TW201638657A - Positive photosensitive resin composition, method of manufacturing pattern cured film, interlayer insulation film, covercoat layer or surface protection film, and electronic component - Google Patents

Abstract

Provided is a positive photosensitive resin composition for multi-step thick film patterning that comprises (a) a polybenzoxazole precursor, (b) a photosensitizer, (c) a solvent, and (d) a crosslinking agent, wherein the (b) constituent comprises a compound represented by general formula (1), and wherein, in general formula (1), X represents a residue of a hydroxy compound or an amino compound.

Description

Positive photosensitive resin composition, method for producing patterned cured film, interlayer insulating film, top coat, surface protective film, and electronic parts

The present invention relates to a positive photosensitive resin composition, a method for producing a patterned cured film using the same, an interlayer insulating film, a top coat or a surface protective film, and an electronic component.

At present, a polyimide film having excellent heat resistance, electrical properties, mechanical properties, and the like is used for the surface protective film and the interlayer insulating film of the semiconductor element. In recent years, when a photosensitive polyimide having a photosensitive property imparted to the polyimide itself is used, when the photosensitive polyimide is used, the production step of the patterned cured film can be simplified, and a complicated manufacturing step can be shortened.

In the manufacturing step of the pattern hardening film, an organic solvent such as N-methylpyrrolidone is used in the development step, but from the viewpoint of the environment, it is proposed to be in the polyimide or polyimine precursor. A resin composition in which a diazide naphthoquinone compound is mixed as a sensitizer and developed with an aqueous alkaline solution (see, for example, Patent Document 1 and Patent Document 2).

However, in recent years, the miniaturization of a transistor that brings about a high-performance computer has reached the limit of the law of proportionality, and in order to further improve the performance and speed, it is considered that a technique of laminating a semiconductor element in three dimensions is required. Based on this background, a 3-dimensional package using a Through Silicon Via (TSV), a 2.5-dimensional package using an interposer, or a 2.1-dimensional package is proposed, in which the laminated device structure represented by the packages is subjected to Concern (for example, refer to Non-Patent Document 1).

In a stacked device structure, a multi-die Fanout Wafer Level Packaging is a package that is manufactured by sealing a plurality of wafers together in one package, which is comparable to the fan-out package of the fan-out package previously proposed. (Manufactured by sealing one wafer in one package) It is expected to be low-component and high-performance, and therefore has attracted much attention.

However, in the fabrication of a stacked-element structure typified by a multi-wafer fan-out wafer-level package, in the outermost portion, in addition to the required opening of the line and the gap, the padding required for the wafer is required. The line is open. In the conventional fan-out wafer level package, the thickness of the interlayer insulating film is about 15 μm or less. In contrast, in the multi-wafer fan-out wafer level package, the process of rewiring becomes complicated, and the number of layers of the interlayer insulating film is complicated. The thickness of the interlayer insulating film is increased to 20 μm or more. At this time, the thickness of the scribe line portion is also 20 μm or more. When the photosensitive resin composition is applied as the outermost layer of the interlayer insulating film, a coating film of about 10 μm to 20 μm is formed on the interlayer insulating film which has been formed, but at the same time, the scribe line portion is also filled with the resin, so the scribe line The resin thickness of the portion is 20 μm to 30 μm. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-265520 [Patent Document 2] International Publication No. WO2014/115233 [Non-Patent Document]

[Non-Patent Document 1] "Semiconductor Technology Yearbook 2013 Package/Installation", Nikkei BP, Pages 41 to 50

Even in this case, in order to simplify the process and reduce the cost, when the outermost layer and the gap portion are exposed and developed to be opened, it is necessary to simultaneously open the scribe line portion. Such a multi-stage film thickness patterning (simultaneous development of a plurality of portions having different thicknesses) is extremely difficult, and the resin composition for forming an interlayer insulating film is extremely difficult, and if it is a conventional resin composition, it is dissolved. The contrast is low and cannot correspond to the process.

An object of the present invention is to provide a positive photosensitive resin composition capable of patterning a multi-stage film thickness and a pattern-cured film using the same in the production of a laminated element structure typified by a multi-wafer fan-out wafer level package. Manufacturing methods and electronic components.

