4-piperidone, 3,5-di (paraazidocinnamylidene) -N-methyl-4-piperidone, 3,5
-Di (paraazidocinnamylidene) -4-piperidone,
3,5-di (paraazidocinnamylidene) -N-acetyl-4-piperidone, 3,5-di (paraazidocinnamylidene) -N-methoxycarbonyl-4-piperidone,
4,4′-diazidochalcone, 3,3′-diazidochalcone, 3,4′-diazidochalcone, 4,3′-diazidochalcone, 4,4′-diazidoacetophenone, 3,
3'-diazido acetophenone etc. are mentioned.

More preferably, 2,6-di (paraazidobenzal) -4-hydroxycyclohexanone, 2,6-
Di (paraazidobenzal) -4-carboxycyclohexanone, 2,6-di (paraazidobenzal) -4-methoxycyclohexanone, 2,6-di (paraazidobenzal) -4-hydroxymethylcyclohexanone, 3, 5
-Di (paraazidobenzal) -1-methyl-4-piperidone, 3,5-di (paraazidobenzal) -4-piperidone, 3,5-di (paraazidobenzal) -N-acetyl-4 -Piperidone, 3,5-di (paraazidobenzal) -N-methoxycarbonyl-4-piperidone, 2,
6-di (paraazidobenzal) -4-hydroxycyclohexanone, 2,6-di (metaazidobenzal) -4-
Carboxycyclohexanone, 2,6-di (metaazidobenzal) -4-methoxycyclohexanone, 2,6-
Di (metaazidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (metaazidobenzal) -N
-Methyl-4-piperidone, 3,5-di (metaazidobenzal) -4-piperidone, 3,5-di (metaazidobenzal) -N-acetyl-4-piperidone, 3,5-di (meta Azidobenzal) -N-methoxycarbonyl-4
-Piperidone, 2,6-di (paraazidocinnamylidene) -4-hydroxycyclohexanone, 2,6-di (paraazidocinnamylidene) -4-carboxycyclohexanone, 2,6-di (paraazidocinnamylidene) )
-4-Hydroxymethylcyclohexanone, 3,5-di (paraazidocinnamylidene) -N-methyl-4-piperidone, 4,4'-diazidochalcone, 3,3'-diazidochalcone, 3,4 ' -Diazide chalcone, 4, 3 '
-Diazido chalcone and the like.

The compounding ratio of the aromatic bisazide photocrosslinking agent is
The amount is preferably 0.1 parts by weight or more and 100 parts by weight or less, more preferably 0.5 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the polymer containing the repeating unit represented by the general formula 1. Is desirable. If it deviates from this range, the sensitivity will be insufficient, and the developability and stability will be adversely affected.

Examples of the amine compound having an unsaturated bond include compounds represented by the general formula 21.

[0042]

[Chemical 21]

(Wherein R ⁸ , R ⁹ and R ¹⁰ are groups selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, R ¹¹ and R ¹² are lower alkyl groups, and R ¹³ is an alkylene group. ) As preferable specific examples, 2- (N, N-dimethylamino) ethyl acrylate, 3- (N, N-dimethylamino) propyl acrylate, 4- (N, N-dimethylamino) butyl acrylate, 5- (N, N-dimethylamino) pentyl acrylate, 6- (N, N-dimethylamino) hexyl acrylate, 2- (N, N-diethylamino) ethyl acrylate, 3- (N, N-acrylate) Diethylamino) propyl, 4- (N, N-ethylamino) butyl acrylate, 5- (N, N-diethylamino) pentyl acrylate, 6- (N, N-diethylamino) acrylic acid Xyl, 2- (N, N-dimethylamino) ethyl methacrylate, 3- (N, N-dimethylamino) propyl methacrylate, 4- (N, N-dimethylamino) butyl methacrylate, 5- (N) methacrylate , N-dimethylamino) pentyl, 6- (N, N-dimethylamino) hexyl methacrylate, 2- (N, N-diethylamino) ethyl methacrylate, 3- (N, N-diethylamino) propyl methacrylate, methacrylic acid 4- (N, N-diethylamino) butyl, 5- (N, N-diethylamino) pentyl methacrylate, 6- (N, N-methacrylic acid)
Diethylamino) hexyl, sorbic acid 2- (N, N-
Dimethylamino) ethyl, 3- (N, N-dimethylamino) propyl sorbate, 4- (N, N-dimethylamino) butyl sorbate, 5- (N, N-dimethylamino) pentyl sorbate, 6-sorbic acid -(N, N-dimethylamino) hexyl, 2- (N, N-diethylamino) ethyl sorbate, 3- (N, N-diethylamino) propyl sorbate, 4- (N, N-diethylamino) butyl sorbate, 5- (N, N-diethylamino) pentyl sorbate, 6- (N, N-diethylamino) hexyl sorbate, 2- (N, N-dimethylamino) ethyl cinnamate, 3- (N, N) cinnamate -Dimethylamino) propyl, cinnamic acid 4- (N, N-dimethylamino) butyl, cinnamic acid 5- (N, N-dimethylamino)
Pentyl, 6- (N, N-dimethylamino) hexyl cinnamate, 2- (N, N-diethylamino) ethyl cinnamate, 3- (N, N-diethylamino) propyl cinnamate, 4-cinnamic acid 4- (N, N-diethylamino) butyl,
Examples include cinnamic acid 5- (N, N-diethylamino) pentyl and cinnamic acid 6- (N, N-diethylamino) hexyl.

More preferably, methacrylic acid 2- (N,
N-dimethylamino) ethyl, methacrylic acid 2- (N,
N-dimethylamino) propyl, methacrylic acid 4-
(N, N-dimethylamino) butyl, methacrylic acid 5-
(N, N-dimethylamino) pentyl, methacrylic acid 6
-(N, N-dimethylamino) hexyl, 2- (N, N-diethylamino) ethyl methacrylate, 3- (N, N-diethylamino) propyl methacrylate, 4- (N, N-diethylamino) butyl methacrylate, Examples thereof include 5- (N, N-diethylamino) pentyl methacrylate and 6- (N, N-diethylamino) hexyl methacrylate.

