JPH05275417A - Wiring structure and its manufacture - Google Patents

Abstract

PURPOSE:To realize a multilayer interconnection structure having high reliability by using polyimide generated through heating a specific polyimide precursor as surface protective coat, alpha-ray shielding film or wiring insulating film. CONSTITUTION:Polyimide generated through heating a polyimide precursor composed of cyclic units with molecular chains respectively represented by formulae I, II and III is used as surface protective coat, alpha-ray shielding film or wiring insulating film. This material is particularly excellent in low dielectric constant, low coefficient of thermal expansion, heat resistance and adhesive property. Thus, it is possible to obtain all sorts of electronic equipments including a semiconductor device and multilayer interconnection structure having high reliability and high performance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention includes a polyimide having a low dielectric constant, a low thermal expansion coefficient, a high glass transition point and high heat resistance as a surface protective film, an α-ray shielding film or an insulating film for wiring. The present invention relates to a wiring structure, and more particularly to a highly integrated semiconductor device, a highly integrated multilayer wiring structure, and manufacturing methods thereof.

[0002]

2. Description of the Related Art In recent years, electronic devices such as semiconductor devices have been multi-layered, highly integrated, and have high performance, and accordingly, insulating materials used therein are required to have high characteristics. Currently, polyimide is widely used as one of the insulating materials. SOG, P used before polyimide
Inorganic films such as SG and silicon nitride films are difficult to make unevenness generated during the semiconductor device manufacturing process flat. In addition, since mechanical properties, especially elongation are poor, there is a defect that cracks are easily generated at a place where stress remains between layers. Polyimide has come to be used to solve these problems, and has been used up to now.

Polyimide is generally obtained by a method in which a diamine component and a tetracarboxylic dianhydride component are polymerized in an organic solvent to produce a polyamic acid, which is subjected to dehydration ring closure.

Examples of these are: (a) General formula (Formula 10) or General formula (Formula 11)

[0005]

[Chemical 10]

[0006]

[Chemical 11]

(In the formula, R'represents a divalent hydrocarbon group.)
There are known novel polyimides containing the structural unit shown by and their precursors, polyamic acid or polyamic acid ester (JP-A-62-265327, JP-A-63-10629).

Further, (b) the general formula (Formula 12)

[0009]

[Chemical 12]

Polyimides in which a repeating unit is represented by (wherein R is a tetravalent aliphatic group or aromatic group, and n is 1 or 2) are known (JP-A-57-114258).
JP-A-57-188883, JP-A-60-250
031, JP-A-60-212426).

Further, (c) general formula (formula 13)

[0012]

[Chemical 13]

(In the formula, Y is --C (CH ₃ ) _2-, --C (CF ₃ ).
₂ -, - SO ₂ - it is. ) Is known to have a repeating unit represented by JP-A-62-231935.
No. 62-231936, 62-231.
937).

(D) Polyimides having excellent low dielectric constant include 2,2-bis (3,4-dicarboxyphenyl) propanoic acid dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexa Fluoropropanoic acid dianhydride and 4,4 '
-Bis (4-aminophenoxy) biphenyl, 4,4 '
A polyimide obtained from an aromatic diamine such as -bis (4-amino-2-trifluoromethylphenoxy) biphenyl is known (Japanese Patent Laid-Open No. 2-60934).

Also, (e) having 2,2-bis (4-aminophenyl) hexafluoropropane and 2,2-bis (3-aminophenyl) hexafluoropropane, pyromellitic dianhydride and a diaryl nucleus. A polyimide obtained from a mixed acid dianhydride consisting of an acid dianhydride (Japanese Patent Application Laid-Open No. 2-6
7320), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride and 2,2-bis (4-aminophenyl) hexafluoropropane and 2,2-bis (3-aminophenyl) ) Polyimide obtained from hexafluoropropane (JP-A-2-86624)
It has been known.

However, the above (a), (b), (c),
The polyimides (d) and (e) have high heat resistance, low dielectric constant,
Various properties such as low coefficient of thermal expansion, high mechanical properties (particularly flexibility), and high glass transition temperature are not taken into consideration at the same time, and the polyimides (d) and (e) above are bonded to the alkyl chain. Since it has a trifluoromethyl group, it has low resistance to organic solvents and alkaline liquids such as electroless plating liquids.
Therefore, when an electronic device such as a semiconductor device or a multilayer wiring structure is formed using these polyimides, there is a possibility that performance improvement may be limited or process may be difficult.

[0017]

[Problems to be Solved by the Invention]
Polyimides (b), (c), (d), and (e) have various properties such as high heat resistance, low dielectric constant, low coefficient of thermal expansion, high mechanical properties (especially flexibility), and high glass transition temperature. Are not considered at the same time. Although (a), (b) and (c) are excellent in high heat resistance, low thermal expansion coefficient and high glass transition temperature, they have high dielectric constant and are not flexible. It has a relatively large number of imide rings in the polymer, and

[0018]

[Chemical 14]

The heat resistance due to containing the structural unit represented by
Although it has a high glass transition temperature and a low coefficient of thermal expansion, it is considered to have a high dielectric constant and poor flexibility. Also (d),
(E) is and include -CF ₃ (trifluoromethyl)
It has a low dielectric constant and excellent flexibility because it has a -O- bond, but it has low heat resistance and glass transition temperature, a high coefficient of thermal expansion, and low resistance to alkaline liquids and organic solvents. it is conceivable that.

First, if the dielectric constant of the insulating film is large, the delay time of the signal propagating in the wiring becomes long and the propagation speed decreases. Further, since the hygroscopicity is high, peeling is likely to occur at the interface, which causes problems such as corrosion of wiring metal and increase of leak current. Therefore, it is desirable that the dielectric constant of the insulating film be as low as possible. Furthermore, when the thermal expansion coefficient of the insulating film is large, stress is generated between the wiring metal and the substrate, which causes warpage of the substrate, disconnection of the wiring, peeling of the insulating film, and cracks. Therefore, it is desirable that the coefficient of thermal expansion of the insulating film be close to that of the substrate or wiring metal. When the glass transition temperature is low, the coefficient of thermal expansion is generally large, and a larger stress is generated at the interface with the wiring metal or the substrate. Therefore, the higher glass transition temperature is desirable. If the heat resistance is poor, the difficulty arises that the operating temperature cannot be raised. Furthermore, if the insulating film does not have sufficient flexibility and elongation, it cannot withstand the stress that is generated and may also cause peeling or cracks of the insulating film.

The inventors of the present invention have possessed various properties that could not be achieved by these conventional techniques, namely, high heat resistance, low dielectric constant, low thermal expansion coefficient, high mechanical properties (particularly flexibility), and high glass transition temperature. ,
Polyimide, which has various properties such as high alkali resistance, is used for the insulating layer, and the signal delay time is short, and it is unlikely to cause problems such as peeling and cracks due to stress, disconnection of wiring, and corrosion, and therefore high reliability. The present invention has been made as a result of intensive studies conducted for the purpose of realizing a multilayer wiring structure having the above.

[0022]

According to the present invention, a molecular chain is composed of a repeating unit represented by the following general formula (Formula 1) and a repeating unit represented by the following general formula (Formula 2). The present invention relates to a wiring structure using a polyimide produced by heating a characteristic polyimide precursor as a surface protective film, an α-ray shielding film or an insulating film for wiring.

