TW201335238A - Polyimide precursor and resin composition using the same, polyimide formed article protective layer, semiconductor device and method for fabricating the same, electronic component, and electric component - Google Patents

Abstract

A polyimide precursor including a structural unit represented by the following formula (I) and having an amino group in a part of terminal groups is provided. Integration value of 1H-NMR spectrum peak (A) of a hydrogen atom bonding with a carbon adjacent to a carbon bonding with the amino group is 3% to 8% of the integration value of 1H-NMR spectrum peak (B) of a hydrogen atom of amide bond in the polyimide precursor. In formula (I), A1 and A2 each independently represent a benzene ring, a group having two benzene rings bonded by a single bond, or a group having two or more aromatic rings bonded by anyone of -O-, -S-, or -CO-. Each R independently represents a hydrogen atom or a methyl group. A1 and A2 may include substituent groups respectively.

Description

Polyimine precursor and resin composition using the same

The present invention relates to a polyimide precursor, a resin composition using the same, a polyimide composition obtained from the resin composition, a protective layer containing the molded body, and a protective layer having the protective layer A semiconductor device, a method of manufacturing a semiconductor device, and an electric component or an electronic component having the semiconductor device.

In recent years, with the miniaturization and high integration of semiconductor packages, attention has been focused on a multilayer wiring structure in which a plurality of layers are formed to connect wirings between semiconductor elements or wirings connecting semiconductor elements and external elements. If the multilayer wiring structure has a structure in which a conductive portion overlaps a plurality of insulating layers. In general, among the above-mentioned conductive portions, a metal having good conductivity such as copper or aluminum can be used. In the insulating layer, an insulating inorganic substance such as SiO ₂ , SiN or SiC can be used.

An insulating layer (hereinafter referred to as an inorganic layer) using an inorganic material is inferior in mechanical properties (for example, elongation at break and elastic modulus), and therefore it is necessary to form a protective layer (stress mitigating material). A polyimine resin (polyimine imide molded body) having excellent mechanical properties and insulating properties can be used as the protective layer (Patent Document 1)

A method of forming an inorganic layer and a protective layer in the case of using a polyimide polyimide as a protective layer will be described with reference to FIG.

First, a polyimide (II) molded body 2 as a protective layer is formed on a substrate (not shown) having an inorganic layer 1 (hereinafter referred to as a first inorganic layer), and then an inorganic layer 3 is further formed (hereinafter referred to as a 2 inorganic layer). The method of forming the inorganic layers 1 and 3 is a plasma chemical vapor deposition (PCVD) method in which a film formation rate is high and a film having high flatness can be formed.

When the insulating layer is formed by PCVD, it is considered that heat treatment at a high temperature is required. However, when the second inorganic layer 3 is formed, if the heat treatment is performed at a high temperature, stress is generated due to the difference in thermal expansion coefficients of the first inorganic layer 1, the polyimide intermediate molded body 2, and the second inorganic layer 3, respectively. The imide molded article 2 is peeled off from the inorganic layer 1 and causes cracks in the inorganic layer. In order to solve such problems, for example, a polyimine molded article having a relatively high Tg has been proposed (Patent Document 2)

However, the present inventors have found that even when the polyimine molded article of Patent Document 2 is used, once the polyimide polyimide molded article is exposed to a high temperature exceeding the glass transition temperature (Tg), polyimine formation occurs. The deformation of the body 2 does not sufficiently suppress the stress caused by the difference in thermal expansion coefficients of each of the first inorganic layer 1, the polyimide intermediate molded body 2, and the second inorganic layer 3, and the polyimine imide molded body 2 cannot be surely prevented. Peeling or cracking of the inorganic layer.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2006-318989

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-272072

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide precursor which can form a polyimine imide formed body which can suppress thermal expansion of the polyimine imide molded body itself even if heat exceeding Tg is applied. The stress caused by the lamination of the inorganic layer can be alleviated.

In particular, it is an object of the present invention to provide a polyimide precursor having a polyimine imide formed in a temperature range higher than the Tg of the polyimide body. Low thermal expansion rate.

Furthermore, it is an object of the present invention to provide a polyimine precursor which provides a high Tg polyimine shaped body.

According to the present invention, the following polyimine precursors and the like are provided:

<1> A polyimine precursor which is a polyimine precursor having a structural unit represented by the following formula (I) and having an amine group in a part of a terminal group; The integral value of the ¹ H-NMR spectral peak (A) of the hydrogen atom bonded to the carbon atom adjacent to the carbon atom of the above-mentioned amino group is a hydrogen atom which represents a guanamine bond of the polyimide precursor. The integral value of the ¹ H-NMR spectral peak (B) is 3% to 8%.

(In the formula (I), A ¹ and A ² each independently represent a benzene ring, two phenyl rings are bonded by a single bond, or two or more aromatic rings are -O-, -S-, or -CO- Any one of the bonded groups. R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. A ¹ and A ² may each have a substituent.

<2> The weight average molecular weight of the above polyimine precursor is from 40,000 to 100,000.