The inventors of the present invention used a positive photosensitive resin composition in which a polybenzoxazole precursor and a diazonaphthoquinone compound were combined to evaluate the photosensitivity in the use of a laminated device. As a result, in the photosensitive resin composition in which the specific diazide naphthoquinone compound and the alkali-soluble resin are combined, in particular, sufficient alkali dissolution rate of the scribe line portion cannot be obtained, and the opening can not be obtained in the development time in the practical range. unit. Further, it has been found that in order to increase the alkali dissolution rate of the scribe portion, a high exposure amount outside the practical range is required.

Therefore, the inventors of the present invention have conducted further studies in view of the above problems, and as a result, surprisingly found that a photosensitive resin composition in which a specific diazonaphthoquinone compound and a polybenzoxazole precursor are combined is used. It is possible to realize multi-level film thickness patterning in development time and exposure amount which can also be used in the production of laminated element.

According to the present invention, the following positive photosensitive resin composition or the like can be provided. <1> A positive-type photosensitive resin composition for multi-stage film thickness patterning, comprising (a) a polybenzoxazole precursor, (b) a photosensitizer, (c) a solvent, and (d) a crosslinking agent. The component (b) comprises a compound represented by the following formula (1); (In the formula (1), X represents a residue of a hydroxy compound or an amine compound). <2> A positive photosensitive resin composition comprising (a) a polybenzoxazole precursor, (b) a photosensitizer, (c) a solvent, and (d) a crosslinking agent, wherein the component (b) comprises a compound represented by the following formula (1), wherein the positive photosensitive resin composition is applied to an outermost layer portion of the laminated portion on a substrate including a laminate portion and a scribe portion, and the plan Forming a patterned cured film on the outermost portion on the line portion; [Chemical 2] (In the formula (1), X represents a residue of a hydroxy compound or an amine compound). The positive photosensitive resin composition as described in claim 1 or 2, wherein the component (b) comprises the following general formula (b-1) and the following general formula (b) -2) or a compound represented by the following formula (b-3); [Chemical 3] [Chemical 4] [Chemical 5] (In the general formula (b-1), the general formula (b-2), and the general formula (b-3), R is independently a group represented by the following formula or a hydrogen atom, and not all of the R of each compound are a hydrogen atom. ) [Chem. 6] . The positive photosensitive resin composition according to any one of the above aspects, wherein the component (a) is a compound represented by the following formula (a-1); 7] (wherein, U is a divalent organic group, a single bond, -O-, or -SO ₂ -, and V represents a divalent organic group; wherein any of V or U is an aliphatic group having 1 to 30 carbon atoms; The basis of the structure). The positive photosensitive resin composition according to any one of the above aspects, wherein the component (d) is a compound having a methylol group or an alkoxyalkyl group. <6> A method of producing a pattern-cured film, comprising: applying a positive photosensitive resin composition according to any one of <1> to <5> on a substrate, and drying to form a photosensitive resin a step of exposing the photosensitive resin film to a predetermined pattern; a step of developing the exposed resin film using an alkaline aqueous solution to form a pattern resin film; and heat-treating the pattern resin film step. <7> The method for producing a pattern cured film according to the above aspect, wherein in the step of heat-treating the pattern resin film, the heat treatment temperature is 250 ° C or lower. <8> An interlayer hardening film, a top coat layer, or a surface protective film, which is a pattern cured film of the positive photosensitive resin composition according to any one of <1> to <5>. <9> An electronic component comprising the interlayer insulating film, the top coat layer or the surface protective film as described in <8>.

According to the present invention, it is possible to provide a positive photosensitive resin composition capable of patterning resin layers having different film thicknesses in the line, the gap portion, and the scribe portion at the same time. The positive photosensitive resin composition of the present invention can be suitably used particularly in the production of a laminated element.

Hereinafter, embodiments of the positive photosensitive resin composition of the present invention, a method for producing a pattern cured film using the same, and an electronic component will be described in detail. In addition, the invention is not limited by the following embodiments. In the present specification, "A or B" means that any one of A and B may be included, and both may be included. Further, the materials exemplified below may be used singly or in combination of two or more kinds, unless otherwise specified. Further, in the present specification, when a plurality of substances corresponding to the respective components are present in the composition as a content of each component in the composition, unless otherwise specified, the various substances present in the composition are indicated. Total measurement.

[Resin Composition] The positive photosensitive resin composition of the present invention contains (a) a polybenzoxazole precursor, (b) a photosensitizer, (c) a solvent, and (d) a crosslinking agent, and the (b) The component contains a compound represented by the following formula (1). [化8] (In the formula (1), X represents a residue of a hydroxy compound or an amine compound)

Hereinafter, each component will be described. There are cases in which the components (a), (b), (c), and (d) are abbreviated as follows.

