KR101217264B1 - Polymer resion compound and photosensitive resin composition comprising the same - Google Patents

Abstract

The present invention relates to a polymer resin compound including a repeating unit having a specific structure and a photosensitive resin composition including the same, wherein using the polymer resin compound realizes high adhesion to a substrate used in a semiconductor device or a display device, It is excellent in physical properties such as chemical resistance, and can exhibit high resolution, high sensitivity, excellent film properties, and improved mechanical properties.

Description

Polymer resin compound and the photosensitive resin composition containing the same {POLYMER RESION COMPOUND AND PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME}

The present invention relates to a polymer resin compound and a photosensitive resin composition comprising the same, and have high adhesion to a substrate used in a semiconductor device or a display device, and are excellent in physical properties such as heat resistance and chemical resistance, and have high resolution, high sensitivity, and excellent film. The present invention relates to a polymer resin compound capable of exhibiting properties and improved mechanical properties and to a photosensitive resin composition comprising the same.

Photosensitive resin is a typical functional polymer material practically used in the production of various precision electronic and information industrial products, and is currently used in the high-tech industry, in particular, the production of semiconductors and displays. In general, the photosensitive resin refers to a polymer compound in which chemical changes in molecular structure occur in a short time due to light irradiation, thereby changing physical properties such as solubility, coloring, and curing in a specific solvent. Photosensitive resins enable fine precision processing, significantly reduce energy and raw materials compared to thermal reaction processes, and can perform operations quickly and accurately in a small installation space, leading to advanced printing, semiconductor production, and display production. It is used in various precision electronic and information industries, such as photocuring surface coating material.

Such photosensitive resins can be broadly divided into negative type and positive type. The negative type photosensitive resin is a type in which the irradiated portion is insolubilized in the developer, and the positive type photosensitive resin is a type in which the irradiated portion is solubilized in the developer. to be. Recently, as electronic devices have been highly integrated and finely patterned, positive photosensitive resins capable of minimizing defect rates and increasing processing efficiency and resolution have been mainly used.

Previously, many positive photosensitive resin compositions including novolak resins and diazonaptoquinone compounds have been used. However, such resin compositions are required for improving the degree of integration of precision electronics and information products, especially semiconductor devices or display devices. There was a limit to meeting this. Accordingly, a method of using various types of positive photosensitive resins, such as polyamic acid or polyamic acid, in photosensitive resins has been introduced. However, the polyamic acid is easily hydrolyzed by water in the air and the like, so that the preservation and stability are not sufficient, and the polyamic acid has low adhesiveness to the substrate to which it is applied. there was. In addition, other types of photosensitive resins also have a problem of peeling off from the substrate during development or curing due to insufficient chemical resistance, heat resistance, and electrical properties in the final cured state, or insufficient adhesion to the metal substrate. Accordingly, there is a need to develop a new type of photosensitive resin material that overcomes the limitations of existing materials, that is, a photosensitive resin material capable of forming an ultra-fine pattern while having excellent mechanical properties and excellent adhesion to a substrate.

The present invention is applied to the photosensitive resin composition, while exhibiting high adhesion to a substrate used in a semiconductor device or a display device, it is excellent in physical properties such as heat resistance and chemical resistance, and exhibits high resolution, high sensitivity, excellent film properties, and improved mechanical properties. It is to provide a novel polymer resin compound that can be.

Moreover, this invention is providing the photosensitive resin composition containing the said novel polymeric resin compound.

The present invention also provides an electronic device comprising an organic insulating film or a photosensitive pattern formed from the photosensitive resin composition.

The present invention is to provide a polymer resin compound containing a repeating unit having a specific structure.

In addition, the present invention is the polymer resin compound; Photo-active compounds; And to provide a photosensitive resin composition comprising an organic solvent.

The present invention also provides an electronic device comprising an organic insulating film or a photosensitive pattern formed from the photosensitive resin composition.

Hereinafter, a polymer resin compound, a photosensitive resin composition, and an electronic device according to specific embodiments of the present invention will be described in detail.

According to one embodiment of the invention, there may be provided a polymer resin compound comprising at least one repeating unit selected from the group consisting of the repeating unit of Formula 1 and the repeating unit of Formula 2.