General formula (Formula 1)

[0024]

[Chemical 1]

General formula (Formula 2)

[0026]

[Chemical 2]

(In the formula, R ¹ is

[0028]

[Chemical 3]

[0029] From at least one tetravalent organic group selected, R ² is (of 4)

[0030]

[Chemical 4]

At least one linear divalent organic group selected from the group consisting of R ³ and R ³ is a divalent organic group containing at least two or more aromatic rings and having a bent structure. ) In the above polyimide precursor, the number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1) and the bent structure represented by R ³ in the general formula (Formula 2) When the total number of divalent organic groups having R is 100, the number of organic groups represented by R ² is 30 to 80, and the number of organic groups represented by R ³ is 70 to 20. Is desirable. When the number of organic groups represented by R ² is 80 or more and the number of organic groups represented by R ³ is 20 or less, the polyimide film produced from this polyimide precursor lacks flexibility and R ² The number of organic groups represented by is 30 or less, and the number of organic groups represented by R ³ is 70
Above, the glass transition temperature Tg is low and the thermal expansion coefficient is high. Further, when applied to a multilayer wiring structure requiring a lower coefficient of thermal expansion, the ratio of the number of organic groups represented by R ² is 50 to 80, and the number of organic groups represented by R ³ is Fifty
It is more desirable that the range is -20.

In the present invention, the molecular chain is represented by a repeating unit represented by the following general formula (Formula 1), a repeating unit represented by the following general formula (Formula 2) and a general formula (Formula 5). The present invention relates to a wiring structure in which a polyimide produced by heating a polyimide precursor including a repeating unit is used as a surface protective film, an α-ray shielding film, or a wiring insulating film.

General formula (Formula 1)

[0034]

[Chemical 1]

General formula (Formula 2)

[0036]

[Chemical 2]

General formula (Formula 5)

[0038]

[Chemical 5]

(In the formula, R ¹ is

[0040]

[Chemical 3]

[0041] From at least one tetravalent organic group selected, R ² is (of 4)

[0042]

[Chemical 4]

R ³ is a divalent organic group having at least one linear structure selected from R ³ , R ³ is a divalent organic group having at least two aromatic rings and having a bent structure, and R ⁴
Is a general formula (Chemical Formula 6) when the part is at the end of the polymer or when it is the main chain of the polymer,

[0044]

[Chemical 6]

General formula (Formula 7)

[0046]

[Chemical 7]

A hydrocarbon group containing a silicon atom represented by the following formulas, wherein R ⁵ and R ⁸ are a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, R
⁶ is a hydrocarbon group having 1 to 3 carbon atoms, R ⁷ is 1 to 5 carbon atoms
One or more groups selected from the group consisting of alkyl groups, alkoxyalkyl groups and trialkylsilyl groups, R ⁹ and R ¹⁰ are alkyl groups having 1 to 3 carbon atoms, and ari- groups having 1 to 9 carbon atoms.
One or more groups selected from the group, n is an integer from 0 to 3, and f is 1 or 2. ) In the above polyimide precursor, the number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1) and the bent structure represented by R ³ in the general formula (Formula 2) When the total number of the divalent organic groups having R and the hydrocarbon group containing silicon represented by R ⁴ is 100, the number of the organic groups represented by R ² is 30 to 80, and the number represented by R ³ is It is preferable that the number of the organic groups is 70 to 20, and the number of the silicon-containing hydrocarbon group represented by R ⁴ is 0.1 to 10. The desirable range of the ratio of the number of organic groups represented by R ² and the ratio of the number of organic groups represented by R ³ is the same as in the case of the above-mentioned polyimide precursor. Furthermore, the introduction of the silicon-containing hydrocarbon group represented by R ⁴ is for improving the adhesiveness, and when the content is 0.1% or less, the effect of the adhesiveness is small and 1
If it is 0% or more, heat resistance and mechanical properties are adversely affected.
More preferably, it is in the range of 0.5 to 5%.

The above polyimide precursor can be manufactured as follows.

That is, tetracarboxylic dianhydride and 2
In the method for producing a polyimide precursor from at least one diamine component, a compound represented by the general formula

[0050]

[Chemical 15]

(In the formula, R ¹ is (formula 3),

[0052]

[Chemical 3]

It is at least one tetravalent organic group selected from ) When the total of the molar ratios of the tetracarboxylic dianhydride component represented by the formula) and each diamine component used is 100, 1) the general formula H ₂ N—R ² —NH ₂ (in the formula, R ² Is (Chemical 4),

[0054]

[Chemical 4]

It is at least one divalent organic group having a linear structure selected from the group consisting of: ) The molar ratio of the diamine component represented by the formula) is 30 to 80, and 2) the general formula H ₂ N—R ³ —NH.
₂ (in the formula, R ³ is a divalent organic group having at least two aromatic rings and having a bent structure), and the molar ratio of the diamine component is 70 to 20, and 3) According to the general formula (Formula 16)

[0056]

[Chemical 16]

Or (Chemical formula 17)

[0058]

[Chemical 17]

(In the formula, R ⁵ and R ⁸ are hydrocarbon groups having 1 to 9 carbon atoms or saturated alkyl groups having 1 to 7 carbon atoms containing an ether bond, and R ⁶ is hydrocarbon groups having 1 to 3 carbon atoms. Group, R ⁷ is at least one group selected from an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or a trialkylsilyl group, and R ⁹ and R ¹⁰ are alkyl groups having 1 to 3 carbon atoms, carbon One or more groups selected from the aryl groups of the numbers 1 to 9,
n is an integer from 0 to 3, and f is 1 or 2. ) Aminosilane compound or siloxanediamine having a molar ratio of 0.1 to 10 is polymerized with a diamine component in an aprotic polar solvent at a temperature of 0 to 30 ° C., and further stirred at 50 to 80 ° C. A polyimide precursor is obtained by heating.

A polyimide cured product is obtained by heating and curing the above polyimide precursor at a temperature of 100 ° C. or higher.

According to experiments conducted by the present inventor, a polyimide film obtained by curing the polyimide precursor obtained by the present invention has a high heat resistance, a low dielectric constant, a low coefficient of thermal expansion, and a high mechanical property (especially flexibility). ), It has also been found to have various properties such as a high glass transition temperature. Further, they have found that an electronic device such as a semiconductor integrated circuit device or a multilayer wiring structure using the polyimide as an insulating film can have high reliability and high performance.

The method for producing the polyimide precursor and the wiring structure used in the present invention will be described below.