The blending ratio of the amine compound having an unsaturated bond is preferably 1 part by weight or more and 400 parts by weight or less, more preferably 100 parts by weight of the polymer containing the repeating unit represented by the general formula 1 as a main component. It is desirable to use 10 parts by weight or more and 200 parts by weight or less. If it deviates from this range, the sensitivity will be insufficient, and the developability and stability will be adversely affected.

Examples of the sulfonamide compound used for improving the developing speed include compounds represented by the general formulas 2, 3, or 4.

[0047]

Embedded image R ³ SO ₂ NHR ⁴

[0048]

Embedded image R ³ SO ₂ NR ⁴ ₂

[0049]

Embedded image R ³ SO ₂ NHR ⁵ NHSO ₂ R ⁴ (wherein R ³ is an aromatic group or an alkyl group, R ⁴ is a group selected from hydrogen, an aromatic group and an alkyl group, and R ⁵ is an alkylene Or represents a divalent organic group having an aromatic ring) As preferable specific examples, benzenesulfonamide, paratoluenesulfonamide, metatoluenesulfonamide, paramethoxybenzenesulfonamide, paraphenoxybenzenesulfonamide, paraacetoxybenzene Sulfonamide, benzenesulfonylanilide, paratoluenesulfonylanilide, metatoluenesulfonylanilide, 4- (methoxy) paratoluenesulfonylanilide, 4- (methyl) paratoluenesulfonylanilide, 4- (acetyl) paratoluenesulfonylanilide, 4- ( Acetyl) paratoluenesul Phonylanilide, paratoluenesulfonyl-N-methylamide, paratoluenesulfonyl-N-ethylamide, paratoluenesulfonyl-Nn-propylamide, paratoluenesulfonyl-N-phenylamide, paratoluenesulfonyl-N-dimethylamide, paratoluenesulfonyl -N
-Diethylamide, paratoluenesulfonyl-N-diphenylamide, 1,3-di (paratolylsulfonylamino) propane, 1,4-di (paratolylsulfonylamino) benzene, 4,4'-di (paratolylsulfonylamino) Diphenylmethane, 4,4′-di (paratolylsulfonylamino) diphenyl ether, 3,3′-di (paratolylsulfonylamino) diphenyl ether,
4,4′-di (paratolylsulfonylamino) diphenylsulfone, 4,4′-di (paratolylsulfonylamino) diphenyl, 3,3′-di (paratolylsulfonylamino) diphenylsulfone, 4,4′-di (Paratolylsulfonylamino) diphenyl sulfide, 4,4 '
-Di (benzenesulfonylamino) diphenylmethane,
4,4'-di (benzenesulfonylamino) diphenyl ether, 3,3'-di (benzenesulfonylamino)
Diphenyl ether, 4,4'-di (benzenesulfonylamino) diphenyl sulfone, 4,4'-di (benzenesulfonylamino) diphenyl, 3,3'-di (benzenesulfonylamino) diphenyl sulfone, 4,4 '
-Di (benzenesulfonylamino) diphenyl sulfide and the like, but not limited thereto.

The blending ratio of the sulfonamide compound is Polymer 1 containing the repeating unit represented by the general formula 1 as the main component.
0.5 parts by weight or more and 50 parts by weight or less, and more preferably 1 part by weight or more and 30 parts by weight or less is preferably used with respect to 00 parts by weight. If it deviates from this range, the improvement of the developing speed will be insufficient, and the developability and stability will be adversely affected.

A sensitizer may be added to the photosensitive heat-resistant polymer composition according to the present invention in order to further improve the sensitivity. Preferred examples of these are Michler's ketone, bis-4,4'-diethylaminobenzophenone, benzophenone, 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone, 3,5
-Bis (dimethylaminobenzylidene) -N-methyl-
4-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 3,3'-carbonylbis (7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropane-1
-One, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, 1
-Phenyl-2- (ethoxycarbonyl) oxyiminopropan-1-one, benzoin ether, benzoin isopropyl ether, 1,9-benzanthrone, 5-nitroacenaphthene, 2-nitrofluorene, anthanthrone, 1,2 -Benzanthraquinone, 1-phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one, 10-thioxanthenone, 3-acetylindole, 2,6-di (4'-dimethylaminobenzal) -4-carboxy Cyclohexanone, 2,6-di (4'-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6-di (4'-diethylaminobenzal) -4-carboxycyclohexanone, 2,6-
Examples thereof include, but are not limited to, di (4′-diethylaminobenzal) -4-hydroxycyclohexanone.

Of these, more preferred examples include Michler's ketone, bis-4,4'-diethylaminobenzophenone, 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (. Dimethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 3,3′-carbonylbis (7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethylthioxanthone, 3,5- Diisopropylthioxanthone, 1-phenyl-2- (ethoxy Lubonyl) oxyiminopropan-1-one, 5-nitroacenaphthene, 2,6-di (4'-dimethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (4'-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6-
Examples thereof include di (4′-diethylaminobenzal) -4-carboxycyclohexanone and 2,6-di (4′-diethylaminobenzal) -4-hydroxycyclohexanone. These may be used alone or as a mixture of several kinds.

The suitable blending ratio of the sensitizer used in the present invention is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer represented by the general formula 1.
It is in the range of 3 to 20 parts by weight. If it deviates from this range, the sensitizing effect may not be obtained, or the developability may be adversely affected.

The photosensitive heat-resistant polymer composition according to the present invention is used in a solution state in which the above-mentioned constituents are dissolved in an appropriate organic solvent. The solvent used in this case is preferably an aprotic polar solvent from the viewpoint of solubility, and specifically, N-
Methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, N
Preferred examples include -acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and γ-butyrolactone. These may be used alone or as a mixed system. Further, in order to improve the coating property, an aromatic solvent such as toluene, xylene, methoxybenzene or the like may be mixed within a range that does not adversely affect the dissolution of the polymer.

In order to improve the adhesion between the dry coating film of the photosensitive heat-resistant polymer composition according to the present invention or the polyimide coating after heat curing and the supporting substrate, the supporting substrate may be treated with an adhesion aid as appropriate.