 [Formula 1]

(2)

In Chemical Formulas 1 and 2, X ₁ , X ₂ , X ₃ and X ₄ may each be a tetravalent organic group, and Y ₁ and Y ₃ may each have a carboxyl group (-COOH) or a hydroxyl group (-OH). And may be a divalent organic group, Y ₂ and Y ₄ may be a divalent organic group derived from dithiodioline, and R ₁ , R ₂ , R ₃ and R ₄ may each be hydrogen or an alkyl or silylalkyl group having 1 to 10 carbon atoms. Can be.

The present inventors reacted a specific tetracarboxylic acid, an acid anhydride thereof, or a polymer thereof with a specific diimine compound to obtain the polymer resin compound, and such a polymer resin compound, for example, a polyimide monomer having a specific structure, When the polymer resin compound containing a polyamic acid monomer or a polyamic acid ester monomer is applied to the photosensitive resin composition, it has been confirmed through experiments that high adhesion to a substrate used in a semiconductor device or a display device can be realized. . In addition, it was confirmed that the photosensitive resin composition including the polymer resin compound may improve physical properties such as heat resistance or chemical resistance, and may realize high resolution, high sensitivity, excellent film properties, and improved mechanical properties.

In particular, the polymer resin compound includes a bifunctional organic group derived from a specific functional group, for example Dithiodianiline, and is used in a semiconductor device or a display device, for example, Au, Cu, Ni, High adhesion can be achieved with respect to a substrate on which a metal film such as Ti is formed, or an inorganic substrate such as Si, SiO ₂ , SiNx, in particular, a substrate on which an Au film is formed. This excellent adhesion property is shown to be due to the polymer resin compound includes a functional group using dithiodinaniline. The disulfide bond of the dithiodinyl may be broken during the process of forming the photosensitive resin film, and the two sulfur atoms appearing at this time are firmly bonded to the metal film on the substrate, and thus have high adhesion to the substrate used in the semiconductor device or the display device. Can be implemented.

The dithiodianiline may be 2,2'-Dithiodianiline, 3,3'-Dithiodianiline or 3,3'-Dithiodianiline or 4,4'-Dithiodianiline. 4'-Dithiodianiline), preferably 2,2'-dithiodianiline or 4,4'-dithiodianiline.

In Formulas 1 and 2, X ₁ , X ₂ , X ₃ and X ₄ may each be a tetravalent organic group. Specifically, X ₁ , X ₂ , X ₃ and X ₄ are tetravalent organic groups each containing an alicyclic ring or aromatic ring having 4 to 40 carbon atoms; Or a tetravalent aliphatic organic group having 4 to 20 carbon atoms.

X ₁ , X ₂ , X ₃ and X ₄ may each be a tetravalent organic group derived from tetracarboxylic acid, anhydrides thereof or derivatives thereof. Specific examples of such tetracarboxylic acid include cyclobutane-1,2,3,4-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, 2, 3,5-tricarboxycyclopentylacetic acid, bicyclo (2,2,2) octo-7-ene-2,3,5,6-tetracarboxylic acid or tetrahydrofuran-2,3,4,5- Alicyclic tetracarboxylic acids such as tetracarboxylic acid; Aliphatic tetracarboxylic acids, such as butanetetracarboxylic acid; Or pyromellitic acid, oxydiphthalic acid, biphenyltetracarboxylic acid, hexafluoroisopropylidenediphthalic acid, hydroquinonebisphthalic acid, diphthalic acid, 3,3 ', 4,4'-benzophenonetetra Aromatic tetracarboxylic acids such as carboxylic acid, benzene tetracarboxylic acid, naphthalene tetracarboxylic acid, anthracene tetracarboxylic acid, pyridine tetracarboxylic acid, and furan tetracarboxylic acid. However, tetravalent organic groups derived from tetracarboxylic acid, anhydrides thereof, or derivatives thereof that may be used for X ₁ , X ₂ , X _3, and X ₄ are not limited to the above examples, and may be applied to photosensitive polymer resins. If it is known, it can be applied without restriction.

Specific examples of such X ₁ , X ₂ , X ₃ and X ₄ may include organic groups represented by the following Chemical Formulas 5 to 23.

