TWI477906B - Negative photosensitive resin composition, method of forming pattern and electronic part - Google Patents

Description

Negative film type photosensitive resin composition, pattern manufacturing method, and electronic part

The present invention relates to a negative-type photosensitive resin composition containing a photosensitive heat-resistant polymer, a pattern production method using the same, and an electronic component.

Conventionally, in a surface protective film or an interlayer insulating film of a semiconductor element, a polyimide resin having excellent heat resistance, electrical properties, mechanical properties, and the like is used. However, with the recent development of high integration and large-scale semiconductor devices, it is required to reduce the thickness and size of the sealing resin package, and to use lead on chip (LOC) or reflow soldering ( The surface mounting of soldering reflow, etc., whereby the resin used requires a polyimide resin having more excellent mechanical properties and heat resistance than before.

On the other hand, when the polyimide polyimide is used in itself, the photosensitive polyimide which imparts the photosensitive property is used, and if it is used, it is characterized in that the pattern forming step can be simplified and the troublesome manufacturing steps can be shortened. It is known that a heat-resistant photoresist formed using a conventional photosensitive polyimide or a precursor thereof is excellent in use. In the negative film type, there is a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, refer to Japanese Patent Laid-Open No. SHO 49-11541, Japanese Patent Laid-Open No. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. 59-108031, Japanese Patent Laid-Open No. Sho 59-220730, Japanese Patent Laid-Open No. Hei 69-232122, Japanese Patent Laid-Open No. Hei 60-6729, and Japanese Patent Laid-Open No. US Pat. No. 60-72925, Japanese Patent Application Laid-Open No. SHO 61-57620, and a benzophenone skeleton having an ortho group having an alkyl group bonded to a nitrogen atom. The self-sensitized polyimine (see, for example, JP-A-59-219330, JP-A-59-231633, JP-A-59-231633).

In the above-mentioned negative film type, since an organic solvent such as N-methylpyrrolidone is required for development, a positive-working photosensitive resin which can be developed in an alkaline aqueous solution has recently been proposed. In the positive type, there is a method of introducing o-nitrobenzyl to a polyimine precursor via an ester bond (for example, refer to J. Macromol. Sci. Chem., A24, 10, 1407, 1987); A method in which a naphthoquinone diazide compound is mixed with a soluble hydroxy quinone or a polyoxazole precursor (for example, refer to Japanese Patent Publication No. Sho 64-θ0630, No. 4,395, 482); A method of introducing a diazonaphthoquinone into a soluble polyimine by an ester bond (for example, refer to Macromolecu.les, 23, 1990); and mixing a diazonaphthoquinone with a polyimine precursor (for example, refer to Japanese Patent Laid-Open) Japanese Patent Publication No. 52-13315).

However, the above-mentioned negative film type has problems in terms of its function and resolution, or there are problems such as a decrease in yield at the time of manufacture depending on the use. Further, since the polymer structure used in the above is limited, the properties of the finally obtained film are limited and cannot be applied to various uses. another On the other hand, in the positive type, the same problem arises because the sensitivity and the resolution are lowered due to the problem of the absorption wavelength of the sensitizer as described above, or the structure is limited.

Further, there is a method in which a diazonaphthoquinone compound is mixed with a polybenzoxazole precursor (for example, refer to Japanese Patent Laid-Open No. Hei 1-468686), or a phenol moiety is introduced into a polyamine via an ester bond. In place of a carboxylic acid, a phenolic hydroxyl group is introduced in place of a carboxylic acid, for example, the acidity is not sufficient, and the film loss of the unexposed portion or the peeling of the resin substrate is caused. . Further, there has been proposed a polylysine having a oxime moiety in a mixed polymer skeleton for the purpose of improving such developability or the like (for example, refer to Japanese Patent Laid-Open No. Hei 4-31861, Japanese Patent No. Hei. Japanese Patent Publication No. 4-46345), however, the storage stability is deteriorated by the use of polyamic acid as described above. In addition, it has been proposed to block the amine terminal group by a polymerizable group for the purpose of improving the storage stability and the purpose of the following (for example, Japanese Patent Laid-Open No. Hei 5-197153, Japanese Patent Laid-Open No. Hei 9-183846, Japanese Patent Laid-Open Publication No. 2001-183835, which uses a diazoquinone compound containing a plurality of aromatic rings as an acid generator, so that sensitivity is low and weight must be increased Since the amount of the nitrogen ruthenium compound added is such a problem that the mechanical properties after heat hardening are remarkably lowered, it is difficult to use it as a practical standard material.