The photosensitive heat-resistant polymer composition of the present invention can be patterned by a usual photolithography technique. The application of the present composition to the supporting substrate can be carried out by spin coating using a spinner, dipping, spray printing, screen printing, or the like, and can be appropriately selected. The coating film thickness can be adjusted by the coating conditions, the solid content concentration of the composition, and the like. The composition according to the present invention formed into a coating film on a supporting substrate through a drying step is irradiated with ultraviolet rays through a photomask, and then the unexposed portion is dissolved and removed with a developing solution to form a desired leaf pattern. obtain.

Drying is carried out at a temperature selected from the range of 50 ° C. to 120 ° C. When the temperature is lower than 50 ° C, it takes a long time to evaporate the solvent and the drying is insufficient, which is not practical. If the temperature is higher than 120 ° C, the developability is impaired due to a partial crosslinking reaction due to a thermal reaction.

The developer is N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, which is a good solvent for the present composition,
N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, triethylene glycol Dimethyl ether, γ-butyrolactone, etc., alone or as a non-solvent for compositions such as methanol, ethanol, isopropyl alcohol, toluene, xylene, 1,2-dimethoxyethane, 2-methoxyethanol, 1-acetoxy-2-methoxyethane, water, etc. It can be used as a mixed solution with.

The relief pattern formed by development is then washed with a rinse solution to remove the developing solvent. Methanol, which has good miscibility with the developer,
Preferable examples include ethanol, isopropyl alcohol, toluene, xylene, 1,2-dimethoxyethane, 2-methoxyethanol, 1-acetoxy-2-methoxyethane, water and the like.

The polymer of the relief pattern obtained by the above treatment is a precursor of polyimide,
By treating at a heating temperature selected from the range of 1 to 500 ° C., a polyimide pattern having high heat resistance and excellent mechanical properties can be obtained. When the heating temperature is lower than 150 ° C., the imide ring forming reaction does not occur or becomes extremely slow, which is not practical. If the temperature is higher than 500 ° C., thermal decomposition of the cured product itself occurs, which is not preferable. Heating temperature is 30
If the temperature exceeds 0 ° C, it is desirable to use an inert gas atmosphere such as N ₂ .

When depositing the upper conductor metal, treating the polyimide in advance in a plasma discharge atmosphere improves the adhesion with the upper conductor. In addition, surface treatment can be performed in order to secure the electrical connection between the lower conductor and the upper conductor at the through hole portion. This is a treatment for removing the thin oxide film formed on the lower conductor surface, and can be achieved by a method using an etching solution for the lower conductor metal, an etching solution for an oxide, Ar plasma, or the like.

[0062]

As described above in detail, since the sulfonamide compound as the photosensitive polymer composition has good compatibility with the aprotic polar solvent used as the main component of the developer, the film solubility of the unexposed portion is improved. It was possible to improve the development speed. In addition, the sulfonamide compound has a good decomposability because it has --SO _2-, which is easily decomposed and desorbed in the molecule, and thus is unlikely to remain in the final film, and is a polyimide film having excellent heat resistance and mechanical properties. Is obtained. Furthermore, when the polyimide film is decomposed and volatilized, fine irregularities are generated on the surface of the polyimide film, and the adhesiveness with the encapsulant resin or the like is improved. Therefore, by using this as a protective film, an α-ray shielding film, and a wiring interlayer insulating film, it is possible to provide a wiring structure having high productivity and reliability and a manufacturing method thereof.

[0063]

EXAMPLES Examples of the present invention will be described below.

A solution of the photosensitive polymer composition was prepared in advance as shown in the following synthesis example.

(Synthesis Example 1) 100 g (0.5 mol) of 4,4'-diaminodiphenyl ether was added to N- under a nitrogen stream.
An amine solution was prepared by dissolving in 1400 g of a 1: 1 mixed solution of methyl-2-pyrrolidone and N, N-dimethylacetamide. Next, 147 g (0.5 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added with stirring while maintaining the solution at a temperature of about 15 ° C. by ice cooling. After the addition was completed, the mixture was reacted at 15 ° C for 5 hours and then heated at 50 ° C for 7 hours to obtain a viscosity of 20 poise (2
A polyamic acid solution (5 ° C.) was obtained.

20 g of this polyamic acid solution was added with 0.14 g of 2,6-di (paraazidobenzal) -4-carboxycyclohexanone, 2.1 g of 3- (N, N-dimethylamino) propyl methacrylate and paratoluenesulfonylanilide. 0.15 g was added to obtain a photosensitive varnish A. Separately from this, a photosensitive varnish B having the same composition as the photosensitive varnish A except that there was no p-toluenesulfonylanilide was prepared. Each solution was filtered under pressure using a filter having 5 μm pores (photosensitive polymer composition No. 1).

The obtained solution was spin-coated on a silicon wafer with a spinner and then dried at 85 ° C. for 30 minutes to obtain 10
A coating film having a thickness of μm was obtained. When this coating film was immersed in a developing solution containing 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water kept at 25 ° C., the time until the film was completely dissolved was measured, and the dissolution rate of the film was measured. The coating film obtained from the photosensitive varnish A had a dissolution rate of 2.6 μm / min, the coating film obtained from the photosensitive varnish B had a dissolution rate of 1.6 μm / min, and the composition containing paratoluenesulfonylanilide was 63%. The dissolution rate was improved.

On the other hand, the photosensitivity of the above-mentioned photosensitive coating film was measured. The above-mentioned photosensitive coating film was uncoated with a photomask having a striped pattern and irradiated with ultraviolet rays from a 500 W high-pressure mercury lamp. After exposure, it was developed with a developing solution consisting of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water, and then rinsed with isopropyl alcohol to obtain a relief pattern. The dependency of the film thickness after development on the exposure amount was measured, and the exposure amount at which the film thickness after development was half of the coating film thickness was taken as the sensitivity.
mJ / cm ² was obtained. A relief pattern having a width of 10 μm and having a sharp end face was obtained with an exposure amount of 5 times the sensitivity. This pattern was heated at 200 ° C. for 30 minutes and 400 ° C. for 30 minutes to finally obtain a polyimide pattern. Separately, except that no pattern is formed, a polyimide film having a thickness of 8 μm, which is treated in exactly the same manner as above, is prepared, and the weight loss starting temperature and the elongation property are measured. The elongation was as good as 12%.