<3> A resin composition comprising the above polyimine precursor and a solvent.

<4> A polyimine molded article obtained by heating the above resin composition at 250 ° C to 500 ° C.

<5> A protective layer comprising the above polyimine molded article.

<6> A semiconductor device having the above protective layer.

<7> A method of producing a semiconductor device, comprising: a step of applying the resin composition on a first inorganic layer; a step of heating the resin composition to obtain a polyimide composition; and The step of forming the second inorganic layer on the polyimine molded article at a temperature higher than the Tg of the polyimine molded article.

<8> A semiconductor device obtained by the above manufacturing method.

<9> A power component or an electronic component having the above semiconductor device.

According to the present invention, there can be proposed a polyimine precursor which provides a polyimine imide having a low thermal expansion rate in a temperature range higher than a Tg of a polyimine molded article. .

Further, according to the present invention, a polyimine precursor which provides a high Tg polyimine shaped body can be proposed.

1‧‧‧1st inorganic layer

2‧‧‧ Polyimine molded body

3‧‧‧2nd inorganic layer

10‧‧‧Semiconductor substrate

20‧‧‧Semiconductor components

30‧‧‧Insulation

40‧‧‧Metal wiring

Fig. 1 is an example of a ¹ H-NMR chart of a polyimide precursor of the present invention.

Fig. 2 is a schematic view showing a thermal expansion curve of a cured polyimine product at a fixed temperature increase rate.

3 is a schematic cross-sectional view showing a multilayer wiring structure of an example of a semiconductor device of the present invention.

4 is a side view showing a part of a multilayer wiring structure in a semiconductor device.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to these embodiments.

[polyimine precursor]

The polyimine precursor (polyglycine) of the present invention has a structural unit represented by the following formula (I) and has an amine group in a part of the terminal group.

Further, an integral value of a ¹ H-NMR (nuclear magnetic resonance spectroscopy) spectral peak (A) indicating a hydrogen atom bonded to a carbon atom adjacent to a carbon atom to which the above-described amino group is bonded is a polyimine. The indole bond of the precursor has a value of 3% to 8% of the integral value of the ¹ H-NMR spectrum peak (B) of the hydrogen atom.

In the formula (I), A ¹ and A ² each independently represent a benzene ring, two phenyl rings are bonded by a single bond, or two or more aromatic rings are -O-, -S-, or -CO- The base of either bond. R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. Further, A ¹ and A ² may each have a substituent.

Examples of A ¹ include a group represented by the following formula. Examples of A ² include a group in which a group represented by the following formula is tetravalent.

A ^{1 is} preferably an aromatic ring or a group in which two aromatic rings are bonded by a single bond (for example, a phenyl group).

A ^{2 is} preferably an aromatic ring or a group in which two aromatic rings are bonded by a single bond (for example, a biphenyl group is changed to a tetravalent group).

The aromatic ring may, for example, be a benzene ring or a benzene ring containing an organic group having 1 to 3 carbon atoms, and is preferably a benzene ring.

The alkyl group as R is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 3 carbon atoms.

In the polyimine precursor of the present invention, the NMR peak (A) having a hydrogen atom of a carbon atom adjacent to a carbon atom to which an amine group is bonded, which is a terminal group of a polyimide precursor, is present. The integral value is 3% to 8% of the integrated value of the NMR peak (B) indicating the hydrogen atom of the guanamine bond of the polyimide precursor.

The terminal group of the polyimine precursor is not a substituent (a substituent of a side chain) contained in the constituent unit represented by the formula (I), but represents a constituent unit represented by the formula (I). The base of both ends.

Fig. 1 is an example of a ¹ H-NMR chart of a polyimide precursor of the present invention.

The peak (A) is a peak of a hydrogen atom possessed by a carbon atom adjacent to a carbon atom to which an amine group is present as a terminal group of a polyimide precursor, and is usually 6 ppm to 7 ppm.

The peak (B) is a peak of a hydrogen atom representing a guanamine bond of the polyimide precursor, and is usually from 10.4 ppm to 10.8 ppm.

When the value obtained by [the integral value of the peak (A)] ÷ [the integral value of the peak (B)] × 100 is 3% to 8%, the integral value of the peak (A) can be regarded as the integral value of the peak (B). 3% to 8%.

When the integral value of the peak (A) is 3% or more of the integral value of the peak (B), since α ₂ becomes small, stress due to lamination of the inorganic layer at a temperature exceeding Tg can be alleviated. When it is 8% or less, the mechanical properties and heat resistance of the polyimine molded article can be improved.

The integral value of the peak (A) is preferably from 5% to 8%, more preferably from 6% to 8%, even more preferably from 6.5% to 8%, of the integral value of the peak (B).

The polyimine precursor of the present invention can provide a high Tg and low alpha ₂ polyimine shaped body. When a low-α ₂ polyimine molded body is used, even if the polyimine molded body is exposed to a temperature higher than Tg, significant thermal expansion can be prevented, and the thermal expansion unlike the inorganic layer can be reduced. The stress generated.