In order to improve the above problem of the diazonium compound, various chemical amplification systems have also been proposed. A chemically amplified polyimine (for example, refer to Japanese Patent Laid-Open No. Hei 3-763), a chemically amplified polyimine or A polybenzoxazole precursor (for example, Japanese Patent Laid-Open No. Hei-50-40922, Japanese Patent Laid-Open Publication No. SHO 54-145794, Japanese Patent Laid-Open No. Hei 56-38038, and Japanese Patent Laid-Open No. 59 Japanese Patent Laid-Open No. 59-220730, Japanese Patent Laid-Open No. SHO-69-232122, Japanese Patent Laid-Open Publication No. SHO-60-6729, Japanese Patent Laid-Open No. Hei 60-72925, Japan JP-A-61-57620, JP-A-59-219330, JP-A-59-231633, JP-A-63-θ0630, and US Pat. No. 4,395,482, Japan Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. Japanese Patent Laid-Open No. Hei 5-197153, Japanese Patent Laid-Open No. Hei 9-183846, Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei No. Hei. No. Hei. Japanese patent special Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No.), but it can be seen that the low-molecular weight of these high-sensitivity materials leads to a decrease in film properties, and those having excellent film properties may cause insufficient solubility and cause a decrease in sensitivity, and it is difficult to become a practical standard material. . Further, it is also proposed to use a negative-type chemical amplification system which utilizes a crosslinking reaction under the presence of an acid catalyst (for example, refer to the above-mentioned Japanese Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. 2001-125267, but the hydroxyl group in the molecular chain becomes a crosslinking point. Actually, the crosslinking reaction efficiency is low and high sensitivity cannot be obtained. As a result, there is a problem that the status quo is insufficient for practical standards.

The present invention has been made to solve the above problems, and provides a heat-resistant negative-type photosensitive resin composition having excellent sensitivity and resolution.

Further, in the present invention, by using the above composition, a pattern producing method which is excellent in sensitivity, resolution, and heat resistance and has a pattern having a good shape can be provided. Further, the present invention provides an electronic component having high reliability by a pattern having good shape and characteristics.

That is, the negative-type photosensitive resin composition of the present invention is a compound containing (a) a heat-resistant polymer, (b) an acid generated by irradiation of active light, and (c) crosslinking by polymerization or polymerization. a crosslinking agent characterized in that: (c) a crosslinking agent which is crosslinked or polymerized by an acid action, and contains at least one methylol group or alkoxy alkyl group in the molecule. Compound.

Further, the negative-type photosensitive resin composition of the present invention is characterized in that the (c) crosslinking agent which is crosslinked or polymerized by an acid action is a compound represented by the formula (I).

(wherein, X represents a single bond or a 1 to 4 valent organic group; and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group; n is an integer of 1 to 4; and p and q are each independently 0. An integer of 4.)

Further, the negative-type photosensitive resin composition of the present invention is characterized in that the (c) crosslinking agent which is crosslinked or polymerized by an acid action is a compound represented by the formula (II).

(wherein, two Y are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may further contain an oxygen atom or a fluorine atom; and R ³ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group; m Independently with z is an integer from 1 to 3; x and y are each independently an integer from 1 to 3.)

Further, the negative-type photosensitive resin composition of the present invention is characterized in that the (c) crosslinking agent which is crosslinked or polymerized by an acid action is a compound represented by the formula (III).

(wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent organic group.)

Moreover, the negative-type photosensitive resin composition of the present invention is characterized in that the (a) heat-resistant polymer is polyimine, polyoxazole or a precursor thereof.

Moreover, the method for producing a pattern of the present invention includes a step of applying the negative-type photosensitive resin composition onto a support substrate and drying the film, and exposing the photosensitive resin film obtained by the drying step; a step of heating the photosensitive resin film after the exposure; a step of developing the heated photosensitive resin film using an alkaline aqueous solution; and a step of heat-treating the developed photosensitive resin film.