(Synthesis Example 2) 2,6-di (paraazidobenzal) -4- was added to 20 g of the polyamic acid solution obtained in Synthesis Example 1.
A photosensitive varnish A was obtained by adding 0.13 g of hydroxycyclohexanone, 2.1 g of 3- (N, N-dimethylamino) propyl methacrylate and 0.15 g of paratoluenesulfonamide. Separately, a photosensitive varnish B having the same composition as the photosensitive varnish A except that there was no paratoluenesulfonamide was prepared. Each solution was pressure-filtered using a filter having a pore size of 5 μm (photosensitive polymer composition N
o2).

The obtained solution was spin-coated on a silicon wafer with a spinner and then dried at 85 ° C. for 30 minutes to obtain 10
A coating film having a thickness of μm was obtained. When this coating film was immersed in a developing solution containing 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water kept at 25 ° C., the time until the film was completely dissolved was measured, and the dissolution rate of the film was measured. The coating film obtained from the photosensitive varnish A has a dissolution rate of 2.5 μm / min, the coating film obtained from the photosensitive varnish B has a dissolution rate of 1.7 μm / min, and the composition containing paratoluenesulfonamide has a dissolution rate of 47%. The dissolution rate was improved.

On the other hand, the photosensitivity of the above-mentioned photosensitive coating film was measured. The above-mentioned photosensitive coating film was uncoated with a photomask having a striped pattern and irradiated with ultraviolet rays from a 500 W high-pressure mercury lamp. After exposure, it was developed with a developing solution consisting of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water, and then rinsed with isopropyl alcohol to obtain a relief pattern. The dependency of the film thickness after development on the exposure amount was measured, and the exposure amount at which the film thickness after development became half of the coating film thickness was taken as the sensitivity, and any composition had a sensitivity of 12
mJ / cm ² was obtained. A relief pattern having a width of 10 μm and having a sharp end face was obtained with an exposure amount of 5 times the sensitivity. This pattern was heated at 200 ° C. for 30 minutes and 400 ° C. for 30 minutes to finally obtain a polyimide pattern. Separately, except that no pattern was formed, a polyimide film having a thickness of 8 μm which was treated in exactly the same manner as above was prepared, and the weight loss starting temperature and the elongation property were measured. At 450 ° C, the elongation was 12%, which was good.

(Synthesis Example 3) 2,6-di (paraazidobenzal) -4- was added to 20 g of the polyamic acid solution obtained in Synthesis Example 1.
Hydroxymethylcyclohexanone 0.15 g, 2- (N, N-dimethylamino) ethyl methacrylate 2.0
Photosensitive varnish A was obtained by adding 0.15 g of g, 4,4′-di (paratolylsulfonylamino) diphenylmethane. Separately, a photosensitive varnish B having the same composition as the photosensitive varnish A was prepared except that 4,4′-di (paratolylsulfonylamino) diphenylmethane was not present. Each solution was pressure filtered using a filter with 5 μm pores.
(Photosensitive polymer composition No. 3).

The obtained solution was spin-coated on a silicon wafer with a spinner, and then dried at 85 ° C. for 30 minutes to obtain 10
A coating film having a thickness of μm was obtained. When this coating film was immersed in a developing solution containing 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water kept at 25 ° C., the time until the film was completely dissolved was measured, and the dissolution rate of the film was measured. The coating film obtained from the photosensitive varnish A has a dissolution rate of 2.7 μm / min, and the coating film obtained from the photosensitive varnish B has a dissolution rate of 1.5 μm / min.
The composition in which di (paratolylsulfonylamino) diphenylmethane was added had an 80% improvement in dissolution rate.

On the other hand, the photosensitivity of the above-mentioned photosensitive coating film was measured. The above-mentioned photosensitive coating film was uncoated with a photomask having a striped pattern and irradiated with ultraviolet rays from a 500 W high-pressure mercury lamp. After exposure, it was developed with a developing solution consisting of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water, and then rinsed with isopropyl alcohol to obtain a relief pattern. The dependency of the film thickness after development on the exposure amount was measured, and the exposure amount at which the film thickness after development was half the coating film thickness was taken as the sensitivity.
mJ / cm ² was obtained. A relief pattern having a width of 10 μm and having a sharp end face was obtained with an exposure amount of 5 times the sensitivity. This pattern was heated at 200 ° C. for 30 minutes and 400 ° C. for 30 minutes to finally obtain a polyimide pattern. Separately, except that no pattern was formed, a polyimide film having a thickness of 8 μm which was treated in exactly the same manner as above was prepared, and the weight loss starting temperature and the elongation property were measured. At 450 ° C, the elongation was 12%, which was good.

(Synthesis Example 4) 2,6-di (paraazidobenzal) -4- was added to 20 g of the polyamic acid solution obtained in Synthesis Example 1.
Hydroxymethylcyclohexanone 0.15 g, 2- (N, N-dimethylamino) ethyl methacrylate 2.0
Photosensitive varnish A was obtained by adding 0.15 g of g, 4,4′-di (paratolylsulfonylamino) diphenylsulfone. Separately, a photosensitive varnish B having the same composition as the photosensitive varnish A was prepared except that 4,4′-di (paratolylsulfonylamino) diphenylsulfone was not present. Each solution was pressure filtered using a filter having 5 μm pores (photosensitive polymer composition No. 4).

The obtained solution was spin-coated on a silicon wafer with a spinner and then dried at 85 ° C. for 30 minutes to obtain 10
A coating film having a thickness of μm was obtained. When this coating film was immersed in a developing solution containing 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water kept at 25 ° C., the time until the film was completely dissolved was measured, and the dissolution rate of the film was measured. The coating film obtained from the photosensitive varnish A has a dissolution rate of 2.6 μm / min, and the coating film obtained from the photosensitive varnish B has a dissolution rate of 1.5 μm / min.
The composition containing di (paratolylsulfonylamino) diphenylsulfone had a 73% dissolution rate improvement.