Further, the polyimine precursor of the present invention can provide a polyimine molded article having a high Tg, a low thermal expansion coefficient (CTE) in a temperature range lower than Tg, and excellent mechanical properties.

The standard polyphenylene of the polybendimimine precursor of the present invention is obtained from the viewpoint of improving heat resistance (Tg, coefficient of thermal expansion (CTE), α _2, etc.) and mechanical properties (breaking elongation, etc.). The weight average molecular weight in terms of ethylene is preferably from 40,000 to 100,000, more preferably from 50,000 to 90,000, still more preferably from 50,000 to 75,000.

When the weight average molecular weight is 40,000 or more, the polyimide polyimide precursor can be easily obtained by heating the polyimide precursor, and the mechanical properties of the obtained polyimide pigment molded body tend to be improved. When the weight average molecular weight is 100,000 or less, in the case of synthesizing a polyimide precursor, there is a tendency that the molecular weight is easily controlled, the viscosity is easily lowered, and the coating is easily applied uniformly to the substrate.

Using gel permeation chromatography (GPC), The weight average molecular weight can be determined by standard polystyrene conversion.

The amine group of the terminal group of the polyimine precursor of the present invention is usually a residue of a diamine used for synthesizing the polyimine precursor described below, but may be a precursor of polyimine. In the synthesis of the substance, an amine group derived from an amine phenol or the like for providing a terminal group.

[Synthesis of Polyimine Precursor]

The polyimine precursor of the present invention is a polyamic acid obtained by polymerizing a tetracarboxylic acid and a derivative thereof (the tetracarboxylic acid and its derivative are collectively referred to as a tetracarboxylic acid) and a diamine. For example, a tetracarboxylic dianhydride and a diamine can be polymerized, and the tetracarboxylic dianhydride is obtained by dehydrocyclizing a tetracarboxylic acid.

The polyimine precursor such as the peak value of the peak (A) having an integral value of 3% to 8% of the integral value of the peak (B) can be obtained, for example, by adjusting the ratio of the polymerized tetracarboxylic acid to the diamine.

For example, by performing polymerization in a ratio of tetracarboxylic acid:diamine (mole ratio)=96:100 to 98:100, an integral value such as a sharp peak (A) can be obtained as 3% of the integral value of the spike (B). ~8% polyimine precursor.

As the tetracarboxylic acid used for the synthesis of the polyimine precursor of the present invention, a general tetracarboxylic acid can be used. From the viewpoint of lowering the CTE, it is preferred to use a tetracarboxylic acid having a rigid structure. Specifically, for example, pyromellitic dianhydride and biphenyl-3,3',4,4'-tetracarboxylic dianhydride are more preferably used.

As the diamine used for synthesizing the polyimine precursor of the present invention, an aromatic diamine which is generally used can be mentioned. For example, one, two or three benzene rings may be linked by a single bond. And a compound in which two amine groups are bonded to the benzene ring, and 1, 2 or 3 benzene rings are linked by -O-, -S-, or -CO-, and two amine groups are bonded to the benzene a compound of the ring.

In the case where the above aromatic diamine has one benzene ring, the two amine groups are preferably bonded in the para or ortho position. When the aromatic diamine has two or more benzene rings, the two amine groups are preferably bonded to different benzene rings. From the viewpoint of lowering the CTE, the aromatic diamine preferably uses, for example, p-phenylenediamine, o-phenylenediamine, and 2,2'-dimethyl-4,4'-diaminobiphenyl.

The polyimine precursor of the present invention can be synthesized by the previously disclosed method for the synthesis of poly-proline. For example, after a predetermined amount of a diamine is dissolved in a solvent, a predetermined amount of tetracarboxylic dianhydride is added to the obtained diamine solution and stirred. The tetracarboxylic dianhydride was obtained by heating a tetracarboxylic acid by a dryer at 160 ° C for 24 hours and dehydrocyclizing.

By adjusting the amount of the diamines and the tetracarboxylic acids, a polyimine precursor can be obtained which is adjacent to the carbon atom to which the amine group is bonded as a terminal group of the polyimide precursor. The integral value of the peak (A) of the NMR spectrum of the hydrogen atom of the carbon atom is 3% of the integral value of the peak (B) of the NMR spectrum of the hydrogen atom representing the indole bond of the polyimide precursor. 8%.

When each monomer component is dissolved, it may be heated as needed. The reaction temperature is preferably from -30 ° C to 200 ° C, more preferably from 20 ° C to 180 ° C, still more preferably from 30 ° C to 100 ° C. Stirring is continued at room temperature (20 ° C to 25 ° C) or at the above reaction temperature, and the viscosity of the poly-proline is set to a fixed value.

Viscosity can be measured using an E-type viscometer (such as manufactured by Toki Sangyo Co., Ltd.). Measured at 25 °C. The above reaction can also be carried out usually in the range of 3 hours to 100 hours depending on the type of the tetracarboxylic acid and the diamine to be used.