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Formula 18]

[Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Formula 22]

(23)

Meanwhile, Y ₁ and Y ₃ may each be a divalent organic group having a carboxyl group or a hydroxyl group, and preferably a divalent aromatic organic group having a carboxyl group or a phenolic hydroxyl group. Applying a polymer resin compound containing such an organic group having a carboxyl group or a hydroxyl group, the photosensitive resin film can be easily dissolved in an alkaline developer, for example, an aqueous tetramethylammonium hydroxide (TMAH) solution or the like after exposure. Accordingly, the process time and cost of the developing step can be reduced, thereby improving the economics and efficiency of the manufacturing process of the semiconductor device or the display device. Accordingly, the polymer resin compound may be alkali soluble.

In addition, Y ₁ and Y ₃ may be a divalent organic group derived from a diamine compound substituted with a carboxyl group or a hydroxyl group, respectively. The diamine compound may be used without particular limitation as long as it can provide a divalent organic group, and specific examples thereof include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3- Phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'- Diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-methylene-bis (2-methylaniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine , One, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane or 2,2-bis [4- (3- Aromatic diamines such as aminophenoxy) phenyl] propane; And 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4, Aliphatic diamines such as 4'-diaminodicyclohexylmethane or 4,4'-diamino-3,3'-dimethyldicyclohexylmethane.

Specific examples of Y ₁ and Y ₃ may include organic groups represented by the following Chemical Formulas 24 to 34.

≪ EMI ID =

(25)

(26)

(27)

(28)

[Formula 29]

(30)

(31)

(32)

(33)

[Formula 34]

The polymer resin compound may have a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000. When the weight average molecular weight is less than 1,000, it may be difficult to realize the desired coating properties and thermal / mechanical properties when the polymer resin compound is applied. When the weight average molecular weight is more than 500,000, the solubility of the developer is lowered, so that high sensitivity and high resolution are realized as a photosensitive material. This can be difficult.

On the other hand, the polymer resin compound may further include one or more repeating units selected from the group consisting of the repeating unit of Formula 3 and the repeating unit of Formula 4.

[Formula 3]

[Formula 4]

X ₅ and X ₆ in Chemical Formulas 3 and 4 each represent a tetravalent organic group including an alicyclic ring or an aromatic ring having 4 to 40 carbon atoms; Or a tetravalent aliphatic organic group having 4 to 20 carbon atoms, Y ₅ and Y ₆ may each be a divalent organic group, and R ₅ and R ₆ may each be hydrogen or an alkyl or silylalkyl group having 1 to 10 carbon atoms. Can be.

Specific examples of the tetravalent organic group usable for X ₅ and X ₆ may be applied in the same manner as described above for X ₁ , X ₂ , X ₃ and X ₄ .

The divalent organic group usable for Y ₅ and Y ₆ may be included without any limitation as long as it is known to be applicable to the photosensitive resin composition, and may be a divalent organic group derived from a diamine compound. Such a diamine compound can be used without particular limitation as long as it can provide a divalent organic group, and specific examples of the diamine compound are as described in the description of Y ₁ and Y ₃ .

On the other hand, specific examples of the Y ₅ and Y ₆ include a divalent organic group represented by the formula (35) to 52.

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

Formula 46

[Formula 47]

(48)

[Formula 49]

[Formula 50]

[Formula 51]

In Formula 51, R ₁ is alkylene or arylene having 2 to 8 carbon atoms, R ₂ is alkylene having 2 to 8 carbon atoms, a and b are each 0 or 1, and c is an integer of 1 to 21, and ,

[Formula 52]

In Chemical Formula 52, d is an integer of 1 to 12.

On the other hand, according to another embodiment of the invention, the polymer resin compound; Photoactive compounds; And the photosensitive resin composition containing an organic solvent can be provided.

As described above, when the polymer resin compound, for example, a polymer resin compound containing a polyimide monomer, a polyamic acid monomer or a polyamic acid ester monomer having a specific structure, is applied to the photosensitive resin composition, it is used in a semiconductor device or a display device. It is possible to realize high adhesion to a substrate, for example, a substrate on which a metal film such as Au, Cu, Ni, Ti, or an inorganic substrate such as Si, SiO ₂ , SiNx, in particular, an Au film is formed, It was confirmed through experiments that the physical properties such as, and can realize high resolution, high sensitivity, excellent film properties and improved mechanical properties.

The polymer resin compound may include one or more repeating units selected from the group consisting of the repeating unit of Formula 1 and the repeating unit of Formula 2. Accordingly, the polymer resin compound may include a polyimide monomer, a polyamic acid monomer or a polyamic acid ester monomer.