The tetracarboxylic dianhydride component used in the polyimide precursor of the present invention includes p-ta-phenyl-3,3 ", 4,4" -tetracarboxylic dianhydride (TPDA) or m-. Terphenyl-3,3 ", 4
4 ″ -tetracarboxylic dianhydride (m-TPDA) or biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (BPDA) can be used. General Formula Used in the Present Invention Examples of the diamine component represented by H ₂ N—R ² —NH ₂ include 4,4 ″ -diamino-p-ta-phenyl, 4,4 ″ -diamino-p-quarta-phenyl,
9,10-bis (p-aminophenyl) anthracene,
2,2'-dimethyl-4,4'-diamino biphenyl _{(2,2'-Me 2 -DABP),} 3,3'- dimethyl-4,4'-diamino biphenyl (3,3'-Me ₂ -
DABP), 3,5,3 ', 5'-tetramethyl-4,
4'-diaminobiphenyl (3,5,3 ', 5'-Me
_4- DABP), 2,2'-di (trifluoromethyl)
-4,4'-Diaminobiphenyl (2,2'-FMe ₂
-DABP), 3,3'-di (trifluoromethyl)-
4,4'-diaminobiphenyl (3,3'-FMe ₂ -
DABP), 2,2'-dimethoxy-4,4'-diaminobiphenyl (2,2 '-(MeO) _2- DABP),
3,3'-Dimethoxy-4,4'-diaminobiphenyl (3,3 '-(MeO) _2- DABP), 3,7-diamino-2,8-diamino-dibenzothiophene-5,5
-Dioxide (o-tolidine sulfone, TSN), and at least one compound thereof can be used.

The diamine component represented by the general formula H ₂ N—R ³ —NH ₂ is, for example, (Chemical formula 8), (Chemical formula 9), (Chemical formula 18)

[0065]

[Chemical 8]

[0066]

[Chemical 9]

[0067]

[Chemical 18]

(In the formula, X is --O--, --S--, --C (CH ₃ ) _2- ,
_{-CH 2 -, - C (CF} 3) 2 -, - C (C 6 H 5) 2 -, - C (C 6 H 5) (CH
₃ )-, -CO- and the like. ), And at least one or more of these compounds can be used.

In addition, other diamines may be used for heat resistance, dielectric constant,
It may be used when adjusting the coefficient of thermal expansion, glass transition temperature, mechanical properties, flexibility, and the like. For example, the general formula H ₂ N-
In the formula of the diamine represented by R ¹¹ —NH ₂ , R ¹¹ is
9)

[0070]

[Chemical 19]

And the like.

The aminosilane compound used in the present invention has a general formula (Chemical Formula 16)

[0073]

[Chemical 16]

(Wherein R ⁵ is a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, R ⁶ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁶ is ⁷ is one or more groups selected from an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or a trialkylsilyl group,
n is an integer of 0 to 3), for example, a monoaminosilane compound represented by 3-aminopropyltrimethylsilane, 3-aminopropyldimethylmethoxysilane, 3-
Aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3
-Aminopropyldimethylpropoxysilane, 3-aminopropylmethyldipropoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyldimethylbutoxysilane, 3-aminopropylmethyldibutoxysilane, 3-aminopropyltributoxysilane, etc. 3-aminopropyldialkylalkoxysilane, 3-
Aminopropylalkyldialkoxysilane, 3-aminopropyltrialkoxysilane, 3- (4-aminophenoxy) propyldialkylalkoxysilane, 3-
(4-Aminophenoxy) propylalkyldialkoxysilane, 3- (4-aminophenoxy) propyltrialkoxysilane, 3- (3-aminophenoxy) propyldialkylalkoxysilane, 3- (3-aminophenoxy) propylalkyldialkoxy Silane, 3-
(3-Aminophenoxy) propyltrialkoxysilane, 4-aminobutyldimethylethoxysilane, 4-aminobutylmethyldiethoxysilane, 4-aminobutyldialkylalkoxysilane such as 4-aminobutyltriethoxysilane, 4-aminobutylalkyl Dialkoxysilane, 4-aminobutyltrialkoxysilane, 3
-Aminopropyltris (trimethylsiloxy) silane, meta-aminophenyldimethylmethoxysilane, meta-aminophenylmethyldimethoxysilane, meta-aminophenyltrimethoxysilane, meta-aminophenyldimethylethoxysilane, meta-aminophenylmethyldiethoxysilane , Meta-aminophenyltriethoxysilane, meta-aminophenyldimethylpropoxysilane, meta-aminophenylmethyldipropoxysilane, meta-aminophenyltripropoxysilane and other meta-aminophenyldialkylalkoxysilanes, meta-aminophenylalkyldialkoxy Silane, meta
Aminophenyltrialkoxysilane, para-aminophenyldimethylmethoxysilane, para-aminophenylmethyldimethoxysilane, para-aminophenyltrimethoxysilane, para-aminophenyldimethylethoxysilane, para-aminophenylmethyldiethoxysilane, para-amino Phenyltriethoxysilane, para-
Para-aminophenyldialkylalkoxysilanes such as aminophenyldimethylpropoxysilane, para-aminophenylmethyldipropoxysilane, para-aminophenyltripropoxysilane, para-aminophenylalkyldialkoxysilanes, para-aminophenyltrialkoxysilane, meta -Aminobenzyldimethylethoxysilane, meta-aminobenzylmethyldiethoxysilane, meta-aminobenzyltriethoxysisilane, meta-aminobenzyldimethylpropoxysilane, meta-
Aminobenzylmethyldipropoxysilane, meta-aminobenzyltripropoxysilane, meta-aminobenzyldimethylpropoxysilane, meta-aminobenzylmethyldipropoxysilane, meta-aminobenzyldialkylalkoxysilane such as meta-aminobenzyltripropoxysilane, meta -Aminobenzylalkyldialkoxysilane, meta-aminobenzyltrialkoxysilane, para-aminobenzyldimethylpropoxysilane, para-aminobenzylmethyldipropoxysilane,
Para-aminobenzyltripropoxysilane and other para-
Para-like aminobenzyldialkylalkoxysilane, para-aminobenzylalkyldialkoxysilane, para-aminobenzyltrialkoxysilane, para-aminophenethyldimethylmethoxysilane, para-aminophenethylmethyldimethoxysilane, para-aminophenethyltrimethoxysilane, etc. Aminophenethyldialkylalkoxysilane, para-aminophenethylalkyldialkoxysilane, para-aminophenethyltrialkoxysilane, or the above meta- or para-benzyl,
Examples include hydrogenated phenethyl compounds.

The diaminosiloxane compound used in the present invention has the general formula

[0076]

[Chemical 17]

(In the formula, R ⁸ is selected from a hydrocarbon group having 1 to 9 carbon atoms, R ⁹ and R ¹⁰ are selected from an alkyl group having 1 to 3 carbon atoms or an aryl group having 1 to 9 carbon atoms. A diaminosiloxane compound represented by one or more groups, and f is 1 or 2.

[0078]

[Chemical 20]

And the like.

The above-mentioned monoaminosilane compound or diaminosiloxane compound is added for the purpose of improving the adhesiveness, and the range of use of the monoaminosilane component or diaminosiloxane component is 100% of all diamine components.
%, 0.1 to 10%, preferably 0.5 to 5%
Is. If the content of the monoaminosilane component or diaminosiloxane component is 0.1% or less, the effect of adhesiveness is small, and 10%.
In the above, heat resistance and mechanical properties are adversely affected.

The solvent used for producing the polyimide precursor and polyimide of the present invention is, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexa Methylphosphoramide, tetramethylene sulfone, para-chlorophenol, para-bromophenol and the like can be mentioned, and at least one kind of them can be used.