(Component (a): Polybenzoxazole Precursor) The polybenzoxazole precursor is not particularly limited, and it is preferred that the light transmittance of the i-ray used as the light source used in the patterning is high. Therefore, the polybenzoxazole precursor preferably has a structural unit represented by the following formula (a-1). [Chemistry 9] (wherein, U is a divalent organic group, a single bond, -O-, or -SO ₂ -, and V represents a divalent organic group. Among them, either V or U is an aliphatic group having 1 to 30 carbon atoms. Base of structure)

The divalent group of U is preferably a group having an aliphatic chain structure having 1 to 30 carbon atoms, more preferably a group having an aliphatic chain structure having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms. A group comprising an aliphatic chain structure. Further, it is more preferably a group containing a structure represented by the following formula (UV1). [化10] (In the formula (UV1), R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms, and a is an integer of 1 to 30)

Examples of R ¹ and R ² include a methyl group and a trifluoromethyl group. From the viewpoint of transparency of the polybenzoxazole precursor, trifluoromethyl group is preferably used. a is preferably an integer of from 1 to 5.

The divalent group of V is preferably a structure derived from a dicarboxylic acid, and examples of such a raw material dicarboxylic acid include dodecanedioic acid, isophthalic acid, terephthalic acid, and 2,2-bis(4-carboxybenzene). 1,1,1,1,3,3,3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenyl Decane, bis(4-carboxyphenyl)anthracene, 2,2-bis(p-carboxyphenyl)propane, 5-t-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid Formic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like.

Polybenzoxazole is obtained from the polybenzoxazole precursor. The polybenzoxazole precursor is usually developed by an aqueous alkaline solution. Therefore, it is preferably soluble in an aqueous alkaline solution. Examples of the alkaline aqueous solution include an organic ammonium aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, and an organic amine aqueous solution. In general, it is preferred to use a TMAH aqueous solution having a concentration of 2.38 wt%. Therefore, it is preferred that the component (a) is soluble relative to the TMAH aqueous solution.

Further, a reference to the component (a) which is soluble in an aqueous alkaline solution will be described below. The component (a) is dissolved in an arbitrary solvent to prepare a solution, and then spin-coated on a substrate such as a tantalum wafer to form a resin film having a thickness of about 5 μm. This is immersed in any one of a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, and an organic amine aqueous solution at 20 to 25 °C. As a result, when it was dissolved to form a solution, it was judged that the component (a) used was soluble in an aqueous alkaline solution.

The molecular weight of the polymer of the component (a) is preferably from 10,000 to 100,000, more preferably from 15,000 to 100,000, still more preferably from 20,000 to 85,000, in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight is 10,000 or more, the solubility in the alkaline developer tends to be excessively high. When it is 100,000 or less, it tends to have good solubility in a solvent. Further, there is a tendency that the viscosity of the solution is increased and the workability is improved. The weight average molecular weight can be determined by gel permeation chromatography and can be determined by conversion using a standard polystyrene calibration curve.

(Component (b): Photosensitive Agent) The positive photosensitive resin composition of the present invention contains a compound represented by the following formula (1) as the component (b). [11] (In the formula (1), X represents a residue of a hydroxy compound or an amine compound)

The compound represented by the above formula (1) can be, for example, in the presence of a dehydrochlorinating agent by using 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and a hydroxy compound or an amine compound. It is obtained by carrying out a condensation reaction.

The hydroxy compound is not particularly limited, and from the viewpoint of improving the dissolution inhibiting effect of the unexposed portion, hydroquinone, resorcin, pyrogallol, bisphenol A, bis(4-hydroxybenzene) are preferred. Methane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2 , 2',4,4'-tetrahydroxybenzophenone, 2,3,4,2',3'-pentahydroxybenzophenone, 2,3,4,3',4',5'- Hexahydroxybenzophenone, bis(2,3,4-trihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)propane, 4b,5,9b,10-tetrahydro-1, 3,6,8-tetrahydroxy-5,10-dimethylindolo[2,1-a]indole, tris(4-hydroxyphenyl)methane, or tris(4-hydroxyphenyl)ethane.

The amine compound may use p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino group. Diphenylanthracene, 4,4'-diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxyl Benzene, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane , bis(3-amino-4-hydroxyphenyl)fluorene, bis(4-amino-3-hydroxyphenyl)fluorene, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis( 4-amino-3-hydroxyphenyl)hexafluoropropane or the like.