In addition, the polymer resin compound may further include one or more repeating units selected from the group consisting of the repeating unit of Formula 3 and the repeating unit of Formula 4.

The photo active compound (PAC) is generally called a photosensitive agent or photosensitive acid generator, and means a compound capable of being activated or generating an acid by light irradiation.

The photoactive compound may include a positive type in which an exposed part is developed by changing to a structure in which solubility is increased in an alkali developer after exposure; A negative type in which a non-exposure portion is developed may be used since the solubility is reduced in an alkali developing solution after exposure, and a positive photoactive compound is preferably applied to the photosensitive resin composition.

As the negative photoactive compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, anthraquinone, naphthoquinone , 3,3-dimethyl-4-methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone (p, p'-bis (diethylamino) benzophenone, p, p'-di Ethylaminobenzophenone, pivalon ethylether, 1,1-dichloro acetophenone, pt-butyldichloroacetophenone, dimer of hexaaryl-imidazole, 2,2'-diethoxyacetophenone, 2,2'-die Methoxy-2-phenylacetophenone, 2,2'dichloro-4-phenoxyacetophenone, phenylglyoxylate, a-hydroxy-isobutylphenone, dibenzospan, 1- (4-isopropylphenyl) -2 -Hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) fetyl] -2-morpholino-1-propanone or tribromomethylphenylsulfone (tribromom ethylphenylsulfone) and the like may be used alone or in combination of two or more thereof.

As the positive photoactive compound, a photoacid-generating photoactive compound which generates an acid by a photoreaction to increase solubility in an alkaline developer of the light irradiation part may be used. Specific examples of photoacid-producing photoactive compounds include diazonaptoquinone compounds, allyl diazonium salts, diallyl iodonium salts, triallylsulfonium salts, o-nitrobenzyl esters, p-nitrobenzyl esters, and trihalomethyl group substituted s-trees. A azine derivative, an imide sulfonate derivative, etc. are mentioned, Preferably a diazonaphthoquinone type compound can be used. In addition, these can be used individually or in mixture of 2 or more types, The positive type photoactive compound which can be used is not limited to the said example.

In particular, it is preferable to use a diazonaphthoquinone-based compound as the positive photoactive compound. Specific examples of such a diazonaphthoquinone-based compound include diazonaphthoquinone-based compounds represented by the following Chemical Formulas 53 to 60.

(53)

[Formula 54]

(55)

(56)

(57)

(58)

[Chemical Formula 59]

(60)

In Formulas 53 to 60, D may be a compound of Formula 61 or 62.

(61)

[Formula 62]

Meanwhile, the photosensitive resin composition may include 1 to 50 parts by weight, preferably 5 to 30 parts by weight of the photoactive compound, based on 100 parts by weight of the polymer resin compound. When the content of the photoactive compound is 1 to 50 parts by weight, the pattern is well formed without the residue by exposure, and a good pattern can be formed without loss of film thickness during development. When the content is less than 1 part by weight, light is irradiated. Even if the acid may not be generated sufficiently, if the content exceeds 50 parts by weight, the physical properties such as dielectric properties, mechanical strength, heat resistance, etc. of the resin film formed from the photosensitive resin composition may be deteriorated, and light transmittance may be deteriorated. Can be.

On the other hand, as the organic solvent, an organic solvent known to be used in the photosensitive resin composition can be used without particular limitation, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacet Amide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, lactic acid Ethyl, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate or mixtures thereof It is preferable to use.

The photosensitive resin composition is 20 to 2,000 parts by weight, preferably 50 to 1,000 parts by weight based on 100 parts by weight of the polymer resin compound. Organic solvents. When the organic solvent is used in the above content range, a pattern having a sufficient thickness can be formed, and solubility and coating property are also excellent, which is preferable.

On the other hand, the photosensitive resin composition may further include additives such as a novolak resin, a dissolution rate regulator, an adhesion promoter, a surfactant, or a mixture thereof.