On the other hand, the photosensitivity of the above-mentioned photosensitive coating film was measured. The above-mentioned photosensitive coating film was uncoated with a photomask having a striped pattern and irradiated with ultraviolet rays from a 500 W high-pressure mercury lamp. After exposure, it was developed with a developing solution consisting of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water, and then rinsed with isopropyl alcohol to obtain a relief pattern. The dependency of the film thickness after development on the exposure amount was measured, and the exposure amount at which the film thickness after development was half the coating film thickness was taken as the sensitivity.
mJ / cm ² was obtained. A relief pattern having a width of 10 μm and having a sharp end face was obtained with an exposure amount of 5 times the sensitivity. This pattern was heated at 200 ° C. for 30 minutes and 400 ° C. for 30 minutes to finally obtain a polyimide pattern. Separately, except that no pattern was formed, a polyimide film having a thickness of 8 μm which was treated in exactly the same manner as above was prepared, and the weight loss starting temperature and the elongation property were measured. At 450 ° C, the elongation was 12%, which was good.

(Synthesis Example 5) 2,6-di (paraazidobenzal) -4- was added to 20 g of the polyamic acid solution obtained in Synthesis Example 1.
Hydroxycyclohexanone 0.08 g, 3- (N, N-dimethylamino) propyl methacrylate 2.1 g, paratoluene sulfonamide 0.15 g, 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone 0. Photosensitive varnish A was obtained by adding 05 g. Separately from this, a photosensitive varnish B having the same composition as the photosensitive varnish A was prepared except that 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone was not present. Each solution was pressure-filtered using a filter having 5 μm pores (photosensitive polymer composition No. 5).

The obtained solution was spin coated on a silicon wafer with a spinner, and then dried at 85 ° C. for 30 minutes to obtain 10
A coating film having a thickness of μm was obtained. This photosensitive coating film was uncoated with a photomask having a striped pattern and was irradiated with ultraviolet rays from a 500 W high-pressure mercury lamp. After exposure, it was developed with a developing solution consisting of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water, and then rinsed with isopropyl alcohol to obtain a relief pattern. Give the exposure latitude of the film thickness after development was measured, as sensitivity exposure film thickness after development is half of the coating film thickness, composition A sensitivity 16 mJ / cm ^2, the composition B is a sensitivity 28 mJ / cm ² The composition A was 75% more sensitive than the composition B. . A relief pattern having a width of 10 μm and having a sharp end face was obtained with an exposure amount of 5 times the sensitivity. This pattern at 200 ℃ 30
Finally, the polyimide pattern was obtained by heating at 400 ° C. for 30 minutes. Separately, except that no pattern was formed, a polyimide film having a thickness of 8 μm which was treated in exactly the same manner as above was prepared, and the weight loss starting temperature and the elongation property were measured. Four
The elongation was as good as 50 ° C. and 12%.

(Synthesis Examples 6-55) In Synthesis Examples 6-55, the same operations as in Synthesis Example 1 were performed with the compositions shown in Tables 1-10. The obtained results are shown in Tables 11 to 20 (photosensitive polymer composition No. 6 to 55).

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

[Table 4]

[0085]

[Table 5]

[0086]

[Table 6]

[0087]

[Table 7]

[0088]

[Table 8]

[0089]

[Table 9]

[0090]

[Table 10]

[0091]

[Table 11]

[0092]

[Table 12]

[0093]

[Table 13]

[0094]

[Table 14]

[0095]

[Table 15]

[0096]

[Table 16]

[0097]

[Table 17]

[0098]

[Table 18]

[0099]

[Table 19]

[0100]

[Table 20]

The polyamic acid represented by Chemical formula 1 was synthesized in N-methyl-2-pyrrolidone, and the polyamic acid concentration was 15% by weight. Bisazide
0), the amine having an unsaturated bond (Chemical Formula 21), the sulfonamide (Chemical Formula 2, 3, 4) and the sensitizer are represented by a weight ratio when the polyamic acid is 100. Also,
The unexposed film dissolution rate is considered good when an improvement of 20% or more is observed as compared to the case where no sulfonamide is added, the sensitivity is 200 mJ / cm ² or less, and the heat resistance is the weight loss starting temperature of 400 ° C. or more. It was good.

Example 1 FIG. 3 shows a sectional view of a dynamic random access memory (DRAM) manufactured according to the present invention and a manufacturing process thereof. A solution of the photosensitive polymer composition No. 1 was spin-coated on a silicon wafer 13 having an element region and a wiring layer formed therein, and then dried on a hot plate in the order of 90 ° C. for 4 minutes and 100 ° C. for 4 minutes to have a thickness of 18 μm. To obtain a photosensitive film (Fig. 3a). This film was irradiated with ultraviolet rays for 20 seconds through a predetermined photomask using a mirror projection type exposure apparatus. After exposure, N-methyl-
2-pyrrolidone 4 volume, developed with a developer consisting of 1 volume of water,
Then, rinsing with isopropyl alcohol and the bonding pad 16 and the scribe area 1 which were not exposed to light
The coating of 7 was removed (Fig. 3b). 200 ℃ 30 minutes,
The polyimide film 15 was cured by heating in order of 350 ° C. for 30 minutes (FIG. 3C). The thickness of the polyimide film was 10 μm. Bonding pad part 1 created as described above
6. The polyimide film 15 whose base was exposed in the scribe region 17 was used as an α-ray shielding film. Next, the substrate prepared as described above was cut in the scribe area and cut into chips (FIG. 3d). On the surface of this chip, there is a polyimide film 19 having a polyamide-imide ether adhesive layer on the bottom.
The external terminals 18 supported above were thermocompression bonded at 400 ° C. (FIG. 3e). Thereafter, the gold wire 20 is wired between the bonding pad portion and the external terminal 18 with a wire bonder (see FIG. 3).
f) Further, a resin-sealed portion 21 was formed by molding using a silica-containing epoxy-based sealing material at a molding temperature of 180 ° C. and a molding pressure of 70 kg / cm ² (FIG. 3g). Finally, by bending the external terminals into a specified shape, DRA
A finished product of M was obtained (Fig. 3h). D produced by the above
In the RAM, no crack was observed in the polyimide film.
No defect was found in a temperature cycle test in which the sample was left in an atmosphere of −55 ° C. and 150 ° C. alternately and repeatedly. Furthermore, after constant temperature and humidity of 85 ° C and 85% for 200 hours, 2
An ultrasonic probe test was performed by heating at 60 ° C. for 10 seconds (solder reflow condition), but no peeling was observed between the polyimide film and the encapsulant resin, and a highly reliable product could be obtained. .