The method for preparing the polyimide precursor for carrying out the present invention is as follows. First, the diamine component is dissolved in the aprotic polar solvent, and then ta-phenyl-3,3 ", 4,4" -tetracarboxylic dianhydride is added, and the temperature is kept at 0 to 30 ° C for about 6 hours. Stir. As a result, the reaction gradually progresses, the viscosity of the varnish increases, and the polyimide precursor is produced. 50 to 80 ° C
Adjust the varnish viscosity by stirring while maintaining The reduced viscosity of the polyimide precursor is, for example, the solvent N-methyl-2.
-Pyrrolidone, concentration 0.1 g / 100 ml, temperature 25 ° C
It is desirable to set it to 0.5 dl / g or more under the above condition.

The method of manufacturing the wiring structure of the present invention will be described below with reference to FIG.

First, the conductor layer 2 having a predetermined pattern is formed on the substrate 1.
Are formed by a well-known photo etching technique. Next, the polyimide precursor (polyamic acid varnish) of the present invention is applied and heat-cured to form a polyimide resin layer 3. (Fig. 1
a). Next, a photoresist 4 is applied on the polyimide resin layer 3 and dried (FIG. 1b). The photoresist 4 is exposed by using a predetermined photomask, developed, rinsed and dried to obtain a predetermined pattern (FIG. 1c). After that, the polyimide resin layer 3 is selectively removed by etching using a photoresist pattern as a mask to form a through hole 5 to expose the conductor layer 2 at this portion (FIG. 1d). ). After that, the photoresist 4 is removed with a resist remover (FIG. 1e). Here, if the processing of the through hole 5 of the polyimide resin layer 3 is carried out by an excimer laser
If using laser light such as laser (Fig. 1a → Fig. 1
e), the step of using the photoresist 4 of FIGS. 1b to 1d can be omitted. When the polyimide resin layer 3 is used as a surface protective film or an α ray shielding film, this through hole is used in order 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 vapor deposition method, a sputtering method, a plating method or the like, and the through conductor of the lower conductor layer 2 and the polyimide resin layer 3 is formed by a well-known photoetching technique.
The two-layer wiring structure is formed by forming a predetermined pattern electrically connected in the portion of the hole 5 (FIG. 1f). Further, by repeating this operation many times, a multilayer wiring structure having three or more layers is formed.

[0085]

As described above, according to the present invention, a polyimide having a low dielectric constant, a low thermal expansion coefficient, a high heat resistance, a high glass transition temperature, a high mechanical property (flexibility), and a high adhesive property, and a precursor thereof are provided. When (polyamic acid) was used, the delay time of the propagation signal could be shortened, the moisture resistance was excellent, and there was no warp of the substrate or disconnection or crack of the wiring, and a highly reliable wiring structure could be found. The polyimide according to the present invention includes:
Since it contains many linearly bonded aromatic rings and relatively few imide rings that cause an increase in dielectric constant, it results in low dielectric constant, low thermal expansion coefficient, high heat resistance, and high glass transition temperature at the same time. Equipped. Furthermore, the polyimide also has high mechanical properties (flexibility) by using a diamine having a flexible (flexible) structure as a part of its diamine component. Therefore, it is considered that a high-performance and highly reliable wiring structure has been achieved.

[0086]

EXAMPLES The present invention will now be described with reference to examples.

Synthesis Example 1 2.842 g (7.393 mmol, molar ratio of 50% in diamine component) of bis [4- (4-aminophenoxy) phenyl] ether and 4,4 "under nitrogen stream at room temperature. -Diamino-p-ta-phenyl (1.924 g, 7.393 mmol, molar ratio of 50% in diamine component) was added to N, N-
Dimethylacetamide (DMAc) and N-methyl-2-
It was dissolved in 53.6 g of a 1: 1 mixed solvent of pyrrolidone (NMP) with stirring. Then p-ta-phenyl-3,
3 ", 4,4" -tetracarboxylic dianhydride (TPD
A) 5.475 g (14.78 mmol) was dissolved in the above solution with stirring under a nitrogen stream (solid content concentration 16%).
At this time, the temperature of the solution rose to around 30 degrees and its viscosity became 150 poise. Further add 55 to 6 to this solution.
Heat the mixture in the temperature range of 5 ° C for about 5 hours to increase its viscosity to 56
Poise and polyamic acid varnish (polyimide precursor) were used. This polyamic acid varnish was applied to a glass wafer.
Was spin coated on and heated at 200 ° C. for 30 minutes and 350 ° C. for 30 minutes to obtain a polyimide film. Dielectric constant ε of this polyimide
= 2.7, glass transition temperature Tg = 390 ° C., thermal expansion coefficient α = 21 ppm / ° C., elongation = 17%.

Synthesis Examples 2 to 12, 20 to 24 Polyamic acid varnishes were synthesized in the same manner as in Synthesis Example 1 using the components shown in Table 1. The solid content concentration and viscosity at that time are also shown in Table 1. Polyimide films were obtained from these polyamic acid varnishes in the same manner as in Synthesis Example 1. The characteristic values were in the following ranges. Dielectric constant ε = 2.7
˜2.8, glass transition temperature Tg = 360 to 410 ° C., thermal expansion coefficient α = 14 to 25 ppm / ° C., elongation rate = 11 to 1
8%

[0089]

[Table 1] (Part 1)

[0090]

[Table 1] (Part 2)

[0091]

[Table 1] (Part 3)

Example 1 FIG. 2 shows a sectional view of a dynamic random access memory (DRAM) manufactured according to the present invention and a manufacturing process thereof. No. 1 polyamic acid varnish in Table 1 was spin-coated on a silicon wafer 7 having an element region and a wiring layer formed therein, and heated at 200 ° C. for 30 minutes and 350 ° C. for 30 minutes in this order.
The polyimide film 8 was cured. The thickness of the polyimide film was 10 μm (FIG. 2a). Next, the polyimide resin layer 8
Plasma resistant positive photoresist 9 (RU-16
00P, trade name of Hitachi Chemical Co., Ltd.) was applied and dried. The photoresist is exposed using a photomask, developed,
After rinsing and drying, a predetermined pattern was obtained. After that, the polyimide resin layer 8 is a pattern 9 of photoresist.
With the mask as a mask, the bonding pad portion 10 and the scribe region 11 are selectively removed by reactive etching (O ₂ -RIE) using oxygen gas (FIG. 2).
b). Then, the photoresist is removed using a resist stripper (S
502A, trade name of Tokyo Ohka) (Fig. 2)
c). Bonding pad part 1 created as described above
0, the polyimide film 8 whose base was exposed in the scribe region 11 was used as an α-ray shielding film. Next, the substrate prepared as described above was cut in the scribe region and cut into chips (FIG. 2d). A polyimide film 13 having an adhesive layer of polyamideimide ether as a base on the surface of this chip
The external terminal 12 supported above was thermocompression bonded at 400 ° C. (FIG. 2e). After that, a gold wire 14 is laid between the bonding pad portion 10 and the external terminal 12 with a wire bonder (see FIG. 2).
f) Further, a resin-sealed portion 15 was formed by molding using a silica-containing epoxy-based encapsulant at a molding temperature of 180 ° C. and a molding pressure of 70 kg / cm ² (FIG. 2g). Finally, by bending the external terminals into a specified shape, DRA
A finished product of M was obtained (Fig. 2h). D produced by the above
No crack was found in the polyimide film of RAM.
Further, no defects were found in a temperature cycle test in which the substrate was repeatedly left in an atmosphere of −55 ° C. and 150 ° C. alternately and in a heat resistance test in which it was heated several times at 260 ° C. for 10 seconds, and a product with high reliability could be obtained.