The ratio of the 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride to the hydroxy compound or the amine compound is preferably 1 molar with respect to 1 mol of 1,2-naphthoquinone-2- The diazide-4-sulfonyl chloride is formulated so that the total of the hydroxyl group and the amine group is from 0.5 equivalent to 1 equivalent. A preferred ratio of the dehydrochlorinating agent to 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride is in the range of from 0.95/1 to 1/0.95. The preferred reaction temperature is from 0 ° C to 40 ° C, and the preferred reaction time is from 1 hour to 10 hours.

The reaction solvent for the reaction is a solvent such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether or N-methylpyrrolidone. Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.

In the above, from the viewpoint of high solubility contrast for patterning of a plurality of layers of film thickness, it is particularly preferable to use the following formula (b-1), the following formula (b-2), or the following formula (b-3). The compound represented is the component (b). Further, R in the following formula (b-1), the following formula (b-2) or the following formula (b-3) may be a part of a hydrogen atom.

[化12]

[Chemistry 13]

[Chemistry 14]

The blending amount of the diazonaphthoquinone compound can be appropriately adjusted in consideration of the dissolution contrast and the like. For example, in the case of a thick film, the amount of the diazonaphthoquinone compound is preferably from 1 part by mass to 30 parts by mass per 100 parts by mass of the component (a) from the viewpoint of the formation of the opening pattern. It is more preferably 1 part by mass to 20 parts by mass, still more preferably 5 parts by mass to 15 parts by mass. In the case of the compounding amount, the i-rays reach the bottom of the film, and the exposure to the diazonaphthoquinone compound tends to be sufficient. Further, the component (b) preferably has high compatibility with the component (a).

(Component (c): solvent) Examples of the component (c) include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, and 3 -methyl methoxypropionate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, six Methylphosphoniumamine, cyclobutyl hydrazine, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, and the like. Usually, it is not particularly limited as long as it can sufficiently dissolve other components in the positive photosensitive resin composition. Among them, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and N-methyl-2- are preferably used from the viewpoint of the solubility of each component and the coating property at the time of formation of a resin film. Pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylhydrazine.

The amount of the component (c) is not particularly limited, and is preferably 50 parts by mass to 300 parts by mass, more preferably 100 parts by mass to 200 parts by mass, per 100 parts by mass of the component (a).

(Component (d): Crosslinking agent) (d) Component: After coating, exposing and developing the alignment photosensitive resin composition, the step of heat-treating the pattern resin film may be carried out with polybenzoxazole. The precursor reaction (crosslinking reaction) or the crosslinking agent itself polymerizes. Thereby, even when the resin composition is cured at a relatively low temperature, for example, 250 ° C or lower, good mechanical properties, chemical resistance, and solder resist resistance can be imparted.

It is not particularly limited, and is preferably a compound having an alkoxyalkyl group such as a methylol group or an alkoxymethyl group, an epoxy group, an oxetanyl group or a vinyl ether group. Preferred are the compounds in which the group is bonded to the benzene ring, the melamine resin or the urea resin in which the N position is substituted with a methylol group or an alkoxymethyl group. Further, the compound in which the base bond is bonded to the benzene ring having a phenolic hydroxyl group is more preferable in terms of increasing the dissolution rate of the exposed portion at the time of development and improving the sensitivity.

Among them, from the viewpoint of good sensitivity and stability of the varnish, and prevention of melting of the photosensitive resin film during curing of the photosensitive resin film after pattern formation, it is preferred to have a methylol group or an alkoxyalkyl group. The compound is more preferably a compound having two or more methylol groups or alkoxyalkyl groups.

When the resin composition is cured at a low temperature of 250 ° C or lower as the component (d), in order to obtain a cured film having excellent chemical resistance, a compound represented by the following formula (d-1) is preferred. .

[化15] (wherein R ³ and R ⁴ are each independently an alkyl group having 1 to 30 carbon atoms)

Further, as the component (d), the following compounds are also preferably used. [Chemistry 16]

The amount of the component (d) is preferably from 1 part by mass to 50 parts by mass per 100 parts by mass of the component (a), and more preferably from 5 parts by mass to 40 parts by mass, in order to secure good mechanical properties. From the viewpoint of mechanical properties and photosensitive properties, it is more preferably from 10 parts by mass to 30 parts by mass.