The polyglycine component (hereinafter referred to as a solute) from the viewpoint of the coating property of the substrate with respect to the total amount of the obtained solution containing the polyimide precursor (hereinafter referred to as polylysine solution) It is preferably from 5% by mass to 60% by mass, further preferably from 10% by mass to 50% by mass, particularly preferably from 10% by mass to 40% by mass.

The ratio of the solute (resin non-volatile component) in the polyaminic acid solution can be determined as follows: in a metal dish of a known quality (on a 1 g basis), a poly-proline solution is taken and the mass is measured (metal The mass of the dish and polylysine, hereinafter referred to as the mass before heating). Then, it was heated on a hot plate having a surface temperature of 200 ° C for 2 hours, and the mass after the solvent was sufficiently volatilized (the mass of the metal dish and the polylysine, hereinafter referred to as the mass after heating) was measured, and the mass after heating (the mass after heating) was calculated. - Quality of metal dish) ÷ (mass before heating - mass of metal dish) × 100.

The solvent used in the synthesis of the polyimine precursor of the present invention is not particularly limited as long as it is a solvent capable of dissolving diamines, tetracarboxylic acids, and polyimine precursors. Specific examples of such a solvent include an aprotic solvent, a phenol solvent, an ether, and a glycol solvent.

Examples of the aprotic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylhexene. a guanamine solvent such as guanamine, 1,3-Dimethylimidazolidinone or tetramethylurea; a lactone solvent such as γ -butyrolactone or γ -valerolactone; a phosphorus-containing amide-based solvent such as Hexamethylphosphoric amide or hexamethylphosphine triamide; a sulfur-containing solvent such as dimethylhydrazine, dimethyl hydrazine or cyclobutyl hydrazine; cyclohexanone; A ketone solvent such as methylcyclohexanone; a tertiary amine solvent such as methylpyridine or pyridine; or an ester solvent such as acetic acid (2-methoxy-1-methylethyl).

Examples of the phenol solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, and 2, 6-xylenol, 3,4-xylenol, and 3,5-xylenol.

Examples of the ether-based and ethylene glycol-based solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, and 1,2-bis(2-methoxyethoxy). Ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether or the like.

From the viewpoint of solubility and coatability to a substrate, N-methyl-2-pyrrolidone is preferred. These solvents may be used singly or in combination of two or more.

The polylysine solution is preferably 500 mPa at 25 ° C. s~200000mPa. s, more preferably 2000 mPa. s~100000mPa. s, further preferably 5000 mPa. s~30000mPa. s. Here, the viscosity is a value measured at 25 ° C using an E-type viscometer (VISCONIC EHD manufactured by Toki Sangyo Co., Ltd.). The rotation speed varies depending on the viscosity range of the measurement object, and is generally measured in the range of 0.5 rpm to 100 rpm.

If the viscosity is 500mPa. When s or more, the coating of the substrate by the polyimide precursor solution becomes easy. If the viscosity is 200,000mPa. When it is s or less, stirring at the time of synthesis becomes easy. However, in order to obtain a viscosity of 200,000 mPa when the polyimine precursor is synthesized. a polytheneimine precursor solution below s, added after the reaction The solvent is stirred and a polyamic acid solution having good handleability is obtained.

[Resin composition]

The resin composition of the present invention comprises a polyimide intermediate and a solvent.

[solvent]

The resin composition of the present invention preferably uses a solvent as needed.

The solvent is not particularly limited as long as it can dissolve the polyimine precursor of the present invention. As the solvent described above, the solvent described can be used as a solvent which can be used in the synthesis of the above polyimine precursor. The solvent may be the same as or different from the reaction solvent used in the synthesis of the polyamic acid.

The solvent content is preferably adjusted to a viscosity of 5 Pa at 25 ° C of the resin composition. s~100 Pa. s to add.

Further, the boiling point of the solvent at normal pressure is preferably from 60 ° C to 210 ° C, more preferably from 100 ° C to 205 ° C, still more preferably from 140 ° C to 180 ° C. When the boiling point is 210 ° C or less, the time required in the drying step can be shortened. Further, when the boiling point is 60 ° C or more, the roughness of the surface of the film can be suppressed, and bubbles can be suppressed from entering the film.

[Other ingredients]

The resin composition of the present invention may contain, in addition to the above-mentioned polyimide precursor and solvent, (1) an adhesiveness imparting agent, (2) a surfactant, a leveling agent, and the like.

[Other Ingredients: (1) Adhesive Substance]

The resin composition of the present invention may contain, for example, an organic decane compound or an aluminum chelate compound (1) an adhesion imparting agent in order to improve the adhesion between the cured film and the substrate.