Examples 2 to 5 DRAMs were prepared in the same manner as in Example 1 except that the materials Nos. 2, 4, 8 and 10 shown in Table 1 were used as the polyamic acid varnish. Manufactured DR
No defects were found in the AM in the temperature cycle test or the heat resistance test, and the product could be made highly reliable.

Examples 6 to 11 A solution of 1% aluminum monoethylacetate diisopropylate was applied to increase the adhesive strength between the polyimide layer and the base, and heat treatment was performed at 350 ° C. in an oxygen atmosphere. Are the same silicon wafers 7 and are used as polyamic acid varnishes in Nos. 3, 5, 6, 7, 9, and 1 of Table 1.
A DRAM was prepared in the same manner as in Example 1 by using the respective materials No. 3 and No. 3. None of the manufactured DRAMs were found to be defective in a temperature cycle test or a heat resistance test, and a highly reliable product could be obtained.

Example 12 FIG. 3 shows an example of a two-layer wiring structure manufactured according to the present invention.
A schematic sectional view of the linear IC is shown in FIG. The manufacturing method is shown below. Collector 17 built in silicon wafer 16,
A through hole was provided in the SiO ₂ layer 20 in order to take out the electrode from each region of the base 18 and the emitter 19. 2 μm of Al21 was deposited by vacuum vapor deposition as the first layer wiring conductor, 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% solution of aluminum monoethyl acetate diisopropylate was applied to the above substrate and heat-treated at 350 ° C. for 5 minutes in an oxygen atmosphere. Next, the polyamic acid varnish No. 1 was spin-coated, and 200 ° C. for 30 minutes and 350 ° C. 3
The polyimide film 22 was cured by heating in the order of 0 minutes. The thickness of this polyimide film (interlayer wiring insulating film) is 2.
It was 5 μm. Next, a plasma resistant positive photoresist (RU-1600P, trade name of Hitachi Chemical Co., Ltd.) was applied on the polyimide resin layer 22 and dried. The photoresist was exposed using a photomask, developed, rinsed, and dried to obtain a predetermined pattern. Then, a predetermined portion 23 to be a through hole of the polyimide resin layer 22 is
Using the photoresist pattern as a mask, it was selectively removed by reactive etching (O ₂ -RIE) using oxygen gas. Next, the photoresist was removed by a resist stripping solution (S502A, trade name of Tokyo Ohka).
Then, the surface of the first-layer Al wiring, which is the base of the through-hole portion, is treated with an aqueous sulfamic acid solution to remove the oxide layer, and an Al etching solution is used to obtain a fresh Al surface. After a short treatment with water, it was washed with water. After the substrate was dried, 2 μm of Al24 was deposited as a second layer wiring conductor by vacuum evaporation, and a predetermined wiring pattern was obtained by a well-known photoetching technique. In the two-layer wiring structure formed as described above, no cracks or defects were found in the wiring interlayer insulating film 22. 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 13 to 16 No. 3, 5, 8, and 11 in Table 1 as polyamic acid varnish
A linear IC having a two-layer wiring structure was prepared in the same manner as in Example 12 except that the above materials were used. In any case, no cracks or defects were observed in the wiring interlayer insulating film 22 which is a cured product (polyimide) from these polyamic acid varnishes. Further, no defects were found in the temperature cycle test and the heat resistance test, and the product could be made highly reliable.

Example 17 A sectional view of an individual transistor manufactured according to the present invention and its manufacturing process are shown in FIG. Base 26 and emitter 2 built in a silicon wafer 25 (also serving as a collector)
A through hole is provided in the SiO ₂ layer 28 to take out the electrode from each region of 7, and 2 μm of Al 29 is deposited by vacuum evaporation as a conductor layer of the bonding pad portion, and a predetermined pattern is formed by a well-known photoetching technique. (Fig. 4a). In order to increase the adhesive strength between the polyimide layer and the base, 1% aluminum monoethyl acetate was added to the above substrate.
Apply a solution of Todiisopropylate and apply in an oxygen atmosphere.
Heat treatment was performed at 50 ° C. for 5 minutes. Next, the polyamic acid varnish No. 5 was spin-coated and heated in the order of 200 ° C. for 30 minutes and 350 ° C. for 30 minutes to cure the polyimide film 32. The thickness of this polyimide film (interlayer wiring insulating film) is 2.5 μm.
Met. Next, a plasma resistant positive photoresist (RU-1600P, trade name of Hitachi Chemical Co., Ltd.) was applied on the polyimide resin layer 32 and dried. The photoresist was exposed using a photomask, developed, rinsed, and dried to obtain a predetermined pattern. After that, the bonding pad portion 30 which becomes the through hole of the polyimide resin layer 32 is formed.
Was selectively removed by reactive etching (O ₂ -RIE) using oxygen gas using the pattern of the photoresist as a mask. Next, the photoresist was removed with a resist stripping solution (S502A, trade name of Tokyo Ohka) (FIG. 4b). Next, the surface of the Al wiring exposed at the bonding pad portion 30 was treated with a sulfamic acid aqueous solution to remove the oxide layer, and further treated with an Al etching solution for a short time to obtain a fresh Al surface. After that, it was washed with water. Next, the substrate prepared as described above was cut in the scribe region 31 and cut into chips 33 (FIG. 4c). This chip is mounted on the lead frame 35 which also serves as an external terminal, and thereafter, the bonding pad portion and the external terminal 34 are attached.
A gold wire 36 is laid between the two with a wire bonder, and a resin-sealed portion 37 is molded by molding a silica-containing epoxy-based encapsulant at a molding temperature of 180 ° C. and a molding pressure of 70 kg / cm ^2. Formed. 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 completed individual transistor (FIG. 4d). No crack or peeling was observed in the polyimide film of the individual transistor manufactured as described above. No defects were found in a temperature cycle test in which the sample was repeatedly left in an atmosphere of −55 ° C. and 150 ° C. or in a heat resistance test in which it was heated several times at 260 ° C. for 10 seconds, and a highly reliable product could be obtained. Examples 18 to 22 No. 1, 7, 10, 1 in Table 1 as polyamic acid varnish
Individual transistors were prepared in the same manner as in Example 17 except that the material of 2 was used. In any case, no crack, defect 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 heat resistance test, and the product could be made highly reliable.