The positive photosensitive resin composition of the present invention may optionally contain a coupling agent, a dissolution promoter, a dissolution inhibitor, a surfactant, a leveling agent, and the like. The positive photosensitive resin composition of the present invention may substantially contain the components (a) to (d). The composition of the present invention may be, for example, 80% by weight or more, 90% by weight or more, or 95% by weight or more of the components (a) to (d).

[Method for Producing Pattern Curing Film] The positive photosensitive resin composition of the present invention can be cured to obtain a cured film (such as a patterned cured film). In the production method of the present invention, the pattern-cured film can be produced by the steps of: applying the positive-type photosensitive resin composition onto a substrate, and drying to form a photosensitive resin film; The step of exposing the photosensitive resin film to a predetermined pattern; the step of developing the exposed resin film using an alkaline aqueous solution to obtain a pattern resin film; and the step of heat-treating the pattern resin film.

(Photosensitive Resin Film Forming Step) Examples of the substrate include a metal oxide insulator such as glass, a semiconductor, TiO ₂ or SiO ₂ , tantalum nitride, copper, or a copper alloy. The coating method is not particularly limited, and it can be carried out using a rotator or the like.

Drying can be carried out using a hot plate, an oven or the like. The heating temperature is preferably from 100 ° C to 150 ° C. The heating time is preferably from 30 seconds to 5 minutes. Thus, a photosensitive resin film in which the positive photosensitive resin composition is formed into a film shape can be obtained. The film thickness of the photosensitive resin film is preferably from 5 μm to 100 μm, more preferably from 8 μm to 50 μm, still more preferably from 10 μm to 30 μm.

(Exposure Step) In the exposure step, it can be exposed to a predetermined pattern via a mask. The active light to be irradiated may be ultraviolet rays, visible rays, radiation, or the like containing i-rays, and is preferably an i-ray. The exposure device can use a parallel exposure machine, a projection exposure machine, a stepper, a scanner, or the like.

(Developing Step) By performing development processing, a resin film (pattern resin film) on which a pattern is formed can be obtained. Usually, when a positive photosensitive resin composition is used, the exposed portion is removed by a developing solution. The alkaline aqueous solution used as the developing solution may, for example, be sodium hydroxide, potassium hydroxide, sodium citrate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine or tetramethylammonium hydroxide. Tetramethylammonium hydroxide. The concentration of the alkaline aqueous solution is preferably from 0.1% by mass to 10% by mass. The development time varies depending on the type of the polymer to be used, and is preferably from 10 seconds to 15 minutes, more preferably from 10 seconds to 5 minutes, and more preferably from 30 seconds to 4 minutes from the viewpoint of productivity.

An alcohol or a surfactant may also be added to the developer. The amount of addition is preferably from 0.01 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass, per 100 parts by mass of the developer.

(Heat Treatment Step) By heat-treating the pattern resin film, a crosslinked structure can be formed between the functional groups of the component (a) or between the component (a) and the component (d) to obtain a pattern-cured film. Further, since the component (a) is a polybenzoxazole precursor, a dehydration ring-closure reaction can be produced by a heat treatment step to prepare a corresponding polybenzoxazole.

The heating temperature is preferably 250 ° C or lower, more preferably 120 ° C to 250 ° C, and still more preferably 160 ° C to 230 ° C. By setting it as the said range, damage to a board|substrate or an element can be suppressed small, and it can manufacture a component with favorable yield, and can implement energy-saving of a process.

The heating time is preferably 5 hours or shorter, more preferably 30 minutes to 3 hours. By setting it as the said range, it can fully carry out a crosslinking reaction or a dehydration ring-closing reaction. Further, the heat treatment environment may be in the atmosphere or in an inert atmosphere such as nitrogen, and is preferably a nitrogen atmosphere from the viewpoint of preventing oxidation of the pattern resin film.

Examples of the apparatus used in the heat treatment step include a quartz tube furnace, a heating plate, a rapid annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[Electronic Parts] The pattern cured film produced by the above method can be used as an interlayer insulating film, a top coat or a surface protective film. By using the interlayer insulating film, the top coat layer, the surface protective film, or the like, it is possible to manufacture electronic parts such as a highly reliable semiconductor device, a multilayer wiring board, and various electronic components.

[Manufacturing Step of Semiconductor Device] Using the method of the present invention, it is possible to manufacture a semiconductor device, particularly a device having a laminated element structure requiring multi-level film thickness patterning. The manufacturing steps of the laminated element structure in which the multi-stage film thickness is patterned are exemplified in (1-1) to (1-4) of Fig. 1 .