Moreover, the electronic component of the present invention includes an electronic component having a pattern layer obtained by the method of pattern formation described above, wherein the pattern layer is provided in the electronic component as An interlayer insulating layer and/or a surface protective layer.

The negative-type photosensitive resin composition of the present invention has excellent sensitivity, resolution, and heat resistance.

Further, according to the method for producing a pattern of the present invention, by using the above composition, a pattern having excellent sensitivity, resolution, and heat resistance and having a good shape can be obtained.

Further, the electronic component of the present invention has good shape and characteristics The pattern is higher and the reliability is higher.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The negative-type photosensitive resin composition of the present invention, the method for producing the pattern, and the embodiment of the electronic component will be described in detail based on the drawings. Further, the present invention is not limited by the embodiment.

[Negative sheet type photosensitive resin composition]

The negative-type photosensitive resin composition of the present invention contains: (a) a heat-resistant polymer, (b) a compound which generates an acid by irradiation with active light, and (c) a crosslinking or polymerization by an acid action in the molecule. A compound having a methylol group or an alkoxy alkyl group.

In this way, it is possible to provide a heat-resistant negative-type photosensitive resin composition which can sufficiently cope with any structure even if the heat-resistant polymer which imparts photosensitivity is provided, and which has good sensitivity and resolution.

In the case of the heat resistant polymer (a) of the present invention, it is not particularly limited in structure. The (a) heat-resistant polymer may, for example, be a polymethyleneimine, a polyoxazole, or a polymer compound known from such precursors, which has, for example, good workability and heat resistance. It is also possible to use a copolymer or a mixture of two or more of the above.

The molecular weight of the component (a) of the heat resistant polymer is preferably from 3,000 to 200,000, more preferably from 5,000 to 100,000. This molecular weight is a value obtained by a gel permeation Chromatography (GPC) method and converted according to a standard polystyrene calibration curve.

The amount of the compound (hereinafter referred to as an acid generator) which generates an acid by irradiation with active light as the component (b) of the composition of the present invention, in order to obtain a good sensitivity and resolution in the case of light-sensing, relative to 100 The component (a) by weight is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 20 parts by weight, still more preferably 0.5 to 20 parts by weight.

The acid generator (b) which is a compound which generates an acid by irradiation with active light as used in the present invention can be made acidic by irradiation with an active light such as ultraviolet rays, and has a component (c) by the action The polyamine derivative as the component (a) is crosslinked or the component (c) is polymerized with each other. (b) component compounds can be specifically used: diaryl sulfonium salt, triaryl sulfonium salt, dialkyl phenacyl sulfonium salt, two Diaryl iodonium salt, alkyl diazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonate, nitrobenzyl ester, oxime sulfonic acid ester , aromatic N-oxo imine sulfonate, aromatic sulphamide, hydrocarbon compound containing a halogenated alkyl group, heterocyclic compound containing a halogenated alkyl group, diazonaphthoquinone-4-sulfonate, etc. . The above compounds may be used in combination of two or more kinds as needed or in combination with other sensitizers. Among them, an aromatic oxime sulfonate and an aromatic N-oxyindenine sulfonate are preferred because of their high effect in terms of high sensitivity.

(c) Crosslinking or crosslinking by acid action used in the present invention The agent is not particularly limited as long as it has at least one methylol group or alkoxyalkyl group in the molecule, but it is preferred to have two or more methylol groups or alkoxy groups in the molecule. And a melamine resin or a urea resin in which the group is bonded to a benzene ring or a melamine resin substituted with a methylol group and/or an alkoxymethyl group at the N position. The compounds which can be used in the present invention are not particularly limited, and among them, those exemplified by the following general formulae (I) and (III) have excellent sensitivity and prevent the effect of melting at the time of exposure of the exposed portion, and The balance of the properties of the cured film is excellent. In particular, those represented by the following general formula (I) can effectively improve the mechanical properties of the cured film, and those having the following general formula (III) have excellent sensitivity.