Example 23 As an example of a multilayer wiring structure manufactured according to the present invention, FIG.
Figure 2 shows a schematic cross-sectional view of a thin-film multilayer wiring board for large-scale computers. The production example is shown below. The ceramic layer 38 has a tungsten wiring 39 inside, a nickel layer 40 formed by plating as an upper electrode on the upper portion of the tungsten wiring, and a nickel layer 41 and a gold layer 42 formed by plating as a lower electrode on the lower portion of the tungsten wiring. 3 μm of Al was deposited as a conductor layer on the ceramic substrate 43 (100 mm square, 1 mm thick) by vacuum vapor deposition, and a predetermined Al pattern 44 covering the nickel layer 40 was obtained by a well-known photoetching technique. Next, a polyamic acid varnish of composition No. 2 was spin-coated and heated in an oven at 140 ° C. 3
The polyimide film 45 was cured by heating in order of 0 minutes, 200 ° C. for 30 minutes, and 350 ° C. for 60 minutes. The thickness of this polyimide film (interlayer wiring insulating film) was 7 μm. Next, an excimer layer manufactured by Lumonix Co., Ltd. is formed on the polyimide resin layer 45.
The (INDEX 200K; KrF, 248 nm, pulse width 16 ns) was irradiated with a pulse through a predetermined mask to form a through hole having a diameter of 70 μm. At this time, the laser irradiation energy density was 0.4 J / cm ² , and the number of pulses in just etching was 60 pulses. 3 μm of Al was deposited thereon by vacuum vapor deposition, and the first layer Al wiring pattern 46 was formed by a well-known photoetching technique. The above operation is repeated until the through-hole diameter is 70 μm.
m, the second layer polyimide film 47 having a film thickness of 7 μm, the film thickness of 3 μm
Second layer Al wiring pattern 48, through hole diameter 70 μm
Insulating layers and wiring layers were alternately formed in this order in the order of m and a third-layer polyimide film 49 having a film thickness of 7 μm. At this time, immediately before spin-coating the second and subsequent layers of polyimide, ashing treatment was performed on the substrate surface in order to improve the adhesiveness between the polyimides.
Thereafter, a chromium film having a thickness of 0.07 μm and a nickel-copper alloy having a film thickness of 0.7 μm are sequentially deposited by a vacuum vapor deposition method,
A chromium / nickel-copper layer 50 having a diameter of 150 μm was patterned at the through-hole portion of the third layer polyimide film by a well-known photoetching technique. 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 51. In the thin-film multi-layer wiring board prepared as described above, the warp of the board was negligibly small, cracks and defects of the polyimide film were not seen, and the coverage of the Al wiring on the through hole was good. Good electrical continuity was obtained over the wiring.

Example 24 FIG. 6 shows a manufacturing process of a copper-polyimide type multilayer wiring structure manufactured by the present invention. A mullite ceramic layer (100 mm square, 5 mm thick) has a tungsten wiring inside, and a chromium layer 53 (0.05 μ) formed on the tungsten wiring as a plating base film by a sputtering method.
m), a positive type resist 55 was spin-coated on top of the ceramic substrate 52 (FIG. 6b) having the copper layer 54 (0.5 μm), and heated at 90 ° C. for 30 minutes in a nitrogen atmosphere. The film thickness of the resist 55 at this time was 10 μm (FIG. 6c).
Then, after exposing, developing and rinsing with a predetermined mask (Fig. 6d),
Copper plating 56 was performed by electroplating. The plating solution composition is CuSO ₄ / 5H ₂ O 70 g / l, H ₂ SO ₄ 14
0 g / l, HCl 50 ppm, current density 1.0 (A
/ Dm ² ) and the time required to obtain 10 μm thick copper was 40 minutes (FIG. 6e). After completion of copper plating, the plate was washed with water and vacuum dried at 80 ° C. for 1 hour. Further, the above process drawings 6c to 6e were repeated (process drawings 6f to 6h). The resist 55 was stripped with a stripping solution (FIG. 6i) and then washed with an alcohol organic solvent. Then, of the copper and chromium as the plating base film, the portions which are not the base of the subsequent copper plating were selectively removed with an ammonium chloride-based etching solution and a potassium ferricyanide / sodium hydroxide mixed solution, respectively (FIG. 6j). ). After thorough washing with water, nickel plating, and washing with water, vacuum drying was performed (Fig. 6k).
By applying this nickel protective film to copper, it is possible to prevent the reaction between copper and the polyamic acid to be applied thereafter (oxidation of copper). Next, spin coat No2 polyamic acid varnish, 140 ° C 30 minutes, 200 ° C 30 minutes, 350 ° C 6
Heated under nitrogen atmosphere for 0 minutes. The film thickness of the cured polyimide was 23 μm (FIG. 6l). Further, the polyimide layer was flattened by polishing with a tape (# 500 to # 4000) having alumina particles attached thereto, and washed with acetone (FIG. 6m). Further, the above process steps 6b to 6m were repeated 9 times while performing ashing treatment with oxygen after 6k to obtain a copper-polyimide multilayer wiring structure (total thin film layer 400 μm thick) consisting of 10 wiring layers. In the multilayer wiring structure completed as described above, the warp of the final substrate was as small as 9 μm, and peeling and cracks of the polyimide film, corrosion and defects of the wiring, etc. were not observed, and good electrical continuity was achieved across all wiring. was gotten.

Examples 25 to 31 Nos. 5, 8, 10 and 2 of Table 1 as polyamic acid varnishes
A copper-polyimide multilayer wiring structure consisting of 10 wiring layers was obtained in the same manner as in Example 24 except that 1 to 24 were used. In the completed multilayer wiring structure, the final warpage of the substrate is as small as 16 μm or less, and peeling and cracks of the polyimide film, corrosion and defects of the wiring, etc. are not seen, and good electrical continuity across all wiring. was gotten.

Comparative Example 1 No. 13 polyamic acid varnish of Table 2 was synthesized in the same manner as in Synthesis Example 1. This varnish was spin-coated on a glass substrate and heated at 200 ° C. for 30 minutes and 350 ° C. for 30 minutes to obtain a polyimide film having a thickness of 8 μm. This film was extremely brittle and had an elongation of 1% or less. A DRAM was manufactured in the same manner as in Example 1 except that the above varnish was used. After forming the α-ray shielding film (polyimide film) 8 of FIG. 2c, the formed substrate was cut in the scribe region and cut into chips (FIG. 2d). The external terminals 12 supported on a polyimide film 13 having a polyamide-imide ether adhesive layer on the bottom were thermocompression bonded at 400 ° C. to the surface of this chip (FIG. 2e). At this time, many cracks were generated in the polyimide film 8 and the finished product was not reached.

Comparative Example 2 In the same manner as in Synthesis Example 1, No. 14 polyamic acid varnish of Table 2 (wherein PMDA is pyromellitic dianhydride) was synthesized. This varnish is spin-coated on a glass substrate and heated at 200 ° C. for 30 minutes and 350 ° C. for 30 minutes to give a thickness of 8
A μm polyimide film was obtained. This film was extremely brittle and had an elongation of 3% or less. A linear IC was manufactured in the same manner as in Example 12 except that the above varnish was used. In this example, the Al wiring pattern of the second layer is used.
When the resin was formed, many cracks were observed in the polyimide layer under the Al wiring, and the finished product was not reached.

Comparative Example 3 In the same manner as in Synthesis Example 1, No. 15 polyamic acid varnish of Table 2 was synthesized. This varnish was spin-coated on a glass substrate and heated at 200 ° C. for 30 minutes and 350 ° C. for 30 minutes to obtain a polyimide film having a thickness of 8 μm. This film was extremely brittle and had an elongation of 2% or less. Using this polyamic acid varnish, individual transistors were manufactured by the same method as in Example 17. In this case, after the polyimide pattern was formed, it was subjected to a temperature cycle test in which it was left in an atmosphere of −55 ° C. and 150 ° C. alternately and repeatedly, and then a large number of cracks were found when the inside was inspected by an ultrasonic probe method. It did not reach the finished product.