The positive photosensitive resin composition 50 is applied to the substrate 10 including the rewiring layer 20, the interlayer insulating film 30, and the scribe line 40, and dried to form a photosensitive resin film. (1-2) The obtained photosensitive resin film 50 is exposed to a predetermined pattern. The exposed resin film is developed with a developing solution (1-3) of FIG. 1 , and the patterned resin film obtained by the development is subjected to heat treatment, and then the conductive bump 60 is mounted (1-4) of FIG. 1 . Thereby, a package having a multi-layer film thickness patterning and having a laminated element structure can be manufactured. In (1-1) to (1-4) of FIG. 1, the rewiring layer 20 and the interlayer insulating film 30 are used as a laminated portion, but other laminated portions include a PoP structure and the like.

In this package, the Under Bump Metal (UBM) may not be used at the connection portion between the conductive bump and the rewiring. When the UBM is not used, the outermost pattern resin film ensures reliability by reinforcing the bumps, and therefore it is preferable to make the thickness of the outermost layer thicker than the conventional film thickness (7 μm or less).

By using the positive photosensitive resin composition of the present invention, the opening for mounting the conductive bumps and the scribe portion can be simultaneously opened by one development, so that the semiconductor device can be manufactured without a complicated forming process.

The semiconductor device is an embodiment of the electronic component of the present invention, but is not limited to the above, and various configurations can be employed. [Examples]

Hereinafter, the present invention will be further specifically described based on examples and comparative examples. Further, the present invention is not limited to the following examples.

[(a) Component: Synthesis of Polybenzoxazole Precursor] <Synthesis Example 1> A 0.2 liter flask equipped with a stirrer and a thermometer was charged with 60 g of N-methylpyrrolidone, and 13.92 g (38 mmol) was added. 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved by stirring. Then, while maintaining the temperature at 0 ° C to 5 ° C, 10.69 g (40 mmol) of dodecanedioxine was added dropwise over 10 minutes, and then the solution in the flask was stirred for 60 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then decompressed to obtain polyhydroxyguanamine (polybenzoxazole precursor) (hereinafter referred to as polymer I). ). The weight average molecular weight of the polymer I (determined by standard polystyrene conversion by Gel Permeation Chromatography (GPC) method) was 33,100, and the degree of dispersion was 2.0.

In addition, the measurement conditions of the weight average molecular weight of the GPC method are as follows. The measurement was carried out using a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] of 1 ml with respect to 0.5 mg of the polymer. Measuring device: L4000 UV pump manufactured by Hitachi, Ltd.: L6000 manufactured by Hitachi, Ltd. C-R4A Chromatopac manufactured by Shimadzu Corporation Ltd. Measurement conditions: Glue Pack GL-S300MDT-5×2 Dissolution 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

<Synthesis Example 2> A 0.2 liter flask equipped with a stirrer and a thermometer was charged with 60 g of N-methylpyrrolidone, and 13.92 g (38 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl group) was added. Hexafluoropropane is stirred and dissolved. Then, while maintaining the temperature at 0 ° C to 5 ° C, 11.86 g (40 mmol) of 4,4'-diphenyl ether dicarboxymethane chloride was added dropwise over 10 minutes, and then the solution was returned to room temperature. Stir for 3 hours. The solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then decompressed to obtain polyhydroxyguanamine (hereinafter referred to as polymer II). The polymer II had a weight average molecular weight of 22,400 and a degree of dispersion of 3.2.

<Synthesis Example 3> 10.69 g (40 mmol) of dodecanedioxin chloride used in Synthesis Example 1 was replaced with 7.48 g (28 mmol) of dodecanedioxin chloride and 3.56 g (12 mmol) of 4,4'. The synthesis was carried out in the same manner as in Synthesis Example 1 except that the diphenyl ether dicarboxymethyl chloride was used, and polyhydroxyguanamine (hereinafter referred to as polymer III) was obtained. The polymer III had a weight average molecular weight of 41,800 and a degree of dispersion of 2.0.

<Examples 1 to 14 and Comparative Examples 1 to 11> The components 1 and 14 and Comparative Examples 1 to 11 of Examples 1 to 14 were prepared by the components and the amounts shown in Tables 1 and 2. A positive photosensitive resin composition. The blending amounts of Tables 1 and 2 are parts by mass relative to the components of 100 parts by mass of the polybenzoxazole (PBO) precursor. In addition, each component used is as follows.