(wherein, X represents a single bond or a 1 to 4 valent organic group, and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, n represents an integer of 1 to 4, and p and q each independently represent 0 to 4 integer).

(wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent organic group).

In the general formula (I), the organic group represented by X may, for example, be an alkylene group having a carbon number of 1 to 10 such as a methylene group, an exoethyl group or a propyl group; or a carbon number such as an ethylene group 2~ An alkylene group; a aryl group having 6 to 30 carbon atoms; a part or all of a hydrogen atom of the hydrocarbon group substituted with a halogen atom such as a fluorine atom; a sulfo group, a carbonyl group, an ether bond, or a thioether; Further, as a bond, a guanamine bond or the like, a divalent organic group represented by the following formula (IV) is preferred.

(wherein each X' is independently selected from a single bond, an alkylene group (for example, a carbon number of 1 to 10), an alkylene group (for example, a carbon number of 2 to 10), or the like. a part or all of a group substituted with a halogen atom, a sulfo group, a carbonyl group, an ether bond, a thioether bond, a guanamine bond or the like; and R ⁹ is a hydrogen atom, a hydroxyl group, an alkyl group or a halogenated alkyl group, and in the case of a plurality of cases, They can be the same or different; m is 1~10.).

Further, those enumerated in the following general formula (II) have excellent sensitivity and resolution, and therefore are particularly preferable.

(wherein, two Y are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may contain an oxygen atom or a fluorine atom, and R ³ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, m and z independently represents an integer from 1 to 3, and x and y respectively represent integers from 1 to 3)

Specifically, Y includes an alkoxy group or the like containing an oxygen atom, and a perfluoroalkyl group or the like containing a fluorine atom. Further, specific examples of the organic group of R ⁵ and R ^{6 include} the following typical examples: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group and the like, but not Limited to this. In the general formulae (I) and (II), those represented by the following chemical formula (V) can be mentioned.

Further, in the general formula (III), the sensitivity is further preferably those exemplified in the following general formula (VI).

(wherein Z represents a monovalent alkyl group having 1 to 10 carbon atoms).

The amount of the component (c) which is a crosslinking agent used in the present invention is preferably such that the sensitivity and the resolution at the time of light absorption are increased, and the pattern melting at the time of curing is suppressed, and it is preferably 100 parts by weight of the component (a). 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, still more preferably 0.5 to 20 parts by weight.

The negative-type photosensitive resin composition of the present invention may contain an organic decane compound, an aluminum chelate compound, or the like in order to improve adhesion to the cured film substrate. Examples of the organic decane compound include vinyl triethoxysilane, γ-glycidoxypropyl triethoxy decane, γ-methyl propylene oxypropyl trimethoxy decane, and urea. Propyltriethoxydecane, methylphenyldecanediol, B Phenyl decane diol, n-propyl phenyl decane diol, isopropyl phenyl decane diol, n-butyl phenyl decane diol, isobutyl phenyl decane diol, tert-butyl phenyl decane Glycol, diphenyldecanediol, ethylmethylphenylstanol, n-propylmethylphenylstanol, isopropylmethylphenylstanol, n-butylmethylphenylstanol, isobutylmethyl Phenyl stanol, tert-butyl methyl phenyl stanol, ethyl n-propyl phenyl decyl alcohol, ethyl isopropyl phenyl stanol, n-butyl ethyl phenyl stanol, isobutyl ethyl benzene Base stanol, third ethyl phenyl decyl alcohol, methyl diphenyl decyl alcohol, ethyl diphenyl stanol, n-propyl diphenyl stanol, isopropyl diphenyl stanol, n-butyl Diphenyl decyl alcohol, isobutyl diphenyl decyl alcohol, tert-butyl diphenyl decyl alcohol, phenyl decane triol, 1,4-bis(trihydroxy decyl) benzene, 1,4-double (Methyldihydroxydecyl)benzene, 1,4-bis(ethyldihydroxydecyl)benzene, 1,4-bis(propyldihydroxydecyl)benzene, 1,4-bis(butyldihydroxy)矽alkyl)benzene, 1,4-bis(dimethyl Base alkyl)benzene, 1,4-bis(diethylhydroxydecyl)benzene, 1,4-bis(dipropylhydroxydecyl)benzene, 1,4-bis(dibutylhydroxydecyl)benzene Wait. Examples of the aluminum chelate compound include aluminum triacetylacetonate and diisopropyl aluminum acetate. When such a tackifier is used, it is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (a).