The novolac resin may serve to adjust the resolution and sensitivity of the photosensitive resin composition. Such novolak resins may include condensates of phenols and aldehydes. Specific examples of the phenol include phenol, 4-t-butyl phenol, 4-t-octyl phenol, 2-ethyl phenol 3-ethyl phenol, 4-ethyl phenol, o-cresol, m-cresol, p-cresol, 2, 5-Xylenol, 3,4-Xylenol, 3,5-Xylenol, 2,3,5-trimethylphenol, 3-methyl-6-t-butylphenol, 2-naphthol, 1,3-dihydroxy Naphthalene or bisphenol-A. Specific examples of the aldehyde include formaldehyde, paraformaldehyde, acetoaldehyde, benzaldehyde or phenylaldehyde. The phenol and the aldehyde can be used alone or in combination of two or more, respectively, organic acids such as oxalic acid, p-toluenesulfonic acid or trichloroacetic acid in the process of forming a condensate; Inorganic acids such as sulfuric acid, hydrochloric acid or phosphoric acid; Or metal salts such as zinc chloride, aluminum chloride, magnesium acetate or zinc acetate can be used as a catalyst.

It is preferable to use a polystyrene reduced weight average molecular weight of 2,500 to 15,000 as the novolak resin. If the weight average molecular weight is less than 2,500, there is a fear of overdevelopment. If the weight average molecular weight is more than 15,000, coating property is not guaranteed and there is a fear of undevelopment.

And it is preferable to add the said novolak resin at 0-50 weight part with respect to 100 weight part of solid content components (sum of components except a solvent part) of the photosensitive resin composition.

It is preferable to use a silane coupling agent having a functional group such as epoxy, carboxyl group or isocyanate as the adhesion promoter, and specific examples thereof include trimethoxysilyl benzoic acid, triethoxysilyl benzoic acid, Gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, Gamma-glycidoxypropyltriethoxysilane or mixtures thereof. Such adhesion promoters may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer resin compound.

The surfactant may be used without particular limitation as long as it is known to be used in the photosensitive resin composition, but it is preferable to use a fluorine-based surfactant or a silicone-based surfactant. Such a surfactant may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polymer resin compound.

On the other hand, it is preferable that the said photosensitive resin composition is a positive type by which an exposure part is developed. When the organic insulating film or the photosensitive pattern is formed using the photosensitive resin composition, fine dust may adhere to the surface. In the negative photosensitive resin composition, since the dust part is unexposed, holes are formed, such as disconnection or surface property degradation. Although it may have a problem, when the positive photosensitive resin composition is applied, holes may not be generated in the dust portion, thereby preventing the above problems. In addition, the positive photosensitive resin composition can not only realize high resolution and high processing efficiency, but also reduce the adverse effect on the environment while increasing the safety of the work by using an alkaline solution as the developer. Therefore, since the positive photosensitive resin composition can minimize the defective rate and increase the processing efficiency and resolution, the positive photosensitive resin composition can be easily applied to highly integrated and micropatterned electronic devices.

On the other hand, according to another embodiment of the invention, an electrical device comprising an organic insulating film or photosensitive pattern formed from the photosensitive resin composition may be provided.

The organic insulating film or the photosensitive pattern may be formed of a substrate used for a semiconductor device or a display device, for example, a metal film such as Au, Cu, Ni, Ti, or the like, due to the properties resulting from the polymer resin compound having the specific chemical formula structure. High adhesion to the formed substrates and inorganic substrates such as Si, SiO ₂ , SiNx, in particular, Au substrates can be achieved, and can have excellent physical properties such as improved heat resistance and chemical resistance, and have high resolution, high sensitivity, excellent film properties, and It can exhibit improved mechanical properties.

Therefore, the electrical device including the organic insulating film or the photosensitive pattern formed from the photosensitive resin composition can implement excellent performance such as high resolution, high sensitivity, and can exhibit excellent film properties and high mechanical properties, as well as excellent heat resistance properties, eg For example, even if it is used for a long time or is exposed for a long time in a high temperature condition, it is possible to implement a property that can be maintained firm without adhesion of the organic insulating film or photosensitive pattern.

The organic insulating layer may include various insulating layers of a semiconductor device or a display device, for example, an interlayer insulating layer, a surface protective layer, an electrode protective layer buffer coat layer, or a passivation layer. The electrical element may include various components of a semiconductor device or a display device.

On the other hand, the organic insulating film or photosensitive pattern, the step of applying the photosensitive resin composition on a support substrate and dried to form a resin film; Exposing the resin film; The exposed resin film may be formed by developing an alkali developer and heat treating the developed photosensitive resin film.