Comparative Example 4 In the same manner as in Synthesis Example 1, No. 16 polyamic acid varnish of Table 2 was synthesized. This varnish was spin-coated on a glass substrate and heated at 200 ° C. for 30 minutes and 350 ° C. for 30 minutes to obtain a polyimide film having a thickness of 8 μm. This film was highly flexible and had an elongation of 50% or more, but had a large coefficient of thermal expansion α of 42 ppm / ° C. Using this polyamic acid varnish, a copper-polyimide multilayer wiring structure was manufactured in the same manner as in Example 24. When the number of wiring layers is 5, polyimide peeling is seen from the ceramic substrate,
It did not reach the finished product. When the warp of the substrate was measured when the number of wiring layers was 4, it was 66 μm. Further, in the process of using a photoresist for copper plating, the mask and the upper layer of the substrate could not be completely adhered, and a large variation was found in the pattern size. Furthermore, disconnection and cracks were found in a part of the copper wirings of the second to fourth layers.

Comparative Examples 5 to 7 Polyamic acid varnishes Nos. 17, 18 and 19 in Table 2 were synthesized in the same manner as in Synthesis Example 1. This varnish was spin-coated on a glass substrate and heated at 200 ° C. for 30 minutes and 350 ° C. for 30 minutes to obtain a polyimide film having a thickness of 8 μm. This film was highly flexible and all had an elongation of 20% or more, but had a large thermal expansion coefficient α of 40 ppm / ° C. Using these polyamic acid varnishes, a copper-polyimide multilayer wiring structure was manufactured in the same manner as in Example 24. When the number of wiring layers was 5, peeling of the polyimide was observed from the ceramic substrate, and the finished product was not reached. When the warpage of the substrate was measured when the number of wiring layers was 4, it was 64 μm, 75 μm and 68 μm for the used polyamic acid varnishes Nos. 17, 18 and 19, respectively. Further, in the photo process, the mask and the upper layer of the substrate could not be brought into close contact with each other, and a large variation in pattern size was recognized. Furthermore, disconnection and cracks were found in a part of the copper wirings of the second to fourth layers.

[0106]

[Table 2]

[0107]

INDUSTRIAL APPLICABILITY As described in the above Examples and Comparative Examples, the novel polyamic acid or polyimide used in the present invention has all characteristics, particularly low dielectric constant, as compared with the conventionally known polyamic acid or polyimide. Since these are excellent in thermal conductivity, low coefficient of thermal expansion, heat resistance, and adhesiveness, it is possible to provide a semiconductor device having high reliability and high performance by using them, and various electronic devices including a multilayer wiring structure.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a manufacturing process of a multilayer wiring structure according to the present invention.

FIG. 2 is a diagram showing an example of a sectional structure of a DRAM and a manufacturing process thereof.

FIG. 3 is a diagram showing a sectional structure of a linear IC according to the present invention.

FIG. 4 is a diagram showing a sectional structure of an individual transistor according to the present invention.

FIG. 5 is a view showing a cross-sectional structure of a thin film multilayer wiring board according to the present invention.

FIG. 6 is a diagram showing an example of a manufacturing process of a copper-polyimide thin film multilayer wiring board 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
... Silicon wafer, 8 ... Polyimide film, 9 ... Photoresist, 10 ... Bonding pad, 11 ... Scribing area, 12 ... External terminal, 13 ... Polyimide film, 14
... gold wire, 15 ... resin sealing part, 16 ... silicon wafer, 1
7 ... Collector, 18 ... Base, 19 ... Emitter, 20 ...
SiO ₂ layer, 21 ... Al, 22 ... Polyimide film, 23 ...
Through-hole, 24 ... Al, 25 ... Silicon wafer, 2
6 ... Base, 27 ... Emitter, 28 ... SiO ₂ layer, 29
... Al, 30 ... Bonding pad section, 31 ... Scribe area, 32 ... Polyimide film, 33 ... Chip, 34 ... External terminal, 35 ... Lead frame, 36 ... Gold wire, 37 ... Resin sealing section, 38 ... Ceramic layer, 39 ... Tungsten wiring, 40 ... Nickel layer, 41 ... Nickel layer, 42 ... Gold layer, 43 ... Ceramic substrate, 44 ... Al pattern, 45
... first layer polyimide film, 46 ... first layer Al wiring pattern
47, second layer polyimide film, 48, second layer Al wiring pattern, 49, third layer polyimide film, 50, chromium /
Nickel-copper layer, 51 ... Nickel / gold composite film, 52 ... Ceramic substrate, 53 ... Chrome layer, 54 ... Copper layer, 55 ... Photoresist, 56 ... Plated copper, 57 ... Nickel protective film, 58 ... Polyimide film

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 23/31

Claims (18)