Further, in the negative-type photosensitive resin composition of the present invention, a suitable surfactant or a leveling agent can be added for improving the coating property, for example, preventing streaks (uneven film thickness) and improving developability. Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether (polyoxyethylene). Laurylether), polyoxyethylene stearyl ether, polyoxyethylene ether ether, polyoxyethylene octylphenol ether, etc., and the above-mentioned commercial products include: Megafax F171, F173, R-08 (Daily Ink Chemical Industry Co., Ltd.) Product name), Fluorad FC430, FC431 (trade name of Sumitomo three-m Co., Ltd.), organic siloxane polymer KP341, KBM303, KBM403, KBM803 (trade name manufactured by Shin-Etsu Chemical Co., Ltd.).

In the present invention, these components are dissolved in a solvent and used in the form of a varnish. The solvent may, for example, be N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide or 2-methoxyethanol. (methoxyethanol), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate (methyl Lactate), ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, 1,3-butanediol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran , THF), etc., may be used singly or in combination.

[Method of manufacturing pattern]

Next, a method of manufacturing the pattern of the present invention will be described. The method for producing a pattern of the present invention comprises the steps of: applying a negative-type photosensitive resin composition of the present invention to a support substrate for drying; performing an exposure step; and heating the exposed photosensitive resin film; a step of developing the above-mentioned heated photosensitive resin film in an aqueous alkaline solution; and a step of heat-treating the developed photosensitive resin film. through Through the above steps, a desired heat resistant polymer pattern can be formed.

In the step of drying on the support substrate, the photosensitive resin composition is spin-coated on a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _{2 ,} etc.) or tantalum nitride using a spinner or the like. After supporting the substrate, it is dried using a hot plate, an oven, or the like.

Next, in the exposure step, the photosensitive resin composition which is a film on the support substrate is irradiated with active light such as ultraviolet rays, visible rays, or radiation through a mask. In the developing step, a pattern is obtained by removing the exposed portion with a developing solution. Preferred developing solutions include alkaline salts such as sodium hydroxide, potassium hydroxide, sodium citrate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (Tetramethyl Ammonium Hydroxide). Aqueous solution. It is preferred to set the alkali concentration of the above aqueous solvent solution to 0.1 to 10% by weight (wt%). Further, an alcohol or a surfactant may be added to the developer to be used. These are preferably added in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.

Next, in the heat treatment step, it is preferred to subject the obtained pattern to heat treatment at 150 to 450 ° C, thereby making it a heat resistant polymer pattern having a quinone ring, an oxazole ring or other functional groups. It is also possible to carry out heat treatment using microwaves. When the microwave frequency is changed while the microwave frequency is changed, it is preferable in that it is possible to prevent a standing wave and uniformly heat the substrate surface. Further, in the case where the substrate, such as an electronic component, includes a metal conductor, it is preferable in the following aspects: When the frequency is changed and the microwave is pulsed, the discharge from the metal or the like can be prevented, and the electronic component can be protected from damage.

In the negative-type photosensitive resin composition of the present invention, when the poly-proline and the polyhydroxyguanamine are dehydrated and closed into a polyimine or a polyoxazole, the frequency of the microwave irradiated is in the range of 0.5 to 20 GHz, and the practical range is 1~10GHz, and the better range is 2~9GHz.

It is desirable to vary the frequency continuity of the irradiated microwaves and actually illuminate the frequency phase changes. At this time, the shorter the time for irradiating the single frequency microwave, the more difficult it is to generate a standing wave or a discharge from the metal, etc., and the time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

The output of the irradiated microwave varies depending on the size of the device and the number of objects to be heated, and is approximately 10 to 2000 W, and practically 100 to 1000 W, and more preferably 100 to 700 W, and most preferably 100 to 500 W. . If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, it is liable to cause an abrupt temperature rise.