[Polybenzoxazole precursor] Polymer I: Polymer I obtained in Synthesis Example 1 (component (a)) Polymer II: Polymer II obtained in Synthesis Example 2 (component (a)) Polymer III : Polymer III obtained in Synthesis Example 3 ((a) component)

[Photosensitive agent] (b-1): a compound having the following structure (manufactured by Daito Chemix Co., Ltd., trade name "TPPA428") (component (b)) [Chem. 17] (b-2): a compound having the following structure (manufactured by Daito Chemix Co., Ltd., trade name "HA4-200") (component (b)) [Chem. 18] (b-3): a compound having the following structure (manufactured by Daito Chemix Co., Ltd., trade name "TKP4-400") (component (b)) [Chem. 19] (b-4): a compound having the following structure (manufactured by Daito Chemix Co., Ltd., trade name "TPPA528") [Chem. 20]

[Solvent] BLO: γ-butyrolactone ((c) component) NMP: N-methylpyrrolidone (component (c))

[Crosslinking agent] (d-1): 1,3,4,6-tetrakis(methoxymethyl)glycolide having the following structure (manufactured by Sanwa Chemical Co., Ltd., trade name "MX-270" ) ((d) component) [Chem. 21] (d-2): "NIKALAC MX-280" (manufactured by Sanwa Chemical Co., Ltd., trade name) ((d) component) [Chem. 22]

<Evaluation of Dissolution Rate and Dissolution Contrast> The positive photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 7 were prepared from the components and the amounts shown in Table 1. Each of the positive photosensitive resin compositions was spin-coated on a ruthenium substrate, and dried at 120 ° C for 3 minutes to form a photosensitive resin film having a film thickness of 10 μm after drying. The obtained photosensitive resin film was exposed to an exposure beam using a proximity exposure apparatus (manufactured by Ngau Electric Co., Ltd., trade name "UX-1000SM-XJ01"), and an i-ray of 600 mJ/cm ^{2 was used} . The irradiation is a prescribed pattern. After the exposure, development was carried out at 23 ° C by a 2.38 mass% aqueous solution of TMAH (the development time required in each case was taken as the respective development time) until the ruthenium substrate of the exposed portion was exposed, and then rinsed with water. A patterned resin film was obtained.

The value obtained by dividing the film thickness after drying by the development time was taken as the exposure speed of the exposure portion. Exposure speed of exposure section (nm/s) = film thickness after drying/development time A case where the exposure portion dissolution rate is 100 nm/s or more is referred to as A, and a case where the exposure portion is slower than 100 nm/s is referred to as B.

Then, the film thickness of the unexposed portion after development was measured, and the film thickness of the unexposed portion after development was subtracted from the film thickness after drying, and the development time was divided to determine the dissolution rate of the unexposed portion. Undissolved part dissolution rate (nm/s) = (thickness after drying - film thickness of unexposed part after development) / development time When the unexposed part dissolution rate is 20 nm/s or less, the ratio is A, and the ratio is 20 nm. The case where /s is fast and is 50 nm/s or less is B, and the case where it is faster than 50 nm/s is taken as C.

Further, the dissolution contrast can be obtained by dividing the exposure portion dissolution rate by the unexposed portion dissolution rate. Dissolution contrast = exposure portion dissolution rate / unexposed portion dissolution rate The dissolution contrast ratio is 8 or more as A, 5 or more and less than 8 as B, and less than 5 as C. The results are shown in Table 1.

[Table 1] The pattern resin film was heat-treated at 200 ° C for 1 hour, and as a result, a good pattern cured film was obtained.

<Evaluation of the Resolution of the Film Thickness of 12 μm> The positive photosensitive resin compositions of Example 13, Example 14, and Comparative Example 8 to Comparative Example 11 were prepared from the components and the amounts shown in Table 2. Using each of the positive photosensitive resin compositions, the film thickness after drying was set to 12 μm, the exposure amount was set to 800 mJ/cm ² , and the development time was set so that the residual film ratio of each unexposed portion was about 75%. The resolution of the pattern resin film was evaluated by exposure and development. Remaining film ratio (%) of the unexposed portion = film thickness (μm) after development / film thickness (μm) before development × 100 in the pattern resin film by a digital microscope (manufactured by KEYENCE Co., Ltd., trade name "VHX-100F") Observe the line and gap pattern with a line width of 20 μm to check for the presence or absence of scum. The case where the scum can be patterned is referred to as A, and the case where scum is present is referred to as B. The results are shown in Table 2.