(Examples 2 to 3) A DRAM was prepared in the same manner as in Example 1 except that the materials Nos. 2 and 3 were used as the photosensitive polymer composition. Manufactured DRA
No defects were found in any of the Ms in the temperature cycle test or the ultrasonic probe test, and the product was highly reliable.

(Examples 4 to 7) In order to increase the adhesive strength between the polyimide layer and the base, a solution of 1% aluminum monoethyl acetate diisopropylate was applied and heat treated at 350 ° C. in an oxygen atmosphere. Using the same silicon wafer 13 used in Example 1 and using the materials Nos. 1 to 4 as the photosensitive polymer composition, a DRAM was prepared in the same manner as in Example 1. Manufactured DR
In any case, no defects were found in the temperature cycle test or the ultrasonic probe test, and AM could be made into a highly reliable product.

(Embodiment 8) As an example of a two-layer wiring structure manufactured according to the present invention, FIG. 4 shows a schematic sectional view of a linear IC. The manufacturing method is shown below. Openings were provided in the SiO ₂ layer 26 in order to take out electrodes from the respective regions of the collector 23, the base 24, and the emitter 25 built in the silicon wafer 22. 2 μm Al27 as the first layer wiring conductor
Was deposited by vacuum evaporation, and a predetermined pattern was obtained by a well-known photoetching technique. In order to increase the adhesive strength between the polyimide layer and the base, a 1% aluminum monoethylacetate diisopropylate solution was applied to the above substrate and heat-treated at 350 ° C. in an oxygen atmosphere. Next, a solution of the photosensitive polymer composition having composition No. 10 was spin-coated, and then dried on a hot plate in the order of 90 ° C. for 3 minutes and 100 ° C. for 3 minutes to obtain a coating film having a thickness of 5 μm. This coating film was irradiated with ultraviolet rays for 15 seconds through a predetermined photomask using a mirror projection type exposure apparatus. After the exposure, it was developed with a developing solution consisting of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of water, and then rinsed with water to obtain a square through hole 29 having a side of 10 μm. Minutes, 35
It was heated in the order of 0 ° C. for 30 minutes to be cured into a polyimide film (inter-wiring interlayer insulating film) 28. The thickness of the polyimide film is 2.5
was μm. Then, the oxide layer is removed from the surface of the first-layer Al wiring exposed at the through-hole portion by an aqueous sulfamic acid solution, and an Al etching solution is used for a short time to obtain a fresh Al surface. After the treatment, it was washed with water. After the substrate was dried, 2 μm of Al30 was used as the second layer wiring conductor.
Was deposited by vacuum evaporation, and a predetermined wiring pattern was obtained by a well-known photo etching technique. In the two-layer wiring structure formed as described above, no crack or peeling was observed in the wiring interlayer insulating film made of the cured product (polyimide) of the No. 10 photosensitive polymer composition. Further, the final product obtained by cutting out the above substrate, attaching external terminals, performing gold wiring, and then sealing with resin was subjected to the reliability test shown in Example 1, but no defect was recognized.

(Examples 9 to 12) A linear IC having a two-layer wiring structure was prepared in the same manner as in Example 8 except that the materials having composition Nos. 20 to 23 were used as the photosensitive polymer composition. In any case, neither crack nor peeling was observed in the wiring interlayer insulating film made of the cured product (polyimide) of the photosensitive polymer composition. Further, no defects were found in the temperature cycle test and the ultrasonic probe test, and the product could be made highly reliable.

(Embodiment 13) A sectional view of an individual transistor manufactured according to the present invention and a manufacturing process thereof are shown in FIG.
An opening is provided in the SiO ₂ layer 34 to take out electrodes from each region of the base 32 and the emitter 33 built in the silicon wafer 31 (also serving as a collector), and 2 μm Al 35 is vacuumized as a conductor layer of the bonding pad. It was deposited by vapor deposition and a predetermined pattern was obtained by a well-known photoetching technique (FIG. 5a). In order to increase the adhesive strength between the polyimide layer and the base, a 1% aluminum monoethylacetate diisopropylate solution was applied to the above substrate and heat-treated at 350 ° C. in an oxygen atmosphere. Next, a solution of the photosensitive polymer composition having composition No. 3 was spin-coated, and then dried on a hot plate in the order of 90 ° C. for 3 minutes and 100 ° C. for 3 minutes to obtain a coating film having a thickness of 7 μm. This coating film was irradiated with ultraviolet rays for 15 seconds through a predetermined photomask using a mirror projection type exposure apparatus. After exposure, N-methyl-
2-pyrrolidone 4 volume, developed with a developer consisting of 1 volume of water,
Then, the substrate is rinsed with water to remove the rectangular bonding pad portion 36 having a side of 100 μm and the scribe region 37 having a width of 40 μm.
Minutes, and heated at 350 ° C. for 30 minutes to cure the polyimide film 38 used as a protective film (FIG. 5B). The thickness of the polyimide film was 3.5 μm. Next, a treatment with a sulfamic acid aqueous solution is performed to remove the oxide layer from the surface of the Al wiring exposed at the bonding pad portion 36.
Further, in order to obtain a fresh Al surface, it was briefly treated with an Al etching solution and then washed with water. Next, the substrate prepared as described above was cut in the scribe region and cut into chips 39 (FIG. 5c). This chip is mounted on a lead frame 41 which also serves as an external terminal, after which a gold wire 42 is laid between the bonding pad section and the external terminal 40 with a wire bonder, and a molding temperature using a silica-containing epoxy-based encapsulant. The resin sealing portion 43 was formed by molding at 180 ° C. and a molding pressure of 70 kg / cm ² . Finally, the resin-sealed chip was cut out from the lead frame and the external terminals were bent into a predetermined shape to obtain a finished individual transistor (FIG. 5d). No crack or peeling was observed in the polyimide film of the individual transistor manufactured as described above. Also, in a temperature cycle test in which it is repeatedly left in an atmosphere of −55 ° C. and 150 ° C. alternately, and in an ultrasonic probe test in which constant temperature of 85 ° C. and 85% for 200 hours and constant humidity and 260 ° C. for 10 seconds (solder reflow condition) are applied. No defects were found, and the product was highly reliable.