Examples of the organic decane compound include vinyl triethoxy decane, γ-glycidoxypropyl triethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, and urea propyl trisole. Ethoxy decane, methyl phenyl decane diol, ethyl phenyl decane diol, n-propyl phenyl decane diol, isopropyl phenyl decane diol, n-butyl phenyl decane diol, isobutyl Phenyl decanediol, tert-butylphenyl decane diol, diphenyl decane diol, ethyl methyl phenyl stanol, n-propyl methyl phenyl stanol, isopropyl methyl phenyl Hydranol, n-butylmethylphenyl stanol, isobutyl methyl phenyl stanol, tert-butyl methyl phenyl stanol, ethyl n-propyl phenyl stanol, ethyl isopropyl phenyl stanol, n-butyl Ethyl phenyl decyl alcohol, isobutyl ethyl phenyl stanol, tert-butyl ethyl phenyl stanol, methyl diphenyl stanol, ethyl diphenyl stanol, n-propyl diphenyl Base stanol, isopropyl diphenyl stanol, n-butyl diphenyl stanol, isobutyl diphenyl stanol, tert-butyl diphenyl Alkanol, phenyl decane triol, 1,4-bis(trihydroxydecyl)benzene, 1,4-bis(methyldihydroxydecyl)benzene, 1,4-bis(ethyldihydroxydecyl) Benzene, 1,4-bis(propyldihydroxydecyl)benzene, 1,4-bis(butyldihydroxydecyl)benzene, 1,4-bis(dimethylhydroxydecyl)benzene, 1,4 - bis(diethylhydroxydecyl)benzene, 1,4-bis(dipropylhydroxydecylalkyl)benzene, 1,4-bis(dibutylhydroxydecyl)benzene, and the like.

Examples of the aluminum chelate compound include aluminum tris(acetylacetonate) and diisopropyl aluminum acetate.

In the case where the (1) adhesion imparting agent is used, the amount of the formulation is not particularly limited, but, for example, from the viewpoint of providing good adhesion, the compounding amount is preferably 0.1 in terms of 100 parts by mass of the polyimide precursor. Parts by mass to 20 parts by mass, more preferably 0.5 part by mass Parts by mass to 10 parts by mass.

[Other Ingredients: (2) Surfactant (also known as leveling agent)]

Further, the resin composition of the present invention may contain a suitable surfactant in order to prevent coating properties such as streaks (non-uniformity in film thickness).

Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.

As a commercial item, Megafac F171, F173, R-08 (trade name; manufactured by Dainippon Ink Chemical Industry (DIC) Co., Ltd.), Fluorad FC430, FC431 (trade name; Sumitomo 3M (share) manufacturing), organic A siloxane polymer KP341, KBM303, KBM403, KBM803 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

In the case of using the (2) surfactant, the amount of the surfactant is not particularly limited. For example, from the viewpoint of providing good coatability, it is equivalent to 100 parts by mass of the polyimide precursor, preferably 0.01 to 10 The mass fraction is more preferably 0.05 to 5 parts by mass.

The method for producing the resin composition of the present invention is not particularly limited. For example, when the reaction solvent and the solvent in synthesizing the polyimide precursor are the same, the synthesized polyaminic acid solution can be used as a resin composition. Further, a method of adding an organic solvent and optionally adding other additives to the polyimide precursor solution in a temperature range of room temperature (25 ° C) to 80 ° C, and stirring and mixing may be mentioned.

For the stirring and mixing, a device such as a three-one motor (manufactured by Shinto Chemical Co., Ltd.), a revolving revolving mixer, or the like can be used. Further, heating at 40 ° C to 100 ° C may be performed as needed. The following methods can be cited: When the reaction solvent in synthesizing the polyimine precursor is different from the organic solvent, the reaction solvent in the synthesized polyaminic acid solution is removed by reprecipitation or solvent distillation to obtain a polyimine. The precursor is then added to an organic solvent and optionally other additives at room temperature to 80 ° C, and stirred and mixed.

The viscosity of the resin composition of the present invention at 25 ° C is preferably 5 Pa from the viewpoint of workability and purpose, and from the viewpoint of workability in the coating step. s~100Pa. s, more preferably 5Pa. s~50Pa. s, further preferably 5Pa. s~30Pa. s.

[Polyimide molded body]

The polyimine molded article of the present invention can be obtained by applying a resin film obtained by applying the resin composition of the present invention and drying it, and subjecting the resin film to heat treatment (imidization).

The method for producing a polyimine molded article preferably comprises: (1) a step of applying the resin composition of the present invention to a substrate; and (2) applying the resin film at 80 ° C to 200 ° C. a step of forming a resin film by heat drying; (3) a step of heat-treating the dried resin film at a temperature of 250 ° C to 500 ° C to imidize the polyimine precursor in the resin composition .

Each step will be described below.

(1) Coating step

The coating method in the coating step is not particularly limited, and a known coating method can be appropriately selected depending on the desired coating thickness or the viscosity of the resin composition. use. Specifically, a coating method of a knife coater, a knife coater, an air knife coater, a roll coater, a spin coater, a flow coater, a die coater, a bar coater, or the like can be applied; spin coating a coating method such as spraying, dip coating, or the like; a printing method using a printing technique such as screen printing or gravure printing.

The base material to which the resin composition is applied is not particularly limited as long as it has heat resistance at the drying temperature in the subsequent step.

For example, a glass substrate, a ruthenium wafer substrate, a metal substrate such as stainless steel, aluminum oxide, copper, or nickel; polyethylene terephthalate (PET), or extended polypropylene (OPP) may be mentioned. ), polyethylene terephthalate, polyethylene terephthalate, polycarbonate, polyimine, polyamidimide, polyether phthalimide, polyether ether ketone, polyether A resin substrate such as ruthenium, polyphenyl hydrazine or polyphenylene sulfide.