<Evaluation of opening of the scribe line equivalent portion> The film thickness after drying was set to 20 μm, and the exposure amount was set to 800 mJ/cm ² , which was the same as the development time used for the evaluation of the resolution in the film thickness portion of 12 μm. The development time was subjected to exposure and development, whereby the opening evaluation of the scribe line equivalent portion having a film thickness of 20 μm was performed. In the pattern resin film, a scribe line having a line width of 100 μm was observed by a digital microscope (manufactured by KEYENCE Co., Ltd., trade name "VHX-100F") to confirm the presence or absence of scum. The case where the scum can be patterned is referred to as A, and the case where scum is present is referred to as B. The results are shown in Table 2.

[Table 2]

The pattern resin film was heat-treated at 200 ° C for 1 hour, and as a result, a good pattern cured film was obtained. [Industrial availability]

The photosensitive resin composition of the present invention can be used in electronic devices such as semiconductor devices, multilayer wiring boards, and various electronic components.

The embodiments and/or embodiments of the present invention have been described in detail above, but those skilled in the art will not be able to practice the embodiments and/or The embodiment is subject to various modifications. 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 Paris priority of the present application are all incorporated in the specification.

10‧‧‧Substrate
20‧‧‧Rewiring layer
30‧‧‧Interlayer insulating film
40‧‧‧Drawing Department
50‧‧‧Photosensitive resin film
60‧‧‧ Conductive bumps

(1-1) to (1-4) of FIG. 1 are views showing a manufacturing procedure of a laminated element structure using multi-stage film thickness patterning according to an embodiment of the method of the present invention.

10‧‧‧Substrate

20‧‧‧Rewiring layer

30‧‧‧Interlayer insulating film

40‧‧‧Drawing Department

50‧‧‧Photosensitive resin film

60‧‧‧ Conductive bumps

Claims (9)

A positive-type photosensitive resin composition for multi-stage film thickness patterning, comprising (a) a polybenzoxazole precursor, (b) a sensitizer, (c) a solvent, and (d) a crosslinking agent, said ( b) the component comprises a compound represented by the following formula (1); (In the formula (1), X represents a residue of a hydroxy compound or an amine compound). A positive photosensitive resin composition comprising (a) a polybenzoxazole precursor, (b) a sensitizer, (c) a solvent, and (d) a crosslinking agent, wherein the component (b) comprises the following a compound represented by the formula (1), wherein the positive photosensitive resin composition is applied to an outermost layer portion of the laminated portion and the scribe line portion on a substrate including a laminate portion and a scribe portion. Forming a patterned cured film on the outermost portion; (In the formula (1), X represents a residue of a hydroxy compound or an amine compound). The positive photosensitive resin composition according to claim 1 or 2, wherein the component (b) comprises the following general formula (b-1) and the following general formula (b-2); Or a compound represented by the following formula (b-3); (In the general formula (b-1), the general formula (b-2), and the general formula (b-3), R is independently a group represented by the following formula or a hydrogen atom, and not all of the R of each compound are a hydrogen atom. ) . The positive photosensitive resin composition according to claim 1 or 2, wherein the component (a) has a structural unit represented by the following formula (a-1); (wherein, U is a divalent organic group, a single bond, -O-, or -SO ₂ -, and V represents a divalent organic group; wherein any of V or U is an aliphatic group having 1 to 30 carbon atoms; The basis of the structure). The positive photosensitive resin composition according to claim 1 or 2, wherein the component (d) is a compound having a methylol group or an alkoxyalkyl group. A method for producing a patterned cured film, comprising: applying a positive photosensitive resin composition according to any one of items 1 to 5 to a substrate, and drying to form a photosensitive resin a step of exposing the photosensitive resin film to a predetermined pattern; a step of developing the exposed resin film using an alkaline aqueous solution to form a pattern resin film; and heat-treating the pattern resin film step. The method for producing a patterned cured film according to claim 6, wherein in the step of heat-treating the patterned resin film, the heat treatment temperature is 250 ° C or lower. An interlayer insulating film, a top coat, or a surface protective film using the pattern-cured film of the positive photosensitive resin composition according to any one of the above-mentioned items of the first aspect of the invention. An electronic component comprising the interlayer insulating film, top coat or surface protective film as described in claim 8 of the patent application.