Example 14 Except that the material of composition No. 31 was used as the photosensitive polymer composition and that no aluminum monoethylacetate diisopropylate treatment was performed to increase the adhesive strength between the polyimide layer and the base. Other than that, the individual transistors were formed by the same method as in Example 13. No crack or peeling was observed in the polyimide film used as the protective layer. Further, no defects were found in the temperature cycle test and the ultrasonic probe test, and the product could be made highly reliable.

(Examples 15 to 26) Individual transistors were prepared in the same manner as in Example 13 except that the materials of Composition Nos. 32, 35 and 37 to 46 were used as the photosensitive polymer composition. In either case, neither crack nor peeling was observed in the polyimide film used as the protective layer.
Further, no defects were found in the temperature cycle test and the ultrasonic probe test, and the product could be made highly reliable.

(Example 27) As an example of the multilayer wiring structure manufactured according to the present invention, FIG. 6 shows a schematic sectional view of a thin film multilayer wiring substrate for a computer. The manufacturing method is shown below. The ceramic layer 44 has a tungsten wiring 45 inside, a nickel layer 46 formed by plating as an upper electrode above the tungsten wiring, and a nickel layer 47 and a gold layer 48 formed by plating as a lower electrode below the tungsten wiring. 3 μm of Al was deposited as a conductor layer on the ceramic substrate 49 by vacuum evaporation, and a predetermined Al pattern 50 covering the nickel layer 47 was obtained by a well-known photoetching technique. Next, a solution of the photosensitive polymer composition having composition No. 43 was spin-coated, and then air-dried in an oven at 100 ° C. for 30 minutes to obtain a coating film having a thickness of 14 μm. This coating film was irradiated with ultraviolet rays for 20 seconds through a predetermined photomask using a mirror projection type exposure apparatus. After exposure, N-methyl-2-pyrrolidone 4 volumes, water 1
And then rinsed with water to form a through hole having a diameter of 70 μm on the Al pattern, and further heated in the order of 200 ° C. for 30 minutes and 350 ° C. for 30 minutes.
It was cured into a layer polyimide film 51. The thickness of the polyimide film was 7 μm. Further, 3 μm of Al was deposited thereon by vacuum vapor deposition, and the first-layer Al wiring pattern 52 was formed by a well-known photoetching technique. By repeating the above operation, the second layer polyimide film 53 having a through hole diameter of 70 μm and a film thickness of 7 μm, and the second layer Al wiring pattern 5 having a film thickness of 3 μm
4. An insulating layer and a wiring layer were alternately formed in this order on the third layer polyimide film 55 having a through hole diameter of 70 μm and a film thickness of 7 μm. Then, a chromium film having a film thickness of 0.07 μm and a nickel-copper alloy film having a film thickness of 0.7 μm are sequentially deposited by a vacuum vapor deposition method, and a film having a diameter of 150 μm is formed in the through hole portion of the third layer polyimide film by a well-known photoetching technique. Chromium / nickel-copper layer 5
6 was patterned. Then, a nickel layer and a gold layer were formed in this order on the upper portion by a plating method to form an upper electrode made of the nickel / gold composite film 57. In the thin-film multi-layer wiring board created as described above, no cracks in the polyimide film and peeling between the polyimide films were observed, and the Al wiring covering the upper part of the through hole was also good and good electrical continuity was achieved across all wiring. was gotten.

(Comparative Example) Japanese Patent Publication No. 63-3193 mentioned above.
The experimental results of No. 9 are shown as comparative examples.

Under a nitrogen stream, 100 g (0.5 mol) of 4,4'-diaminodiphenyl ether was added to N-methyl-2.
1: 1 of pyrrolidone and N, N-dimethylacetamide
The mixture was dissolved in 1791 g to prepare an amine solution. Next, while keeping the solution at a temperature of about 15 ° C. by ice cooling, 109 g (0.5 g of pyromellitic dianhydride was added under stirring.
Mol) was added. After the addition was completed, the mixture was further reacted at 15 ° C. for 5 hours, and the viscosity was adjusted by heating to obtain a polyamic acid solution having a viscosity of 20 poise (25 ° C.).

To 20 g of this polyamic acid solution, 2- (N,
N-Dimethylamino) ethyl methacrylate 1.57
g, 2,6-di (4′-azidobenzal) -4-hydroxycyclohexanone (0.37 g) was dissolved, and then 5 μm
A solution of the photosensitive polymer composition was prepared by pressure filtration using an m-hole filter.

An α-ray shielding film for DRAM was manufactured in the same manner as in Example 1 except that the above-mentioned materials were used as the photosensitive polymer composition. Since it takes 6 minutes or more, it is not suitable for the throughput of the single-wafer type automatic developing device, and it has been forced to manufacture by manual development. Further, peeling occurred between the polyimide film after solder reflow and the encapsulant resin, and a good wiring structure could not be obtained.

[0115]

As described in detail above, the photosensitive polymer composition constituting the wiring structure of the present invention can form a photosensitive coating film having a high development rate, and also has a high heat resistance, mechanical properties and sealing. A final polyimide film having excellent adhesiveness to the material resin or the like can be obtained. Therefore, by using this as a protective film, an α-ray shielding film, and a wiring interlayer insulating film, a wiring structure having high productivity and reliability and a manufacturing method thereof can be formed.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a method for manufacturing a wiring structure according to the present invention.

FIG. 2 is a cross-sectional view showing a method of manufacturing a wiring structure according to a conventional technique.

FIG. 3 is a sectional view showing a sectional structure of a dynamic random access memory according to the present invention and a manufacturing method thereof.

FIG. 4 is a sectional view showing a sectional structure of a linear IC manufactured by the present invention.

FIG. 5 is a sectional view showing a sectional structure of an individual transistor and a manufacturing method thereof according to the present invention.