[Claims] 1. A surface protective film is obtained by heating and dehydrating a polyimide precursor comprising a repeating unit represented by the following general formula (Formula 1) and a repeating unit represented by the following general formula (Formula 2). A wiring structure characterized by being a polyimide. General formula (Formula 1) General formula (Formula 2) (In the formula, R ¹ is (Chemical Formula 3) R is at least one tetravalent organic group selected from
² is (Chemical 4) [Chemical 4] Is a divalent organic group having at least one linear structure selected from R ³ and R ³ is a divalent organic group having at least two aromatic rings and having a bent structure. ) 2. The wiring structure according to claim 1, wherein the number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1) and R ³ in the general formula (Formula 2). When the total number of divalent organic groups having a bent structure represented by
^A polyimide obtained by heating and dehydrating a polyimide precursor in which the number of organic groups represented by ² is 30 to 80 and the number of organic groups represented by R ³ is 70 to 20 is used as a surface protective film. Wiring structure characterized by. 3. The surface protective film comprises a repeating unit represented by the following general formula (Formula 1), a repeating unit represented by the following general formula (Formula 2) and a repeating unit represented by the following general formula (Formula 5). A wiring structure, which is a polyimide obtained by heating and dehydrating a polyimide precursor composed of units. General formula (Formula 1) General formula (Formula 2) General formula (Formula 5) (In the formula, R ¹ is (Chemical Formula 3)) R is at least one tetravalent organic group selected from
² is (Chemical 4) [Chemical 4] Is a divalent organic group having at least one linear structure selected from among R ³ , R ³ is a divalent organic group having at least two aromatic rings and having a bent structure, and R ⁴ is a polymer having a portion thereof. At the end of or the main chain of the polymer, respectively, General formula (Formula 7) A hydrocarbon group containing a silicon atom represented by R ⁵ ,
R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, and R ⁶ is 1 carbon atom
1 to 3 hydrocarbon groups, R ⁷ is at least one group selected from an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or a trialkylsilyl group, and R ⁹ and R ¹⁰ are each having 1 carbon atoms.
To 3 or more, one or more kinds of groups selected from an alkyl group having 1 to 9 carbon atoms, n is an integer of 0 to 3, and f is 1 or 2. ) 4. The wiring structure according to claim 3, wherein the number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1) and R ³ in the general formula (Formula 2). The number of organic groups represented by R ² when the total number of divalent organic groups represented by R and the number of silicon-containing hydrocarbon groups represented by R ⁴ is 100. Is 30 to 80, the number of organic groups represented by R ³ is 70 to 20, and the number of hydrocarbon groups containing silicon represented by R ⁴ is in the range of 0.1 to 10 by heat dehydration. A wiring structure characterized by using the polyimide obtained by the method as a surface protective film. 5. The divalent organic group having a bent structure represented by R ³ in the general formula (Formula 2) is represented by the formula (Formula 8) ), (Chemical formula 9) [Chemical 9] A wiring structure comprising a polyimide obtained by heating and dehydrating a polyimide precursor which is one or more divalent organic groups selected from the structural formulas represented by: 6. An α-ray shielding film obtained by heating and dehydrating a polyimide precursor comprising a repeating unit represented by the following general formula (Formula 1) and a repeating unit represented by the following general formula (Formula 2). A wiring structure, characterized in that it is a polyimide. General formula (Formula 1) General formula (Formula 2) (In the formula, R ¹ is (Chemical Formula 3) R is at least one tetravalent organic group selected from
² is (Chemical 4) [Chemical 4] Is a divalent organic group having at least one linear structure selected from R ³ and R ³ is a divalent organic group having at least two aromatic rings and having a bent structure. ) 7. The wiring structure according to claim 6, wherein the number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1) and R ³ in the general formula (Formula 2). When the total number of divalent organic groups having a bent structure represented by
^A polyimide obtained by heating and dehydrating a polyimide precursor having the number of organic groups represented by ² in the range of 30 to 80 and the number of organic groups represented by R ³ in the range of 70 to 20 is used as an α-ray shielding film. A wiring structure characterized by the above. 8. An α-ray shielding film is represented by a repeating unit represented by the following general formula (Formula 1), a repeating unit represented by the following general formula (Formula 2) and a general formula (Formula 5) below. A wiring structure, which is a polyimide obtained by heating and dehydrating a polyimide precursor comprising a repeating unit. General formula (Formula 1) General formula (Formula 2) General formula (Formula 5) (In the formula, R ¹ is (Formula 3) R is at least one tetravalent organic group selected from
² is (Chemical 4) [Chemical 4] Is a divalent organic group having at least one linear structure selected from R ³ , R ³ is a divalent organic group having at least two aromatic rings and having a bending structure, and R ⁴ is a polymer having a portion thereof. At the end of or the main chain of the polymer, respectively. General formula (Formula 7) A hydrocarbon group containing a silicon atom represented by R ⁵ ,
R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, and R ⁶ is 1 carbon atom
1 to 3 hydrocarbon groups, R ⁷ is one or more groups selected from an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or a trialkylsilyl group, and R ⁹ and R ¹⁰ are each having 1 carbon atoms.
To 3 alkyl groups, one or more groups selected from aryl groups having 1 to 9 carbon atoms, n is an integer from 0 to 3, and f is 1 or 2. ) 9. The wiring structure according to claim 8, wherein the number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1) and R ³ in the general formula (Formula 2). The number of organic groups represented by R ² when the total number of divalent organic groups represented by R and the number of silicon-containing hydrocarbon groups represented by R ⁴ is 100. Is 30 to 80, the number of organic groups represented by R ³ is 70 to 20, and the number of hydrocarbon groups containing silicon represented by R ⁴ is in the range of 0.1 to 10 by heat dehydration. A wiring structure comprising the obtained polyimide as an α-ray shielding film. 10. The divalent organic group having a bending structure represented by R ³ in the general formula (Formula 2) is represented by (Formula 8) ), (Chemical formula 9) [Chemical 9] A wiring structure comprising a polyimide precursor obtained by heating and dehydrating a polyimide precursor which is one or more kinds of divalent organic groups selected from the structural formulas represented by: 11. An insulating film for wiring is obtained by heating and dehydrating a polyimide precursor comprising a repeating unit represented by the following general formula (Formula 1) and a repeating unit represented by the following general formula (Formula 2). A wiring structure, characterized in that it is a polyimide.
General formula (Formula 1) General formula (Formula 2) (In the formula, R ¹ is (Chemical Formula 3) R is at least one tetravalent organic group selected from
² is (Chemical 4) [Chemical 4] Is a divalent organic group having at least one linear structure selected from R ³ and R ³ is a divalent organic group having at least two aromatic rings and having a bent structure. ) 12. The wiring structure according to claim 11,
The number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1) and the number of divalent organic groups having a bent structure represented by R ³ in the general formula (Formula 2) When the total of 100 is 100, the number of organic groups represented by R ² is 30 to 80, and the number of organic groups represented by R ³ is 70 to 20. A wiring structure comprising the obtained polyimide as an insulating film. 13. A wiring insulating film is represented by a repeating unit represented by the following general formula (Formula 1), a repeating unit represented by the following general formula (Formula 2), and a general formula (Formula 5) below. A wiring structure, which is a polyimide obtained by heating and dehydrating a polyimide precursor composed of a repeating unit. General formula (Formula 1) General formula (Formula 2) General formula (Formula 5) (In the formula, R ¹ is (Chemical Formula 3)) R is at least one tetravalent organic group selected from
² is (Chemical 4) [Chemical 4] Is a divalent organic group having at least one linear structure selected from among R ³ , R ³ is a divalent organic group having at least two aromatic rings and having a bent structure, and R ⁴ is a polymer having a portion thereof. At the end of or the main chain of the polymer, respectively, General formula (Formula 7) A hydrocarbon group containing a silicon atom represented by R ⁵ ,
R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, and R ⁶ is 1 carbon atom
1 to 3 hydrocarbon groups, R ⁷ is at least one group selected from an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or a trialkylsilyl group, and R ⁹ and R ¹⁰ are each having 1 carbon atoms.
To 3 or more, one or more kinds of groups selected from an alkyl group having 1 to 9 carbon atoms, n is an integer of 0 to 3, and f is 1 or 2. ) 14. The wiring structure according to claim 13,
Number of divalent organic groups having a linear structure represented by R ² in the general formula (Formula 1), number of divalent organic groups having a bent structure represented by R ³ in the general formula (Formula 2) , And R ⁴ when the total number of silicon-containing hydrocarbon groups represented by R ⁴ is 100,
The number of organic groups represented by ² is 30 to 80, the number of organic groups represented by R ³ is 70 to 20, and the number of silicon-containing hydrocarbon groups represented by R ⁴ is 0.1 to 10. A wiring structure comprising a polyimide obtained by heating and dehydrating a polyimide precursor within a range as an insulating film. 15. In claim 11, claim 12, claim 13 or claim 14, the divalent organic group having a bending structure represented by R ³ in the general formula (Formula 2) is ), (Chemical formula 9) [Chemical 9] A wiring structure comprising a polyimide precursor obtained by heating and dehydrating a polyimide precursor which is one or more kinds of divalent organic groups selected from the structural formulas represented by: 16. The wiring structure according to claim 1, wherein the wiring structure is a semiconductor integrated circuit device. 17. The wiring structure according to claim 1, wherein the wiring structure is an individual transistor element. 18. The wiring structure according to claim 11, wherein the wiring structure is a thin film multilayer wiring board.