Further, the resin composition of the present invention is particularly useful for coating on an inorganic layer of SiN, SiC, SiO ₂ or the like to form a protective layer. Therefore, it is preferred to use a substrate comprising such inorganic layers.

The thickness of the resin composition of the present invention is appropriately adjusted depending on the thickness of the target polyimide body and the ratio of the resin nonvolatile component in the resin composition, and is usually about 0.1 μm to 100 μm. The resin non-volatile component can be obtained by the above method. The coating step is usually carried out at room temperature, and the resin composition can be heated at a temperature ranging from 40 ° C to 80 ° C for the purpose of lowering the viscosity and improving workability.

After the coating step, a (2) drying step is then carried out. The drying step is for It is carried out by removing the solvent. The drying step may be performed by means of a heating plate, a box dryer, a conveyor type dryer, or the like. The drying temperature is preferably from 80 ° C to 200 ° C, more preferably from 100 ° C to 150 ° C.

Next, a (3) heating step is performed. The heating step is a step of removing (2) the solvent remaining in the resin film in the drying step, and subjecting the oxime imidization reaction of the polyimide precursor in the resin composition.

The heating step can be carried out using an inert gas oven, a heating plate, a box dryer, a conveyor type dryer, or the like. Further, this step may be carried out simultaneously with the above (2) drying step, or may be carried out successively.

The heating step can be carried out in an air atmosphere, but it is preferably carried out under an inert gas atmosphere from the viewpoint of safety and oxidation resistance. Examples of the inert gas include nitrogen gas, argon gas, and the like.

The heating temperature is appropriately adjusted depending on the type of the organic solvent, and from the viewpoint of providing a cured film having good mechanical properties, the heating temperature is preferably from 250 ° C to 400 ° C, more preferably from 350 ° C to 400 ° C. In the case of smoothly carrying out the imidization, it is preferably 250 ° C or more. Further, from the viewpoint of excellent heat resistance, it is preferably 400 ° C or lower. The heating time is usually from about 0.5 hours to about 3 hours.

The obtained polyimine imide formed body can be patterned by a photoresist process depending on the use.

Examples of the photoresist process include a method in which a photoresist is applied after the (3) heating step, and a pattern is formed by exposure and development.

The photoresist material and the material used for etching and the like can be used for general photoresist There are no special restrictions on the materials of Cheng. For example, the etching method can apply either of wet etching and dry etching. Examples of the etching solution used for the wet etching include a hydrazine hydrate, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, and the like.

Further, the dry etching may employ a method such as oxygen plasma etching and oxygen sputtering etching. After the above pattern is formed, the photoresist can be peeled off from the polyimide body using an organic solvent. Examples of the organic solvent include ethanolamine, NMP (N-methyl-2-pyrrolidone), and DMSO (dimethylammonium), and a mixture of these may be used.

The amount of the residual organic solvent after the production of the polyimine molded article of the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less. The amount of residual solvent can be determined by GC-MS (Gas Chromatograph-Mass Spectrometer).

The mechanical properties of the polyimine molded article of the present invention are preferably 3 GPa or more in both the width direction and the operation direction. The tensile strength is preferably 100 MPa or more, more preferably 200 MPa or more. The elongation at break is preferably from 30% to 100%.

These mechanical properties can be obtained by a tensile test of a tensile tester.

If the polyimine molded body has these mechanical properties, the inorganic layer can be sufficiently protected in the multilayer wiring structure. Further, the polyimine molded article used for a semiconductor device has sufficient toughness and can be used in practical applications.

The glass transition temperature (Tg) of the polyimine molded article of the present invention is preferably from 250 ° C to 440 ° C, more preferably from 350 ° C to 400 ° C. When Tg is 350 ° C to 400 ° C, it is evaluated as having excellent heat resistance when used in a semiconductor device. Tg can be described later The method described in the examples was measured.

[Protective layer / semiconductor device / method of manufacturing semiconductor device / electric power, electronic parts]

As the protective layer of the present invention, the above polyimine molded body can be used. For example, in the semiconductor device, a protective layer for protecting the first inorganic layer of SiN, SiC, SiO ₂ or the like can be used.

The semiconductor device of the present invention includes, for example, a multilayer wiring structure. The semiconductor device of the above may be manufactured by the steps of applying a resin composition onto a substrate having an inorganic layer (referred to as a first inorganic layer), and heating the resin composition to obtain a polyimide composition. And a step of forming an inorganic layer (referred to as a second inorganic layer) on the polyimine molded article at a higher temperature than the Tg of the polyimine molded article.

The method of forming the first inorganic layer or the second inorganic layer is PCVD in which a film formation rate is high and a film having high flatness can be formed.