In the negative-type photosensitive resin composition of the present invention, it is preferred that the polypyridic acid and the polyhydroxyguanamine are separately dehydrated and closed into a polyimine or a polyoxazole, and the microwave pulse of the irradiation is input. Switch. By irradiating the microwave in a pulsed manner, it is preferable that the set heating temperature can be maintained, and the polyoxazole film or the substrate can be prevented from being damaged. The time during which the pulsed microwave is irradiated once differs depending on conditions, and is approximately 10 seconds or less.

In the negative-type photosensitive resin composition of the present invention, when the polyglycolic acid and the polyhydroxyguanamine are respectively dehydrated and closed into a polyimidazole or a polyoxazole The time until the sufficient dehydration ring-closure reaction is carried out is approximately 5 hours or less from the viewpoint of compatibility with work efficiency. Further, the other environment of the dehydration ring closure may be any one of an atmosphere such as an atmosphere or an inert gas such as nitrogen.

When the negative-type photosensitive resin composition of the present invention is used as a substrate of a layer, microwaves are irradiated under the above conditions, and polylysine and polyhydroxyguanamine in the negative-type photosensitive resin composition of the present invention are used. In the dehydration ring closure, even if a dehydration ring-closing process using microwaves at a low temperature is performed, a polyimine or a polyoxazole having the same physical properties as a dehydration ring-closure film at a high temperature using a thermal diffusion furnace can be obtained.

[electronic parts]

Next, the electronic component of the present invention will be described. The negative-type photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices or multilayer multilevel interconnect boards, and more specifically, can be used for forming a surface protective film or an interlayer insulating film of a semiconductor device, and a multilayer conductor wiring. Interlayer insulating film of the board. The electronic component of the present invention is not particularly limited as long as it has a surface protective film or an interlayer insulating film formed using the negative photosensitive resin composition, and can have various structures.

Hereinafter, an example of a manufacturing procedure of a semiconductor device (electronic component) using the negative-type photosensitive resin composition of the present invention will be described. Fig. 1 is a view showing a manufacturing step of a semiconductor device having a multilayer conductor wiring structure. In FIG. 1, a semiconductor substrate 1 such as a germanium substrate having a circuit element is covered with a protective film 2 such as a tantalum oxide film except for a specific portion of the circuit element, and the first conductive layer 3 is formed on the exposed circuit element. A film such as a polyimide resin is formed on the semiconductor substrate 1 by spin coating or the like as the interlayer insulating layer 4 (step (a)).

Next, a chlorinated rubber-based or phenol novolak-based photosensitive resin layer 5 is formed on the interlayer insulating layer 4 by spin coating, and a specific portion of the interlayer insulating layer is exposed by photo-etching using a well-known photo-etching technique. The opening 6A is set in a manner (step (b)). The interlayer insulating layer 4 exposed from the opening 6A is selectively etched by dry etching using a gas such as oxygen or carbon tetrafluoride to open the opening 6B. Thereafter, the photosensitive resin layer 5 is completely removed by etching the first conductive layer 3 exposed from the opening 6B without etching the photosensitive resin layer 5 (step (c)).

Further, the second conductor layer 7 is formed using a well-known photolithography technique and is electrically connected completely to the first conductor layer 3 (step (d)). In the case where a three-layer or three-layer multilayer conductor wiring structure is formed, the above steps may be repeated to form each layer.

Thereafter, a surface protective layer 8 is formed. In the example of FIG. 1, the photosensitive resin composition is applied to a surface protective film by a spin coating method, and dried, and light is irradiated from a mask on which a pattern 6H is formed in a specific portion to form a pattern, and then alkaline is used. The aqueous solution is developed to form a pattern, and heated to form a heat-resistant polymer film. The heat-resistant polymer film protects the conductor layer from external stress, α-ray, etc., and the obtained semiconductor device has excellent reliability. Further, in the above examples, the interlayer insulating layer may be formed using the negative photosensitive resin composition of the present invention.

[Examples 1 to 24]

Hereinafter, the present invention will be specifically described by way of examples.