FIG. 6 is a cross-sectional view showing the cross-sectional structure of a thin film multilayer wiring board manufactured according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Conductor layer, 3 ... Polyimide resin layer, 4 ... Photoresist, 5 ... Through hole, 6 ... Upper conductor layer, 7 ... Substrate, 8 ... Conductor layer, 9 ... Photosensitive coating, 10 ... Through hole , 11 ... Hardened material layer (polyimide), 12 ... Upper conductor layer, 13 ... Silicon wafer, 14 ... Coating film, 15 ... Polyimide film, 16 ... Bonding pad part, 17 ... Scribing area, 18 ... External terminal, 19 ... Polyimide Film, 20 ... Gold wire, 21 ... Resin sealing part, 22 ... Silicon wafer, 23 ... Collector, 24 ... Base, 25 ... Emitter, 26 ... SiO ₂ layer, 27 ... Al, 28 ... Polyimide film, 29 ... Through hole , 30 ... Al, 31 ... Silicon wafer, 32 ... Base, 33 ... Emitter, 34 ... SiO ₂ layer, 35 ... Al, 36 ... Bonding pad portion, 37 ... Scribing region, 38 ... Polyimide film, 39 ... Chip, 40 ... External terminal, 41 ... Lead frame, 42 ... Gold wire, 43 ... Resin sealing part, 44 ... Ceramic layer, 45 ... Tungsten wiring, 46 ... Nickel layer, 47 ... Nickel layer , 48 ... Gold layer, 49 ... Ceramic substrate, 50 ... Al pattern, 51 ... First layer polyimide film, 52 ... First layer Al wiring pattern, 53 ... Second layer polyimide film, 54 ... Second layer Al wiring pattern, 55 ... Third layer polyimide film, 56 ... Chromium / nickel-copper layer, 57 ... Nickel / gold composite film,

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isao Ohara 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Stock, Ltd., Institute of Industrial Science, Hitachi, Ltd. (72) Inventor Jun Tanaka 292 Yoshida-cho, Totsuka-ku, Yokohama, Kanagawa Production Engineering Research Laboratory, Hitachi, Ltd.

Claims (12)

[Claims] 1. A method for producing a wiring structure, wherein the surface protective film is a cured product of a photosensitive heat-resistant polymer composition represented by the following [A]. [A] General Formula 1 (In the formula, R ¹ contains at least 4 or more carbons 4
A divalent organic group, R ² represents a divalent organic group containing an aromatic ring or silicon), based on 100 parts by weight of a polymer containing a repeating unit represented by the formula: To 100 parts by weight, 1 to 400 parts by weight of an amine compound having an unsaturated bond, and 0.5 to 50 parts by weight of a sulfonamide compound represented by the general formula (2), (3) or (4). Composition. ## STR2 ## R ³ SO ₂ NHR ⁴ ## STR3 ## R ³ SO ₂ NR ⁴ ₂ ## STR4 ## _{^{R 3 SO 2 NHR 5 NHSO 2}} R 4 ( where, wherein R ³ is an aromatic group or an alkyl group, R ⁴ is hydrogen, an aromatic group, a group selected from an alkyl group, R ⁵ is an alkylene or a divalent organic group having an aromatic ring), or a photosensitivity obtained by further adding a sensitizer to the above composition. Heat resistant polymer composition. 2. A method for producing a wiring structure, wherein the α-ray shielding film is a cured product of a photosensitive heat-resistant polymer composition represented by the following [A]. [A] General Formula 1 (In the formula, R ¹ contains at least 4 or more carbons 4
A divalent organic group, R ² represents a divalent organic group containing an aromatic ring or silicon), based on 100 parts by weight of a polymer containing a repeating unit represented by the formula: To 100 parts by weight, 1 to 400 parts by weight of an amine compound having an unsaturated bond, and 0.5 to 50 parts by weight of a sulfonamide compound represented by the general formula (2), (3) or (4). Composition. ## STR2 ## R ³ SO ₂ NHR ⁴ ## STR3 ## R ³ SO ₂ NR ⁴ ₂ ## STR4 ## _{^{R 3 SO 2 NHR 5 NHSO 2}} R 4 ( where, wherein R ³ is an aromatic group or an alkyl group, R ⁴ is hydrogen, an aromatic group, a group selected from an alkyl group, R ⁵ is an alkylene or a divalent organic group having an aromatic ring), or a photosensitivity obtained by further adding a sensitizer to the above composition. Heat resistant polymer composition. 3. A method for producing a wiring structure, wherein the wiring insulating film is a cured product of a photosensitive heat-resistant polymer composition represented by the following [A]. [A] General Formula 1 (In the formula, R ¹ contains at least 4 or more carbons 4
A divalent organic group, R ² represents a divalent organic group containing an aromatic ring or silicon), based on 100 parts by weight of a polymer containing a repeating unit represented by the formula: To 100 parts by weight, 1 to 400 parts by weight of an amine compound having an unsaturated bond, and 0.5 to 50 parts by weight of a sulfonamide compound represented by the general formula (2), (3) or (4). Composition. ## STR2 ## R ³ SO ₂ NHR ⁴ ## STR3 ## R ³ SO ₂ NR ⁴ ₂ ## STR4 ## _{^{R 3 SO 2 NHR 5 NHSO 2}} R 4 ( where, wherein R ³ is an aromatic group or an alkyl group, R ⁴ is hydrogen, an aromatic group, a group selected from an alkyl group, R ⁵ is an alkylene or a divalent organic group having an aromatic ring), or a photosensitivity obtained by further adding a sensitizer to the above composition. Heat resistant polymer composition. 4. The method for manufacturing a wiring structure according to claim 1, wherein the wiring structure is a semiconductor integrated circuit device. 5. The method for manufacturing a wiring structure according to claim 1, wherein the wiring structure is an individual transistor element. 6. The method for manufacturing a wiring structure according to claim 1, wherein the wiring structure is a thin film multilayer wiring board. 7. A wiring structure in which the surface protective film is manufactured by the method according to claim 1. 8. A wiring structure in which the α-ray shielding film is manufactured by the method according to claim 2. 9. A wiring structure in which the wiring insulating film is manufactured by the method according to claim 3. 10. The wiring structure according to claim 7, wherein the wiring structure is a semiconductor integrated circuit device. 11. The wiring structure according to claim 7, wherein the wiring structure is an individual transistor element. 12. The wiring structure according to claim 7, wherein the wiring structure is a thin film multilayer wiring board.