Fig. 4 shows an example of a multilayer wiring structure, and an enlarged multilayer wiring structure and a part thereof. In FIG. 4, 10 is a semiconductor substrate, 20 is a semiconductor element, 30 is an insulating layer, and 40 is a metal wiring. The insulating layer contains SiN, SiC, SiO ₂ , and the polyimine (PI) shaped body of the present invention can be used as a protective layer.

The polyimine molded article of the present invention has a small coefficient of thermal expansion (α ₂ ) in a temperature range higher than Tg, so that even when the second inorganic layer is formed at a temperature higher than Tg, the film can be prevented from being marked. Expands and prevents deformation or positional displacement of the film.

When a polyimine molded article having a low α ₂ is used, it is considered that even if the polyimide polyimide molded body is exposed to a temperature higher than Tg, significant thermal expansion can be prevented, and generation due to thermal expansion unlike the inorganic layer can be prevented. The reduction in stress or the deformation of the polyimide body.

Since the polyimide body has heat resistance and mechanical properties, the semiconductor device of the present invention can be used for electronic parts. Here, the electronic component includes a semiconductor device and various electronic devices for a multilayer wiring board, a mobile phone, a smart phone, a computer, and the like.

[Example]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the invention is not limited to these examples.

Synthesis Example 1 [Synthesis of Polymer A]

In a 0.3-liter flask equipped with a stirrer and a thermometer, 238 g of N-methylpyrrolidone (NMP) and 10.8 g (100 mmol) of p-phenylenediamine were placed, stirred and dissolved, and then biphenyl-3,3',4 was added. , 4'-tetracarboxylic dianhydride 28.25 g (96 mmol), and fully stirred to completely dissolve. Thereafter, the mixture was stirred for about 24 hours until the molecular weight became a constant value to obtain a polyimide intermediate solution (polymer A solution). Further, the resin A solution had a resin nonvolatile content (NV) of 14.1%.

Furthermore, the content of the polyimine precursor (resin non-volatile component) is calculated as follows: in a metal dish of a known quality (on a 1 g basis), the composition of the polyimide precursor is taken and the mass is measured. (The mass of the metal dish and the polyimide precursor composition, hereinafter referred to as the mass before heating). Thereafter, it was heated on a hot plate for 2 hours. And measure the mass of the solvent after evaporation (the mass of the metal dish and the polyimide precursor, hereinafter referred to as the mass after heating), calculate (mass after heating - the quality of the metal dish) ÷ (mass before heating - metal The quality of the dish) × 100.

The weight average molecular weight of the polymer A can be determined by standard method using a gel permeation chromatography. The weight average molecular weight of the polymer A was 50,000.

Specifically, the weight average molecular weight was measured by the following apparatus and conditions.

Measuring device: detector L4000UV manufactured by Hitachi, Ltd.

Pump: L6000 manufactured by Hitachi, Ltd.

C-R4A Chromatopac manufactured by Shimadzu Corporation

Measurement conditions: column Gelpack GL-S300MDT-5×2

Dissolved solution: THF/DMF=1/1 (volume ratio)

LiBr (0.03 mol/l), H ₃ PO ₄ (0.06 mol/l)

Flow rate: 1.0 ml/min, detector: UV270 nm

The measurement was carried out using a solution of 1 ml of a solvent [THF/DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

Further, the H-NMR spectrum of the polymer A was measured, and the measurement conditions were as follows.

Measuring machine: AV400M manufactured by BRUKER BIOSPIN

Magnetic field strength: 400MHz

Reference material: tetramethylsilane (TMS)

Solvent: DMSO

Table 1 shows that, in the obtained NMR spectrum, a value obtained by [integral value of peak (A)] ÷ [integral value of peak (B)] × 100 is taken as an integral value with respect to the peak (B). The ratio of the integral value of the spike (A).

In the formula, the peak (A) is a peak indicating a hydrogen atom bonded to a carbon atom adjacent to a carbon atom to which an amine group of the terminal group is bonded. The peak (B) is a peak of a hydrogen atom possessed by a guanamine bond in the polyimide precursor.

Further, the ratio of the integral value of the peak (A) with respect to the integral value of the peak (B) reflects the ratio of the amine group of the terminal group in the polymer A.

Synthesis Example 2~7 [Synthesis of Polymer B~I]

The polyimine precursor (polymer B~I) was synthesized in the same manner as in Synthesis Example 1, except that the amounts of the amine, the acid, and the NMP were changed as shown in Table 1, and the amine and the acid were used in the same manner as the polymer A. Ingredients. Further, the ratio of the weight average molecular weight (Mw) and the integral value of the peak (A) with respect to the integral value of the peak (B) was determined in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Example 1 [Production of hardened film]

The polymer A solution (resin composition) was filtered using a 5 μm filter (manufactured by Millipore Corporation, SLLS025NS).

The obtained resin composition was spin-coated on a tantalum wafer, dried at 110 ° C for 3 minutes, and dried at 140 ° C for 3 minutes to form a resin film having a film thickness of 10 μm. Further, the resin film is heated in an inert gas oven under a nitrogen atmosphere to obtain a film thickness. 5 μm cured film (polyimine molded body).

The heating conditions by an inert gas oven are as follows.