[Synthesis Example 1] Synthesis of polybenzoxazole precursor

In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4'-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and then the flask was cooled to 5 ° C, and 23.9 g (23.9 g) was dropped. 120 mmol of thionyl chloride was allowed to react for 30 minutes to obtain a 4,4'-diphenyl ether tetracarboxylic acid chloride solution. Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 87.5 g of N-methylpyrrolidone was charged, and 18.30 g (50 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g ( 20 mmol) of m-aminophenol, after stirring and dissolving, adding 9.48 g (120 mmol) of pyridine, maintaining the temperature at 0 to 5 ° C, and dropping the 4,4'-diphenyl ether tetracarboxylic acid chloride solution for 30 minutes, Stir continuously for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was collected and washed with pure water for 3 times, and then dried under reduced pressure to obtain polyhydroxyguanamine (hereinafter referred to as polymer I). The weight average molecular weight of the polymer I obtained by standard polystyrene conversion was 17,600, and the degree of dispersion was 1.6.

[Synthesis Example 2]

The synthesis was carried out under the same conditions as in Synthesis Example 1 except that 50 mmol% of 4,4'-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was replaced with cyclohexane 1,4-dicarboxylic acid. The obtained polyhydroxyguanamine (hereinafter referred to as polymer II) had a weight average molecular weight of 18,580 and a degree of dispersion of 1.5 in terms of standard polystyrene.

[Synthesis Example 3] Synthesis of Polyimine Precursor

10 g (32 mmol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA, 3,3',4,4'-diphenylether tetracarboxylic dianhydride in a 0.2 liter flask with a stirrer and a thermometer. ) with 3.87 g (65 mmol) isopropanol was dissolved in 45 g of N-methylpyrrolidone, and a catalyst amount of 1,8-diazabicycloundecene was added thereto, followed by heating at 60 ° C for 2 hours, followed by room temperature. (25 ° C) was stirred for 15 hours to cause esterification.

Thereafter, 7.61 g (64 mmol) of sulfinium chloride was added under ice bath, and the mixture was returned to room temperature and reacted for 2 hours to obtain an acid chloride solution. Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 40 g of N-methylpyrrolidone was charged, and 10.25 g (28 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.87 g (8 mmol) were added. After the m-aminophenol was stirred and dissolved, 7.62 g (64 mmol) of pyridine was added, the temperature was maintained at 0 to 5 ° C, and the previously prepared acid chloride solution was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The reaction was dropped to distilled water, filtered, and the precipitate was collected, and dried under reduced pressure to obtain a polyamine. (Hereafter, it is set as the polymer III).

The weight average molecular weight was 19,400. The esterification rate of the polylysine obtained by NMR spectrum (nuclear magnetic resonance spectrum) was 100%.

[Photographic evaluation]

With respect to 100 parts by weight of each of the above polymers I to III, (b) a compound which generates an acid by irradiation with active rays, and (c) a crosslinking agent are added in a specific amount shown in Table 1.

The above solution was spin-coated on a tantalum wafer to form a coating film having a dry film thickness of 3 to 10 μm, which was subjected to i-line (365 nm) exposure using an ultrahigh pressure mercury lamp via an interference filter. After exposure, heat at 120 ° C After 3 minutes, development was carried out with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide until the exposed wafer was exposed, and then washed with water to obtain a pattern having a residual film ratio of 90% or more (film thickness ratio before and after development). The minimum exposure (sensitivity) and resolution necessary. The results are shown in Table 2.

In the table, the amount of addition in the parentheses relative to 100 parts by weight of the polymer is expressed in parts by weight.

In Table 1, B1 and B2 used as the component (b) and C1 to C11 used as the component (c) are the compounds represented by the following chemical formulas (VII) and (VIII), respectively.

In the above, high sensitivity and high resolution can be obtained.

(Examples 25 to 30)

The materials used in Examples 1, 6, 7, 10, 13, and 21 shown in Table 1 were changed to study the hardening method. These negative-type photosensitive resin composition solutions were spin-coated on a ruthenium wafer, and heated at 120 ° C for 3 minutes to form a coating film having a film thickness of 15 μm. Thereafter, the coating film was cured by Microcure 2100 manufactured by Lambda Technology Co., Ltd., microwave output of 450 W, microwave frequency of 5.9 to 7.0 GHz, substrate temperature of 250 ° C, and curing for 2 hours to obtain a cured film having a film thickness of about 10 μm.