Device: Inert gas oven manufactured by KOYO THERMO SYSTEMS Co., Ltd.

Condition: Temperature rise Room temperature ~ 200 ° C (5 ° C / min)

Maintain 200 ° C (30 minutes)

Temperature rise 200 ° C ~ 375 ° C (5 ° C / min)

Maintain 375 ° C (60 minutes)

Cooling 375 ° C ~ room temperature (60 minutes)

[Tg, CTE, α ₂ and evaluation of elongation at break]

Next, using a 4.9% by mass aqueous hydrofluoric acid solution, the cured film was peeled off from the tantalum wafer, and after washing with water, drying, measurement of glass transition temperature (Tg), coefficient of thermal expansion (CTE), and temperature higher than Tg were carried out. Thermal expansion rate (α ₂ ), elongation at break.

Fig. 2 is a schematic view showing a thermal expansion curve of a cured polyimine product at a fixed temperature increase rate. Tg is the temperature at the intersection of the tangent a and the tangent b, CTE is the slope of the tangent b, and α ₂ is the slope of the tangent a.

In this example, TMA/SS6000 manufactured by Seiko Instruments Inc. was used, and the load was 10 g, the measurement temperature was 23 ° C to 500 ° C, and the temperature increase rate was 5 ° C / min. According to the inflection point of thermal expansion, it was automatically Tg, CTE, and α _{2 were obtained} . The elongation at break was determined by a tensile test at room temperature (15 ° C to 30 ° C) using an autostereoscopic round gauge AGS-100NH manufactured by Shimadzu Corporation.

Example 2~5, Comparative Example 1~4

The resin composition and the cured film were produced and evaluated in the same manner as in Example 1 except that the kind of the polymer and the amount of the solvent (NMP, water) were changed as shown in Table 1. The results are shown in Table 1.

As shown in Examples 1 to 5, in the case of using a polyimine precursor having a ratio of the integral value of the peak (A) with respect to the integral value of the peak (B) of 3% to 8%, it exhibited good. Tg, CTE, α ₂ , elongation at break.

On the other hand, as shown in Comparative Example 1 or Comparative Example 2, in the case where the ratio of the integral value of the peak (A) with respect to the integral value of the peak (B) is more than 8%, the Tg is low and the fracture is broken. The elongation also decreases. As shown in Comparative Example 2 or Comparative Example 3, when the ratio of the integral value of the peak (A) with respect to the integral value of the peak (B) is less than 3%, α ₂ becomes large.

As described above, the polyimine molded article using the resin composition of the present example has a high Tg, low α ₂ , and even low CTE, and is excellent in mechanical properties.

Since the polyimine molded article of the present example has a high Tg and a low α ₂ , a multilayer wiring structure is formed by forming an inorganic layer on a polyimide polyimide at a temperature higher than Tg. Next, deformation and positional deviation of the polyimide body formed by thermal expansion can be prevented.

[industrial use]

The quinone imide molded article of the present invention can be used as a display substrate, a protective film or the like.

The embodiments and/or examples of the present invention have been described in detail above, but those skilled in the art can easily devise these exemplary embodiments without departing from the spirit and scope of the invention. / or the instance applies a variety of changes. Accordingly, these various modifications are included in the scope of the present invention.

The contents of the documents described in the specification and the Japanese application specification which is the basis of the priority of the Paris Convention of the present application are all incorporated herein by reference.

Claims (9)

A polyimine precursor having a structural unit represented by the following formula (I) and having an amine group at a part of a terminal group; representing a carbon atom phase adjacent to a carbon atom to which the amine group is bonded The integral value of the ¹ H-NMR spectral peak (A) of the bonded hydrogen atom is the integral of the ¹ H-NMR spectral peak (B) indicating the hydrogen atom possessed by the indole bond of the polyimide precursor. 3% to 8% of the value; (In the formula (I), A ¹ and A ² each independently represent a benzene ring, two phenyl rings are bonded by a single bond, or two or more aromatic rings are -O-, -S- or -CO- Any of the groups bonded; R ¹ and R ² each independently represent a hydrogen atom or an alkyl group; and A ¹ and A ² may each have a substituent. The polyimine precursor described in claim 1 has a weight average molecular weight of 40,000 to 100,000. A resin composition comprising the polyimine precursor as described in claim 1 or 2 and a solvent. A polyimine imide molded article obtained by heating a resin composition as described in claim 3 of the invention at 250 ° C to 500 ° C. A protective layer comprising the polyimine molded article according to item 4 of the patent application. A semiconductor device having the protective layer as described in claim 5 of the patent application. A method of producing a semiconductor device, comprising: a step of coating a resin composition according to claim 3 of the patent application on the inorganic layer of a substrate having an inorganic layer; and heating the resin composition to obtain a step of forming a polyimide body; and a step of forming an inorganic layer on the polyimide body at a temperature higher than a Tg of the polyimide body. A semiconductor device obtained by the manufacturing method as described in claim 7 of the patent application. A power component or an electronic component having the semiconductor device as described in claim 8 of the patent application.