Next, the cured film was peeled off using a hydrofluoric acid aqueous solution, washed with water, dried, and measured for glass transition point (Tg), elongation, and 5% weight reduction temperature. These results are shown in Table 4.

As described above, it is clear that the negative-type photosensitive resin composition of the present invention has a frequency change even when the substrate temperature is maintained at 260 ° C. The method of irradiating the microwaves in a pulsed manner can also obtain sufficient physical properties, and effectively perform dehydration ring closure of polyamine or polyimine, and harden them.

(Comparative examples 1 to 7)

The components (b) and (c) were added in a specific amount shown in Table 5 with respect to 100 parts by weight of the polymer, and evaluated in the same manner as in the following examples. The results of these are shown in Table 6. In Comparative Examples 1 and 2, the results did not cause insolubilization due to crosslinking reaction or polymerization in the exposed portion, and the pattern could not be obtained. In Comparative Examples 3 to 5, although a negative image was obtained, the residual film ratio was remarkably lower than in the examples, and the residual film ratio was not increased even if the exposure amount was increased. From this, it can be understood that the methylol group or the alkoxyalkyl group of the crosslinking agent component contributes to the improvement of the photosensitive property.

In Table 5, B1 used as the component (b) is the same as those in Table 1, and C12, 13, and 14 used as the component (c) are compounds represented by the following chemical formula (IX).

As described above, the negative-type photosensitive resin composition of the present invention has excellent sensitivity, resolution, and heat resistance. Further, according to the method for producing a pattern of the present invention, it is possible to obtain a pattern having excellent sensitivity, resolution, and heat resistance and having a good shape by using the above composition. Moreover, the electronic component of the present invention has a better reliability by having a pattern with good shape and characteristics. high. Thus, the present invention is useful for electronic components such as electronic components.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

1‧‧‧Semiconductor substrate

2‧‧‧Protective film

3‧‧‧First conductor layer

4‧‧‧Interlayer insulation

5‧‧‧Photosensitive resin layer

6A, 6B, 6C‧‧‧ openings

7‧‧‧Second conductor layer

8‧‧‧Surface protection layer

Fig. 1 is a view showing a manufacturing step of a semiconductor device in which a multilayer conductor wiring structure is constructed.

1‧‧‧Semiconductor substrate

2‧‧‧Protective film

3‧‧‧First conductor layer

4‧‧‧Interlayer insulation

5‧‧‧Photosensitive resin layer

6A, 6B, 6C‧‧‧ openings

7‧‧‧Second conductor layer

8‧‧‧Surface protection layer

Claims (4)

A negative-type photosensitive resin composition containing (a) a heat-resistant polymer, (b) a compound which generates an acid by irradiation with active light, and (c) crosslinking or polymerization by an acid action The cross-linking agent is characterized in that the (a) heat-resistant polymer has a phenolic hydroxyl group at the terminal, and the (c) crosslinking agent which is cross-linked or polymerized by an acid action, and contains at least one hydroxyl group in the molecule. a compound of a group or an alkoxyalkyl group, and the above (b) a compound which illuminates the active light to generate an acid is an aromatic sulfonate or an aromatic N-oxyindenine sulfonate; and the above (c) acts as an acid The crosslinking agent to be crosslinked or polymerized includes at least one compound selected from the group consisting of a compound represented by the general formula (C5) and a compound represented by the general formula (C9): The negative-type photosensitive resin composition according to claim 1, wherein the (a) heat-resistant polymer is a polyimine, a polyoxazole or a precursor thereof, and has an amino-based phenol. Hydroxyl group. A method for producing a pattern comprising: applying a negative-type photosensitive resin composition according to claim 1 of the invention to a support substrate, and drying the film; and performing the photosensitive resin film obtained by the drying step Exposure a step of heating the photosensitive resin film after the exposure, a step of developing the heated photosensitive resin film using an alkaline aqueous solution, and a step of heat-treating the developed photosensitive resin film. An electronic component comprising an electronic component comprising a film layer of a pattern obtained by the manufacturing method according to claim 3, wherein the electronic component is provided with the above-mentioned pattern The layer serves as an interlayer insulating layer and/or a surface protective layer.