When the photosensitive resin composition is used, a patterned photosensitive resin film may be easily formed on a substrate such as glass or a silicon wafer. In this case, a method of applying the photosensitive resin composition may include spin coating and slit spin. Coating, roll coating, die coating, curtain coating, bar coating, screen printing and the like can be used.

The supporting substrate that can be used in the process of forming the photosensitive resin film can be used without any limitation as long as it is known to be commonly used in the field of electronic communication or semiconductor or display, but specific examples thereof include a silicon wafer, a glass substrate, a metal substrate, Ceramic substrates, polymer substrates, and the like.

In the drying process after the application, a prebaked film may be formed by prebaking the solvent at 50 to 150 ° C. for about 20 minutes to volatilize the solvent. If the drying temperature is too low, the amount of the remaining solvent is too large to dissolve the non-exposed areas in the developer during development, it is difficult to implement the pattern, if the drying temperature is too high, the curing reaction is promoted, the exposure area may not be developed .

In the exposing the resin film, ultraviolet rays or visible rays having a wavelength of 200 nm to 500 nm may be irradiated using a photomask on which a pattern to be processed is formed, and the exposure amount is preferably 20 to 4,000 mJ / cm 2. Exposure time is not specifically limited, either, According to the exposure apparatus used, wavelength of an irradiation light, or exposure amount, it can change suitably.

In the step of forming the photosensitive resin film, an alkaline aqueous solution may be used as a developer. Such alkaline aqueous solution is more environmentally friendly than general organic solvents and is economical because the cost of the product is low. Specific examples of the alkaline aqueous solution include aqueous solutions of metal hydroxides such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide and potassium carbonate; Aqueous solutions of ammonium hydroxides such as tetramethylammonium hydroxide (TMAH) and tetraammonium hydroxide; Or an amine-based aqueous solution such as ammonia, ethylamine, propylamine, diethylamine, or triethylamine, and the like, and one type of such alkaline aqueous solution can be used, and two or more kinds thereof can be used in combination. However, the alkaline aqueous solution which can be used is not limited to this example, and the alkaline aqueous solution commonly known to be usable in the semiconductor or display production stage can be used without any particular limitation.

If necessary, additives such as water-soluble organic solvents such as methanol, ethanol, propanol and ethylene glycol, various surfactants, various storage stabilizers, and resin dissolution inhibitors may be added to the aqueous alkali solution. The addition amount of these additives is not specifically limited, An appropriate amount can be set according to the kind of alkali aqueous solution, the image development conditions, and the composition of a resin composition.

According to the present invention, a polymer resin compound having high physical properties such as heat resistance and chemical resistance while exhibiting high adhesion to a substrate used in a semiconductor device or a display device, and exhibiting high resolution, high sensitivity, excellent film properties, and improved mechanical properties And a photosensitive resin composition including the same.

1 shows an electron micrograph of a pattern prepared from the photosensitive resin composition of Example 1. FIG.
2 shows an image of an Au electroplating pattern in Experimental Example 2. FIG.
3 shows a cross cutting method in Experimental Example 2. FIG.
4 shows the results of the first taping test on the photosensitive resin film of Example 1. FIG.
Figure 5 shows the results of the first taping test for the photosensitive resin film of Comparative Example 1.
6 shows the results of the secondary taping test on the photosensitive resin film of Example 1. FIG.
7 shows the results of the secondary taping test on the photosensitive resin film of Comparative Example 1. FIG.

The invention is explained in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Synthetic example : Synthesis of Polymer Resin Compound>

Synthesis Example 1 Polyimide Mw .40,000) Synthesis (P-1)

Into a 100 mL round bottom flask, 7.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2.5 g of 4,4'-dithiodianiline and 40 g of gamma-butyrolactone were sequentially added. After stirring slowly to completely dissolve the flask, 9.3 g of 3,3 ', 4,4'-oxydiphthalic dianhydride (3,3', 4,4'-Oxydiphthalic anhydride) was added while maintaining the flask in water. Added slowly. After the mixture solution was stirred at room temperature for 16 hours, 7 g of toluene was added thereto, and the mixture solution was installed to remove water through a dean stark distillation and refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and then dried in a 40 ° C. vacuum drying oven for one day to obtain 14 g of polyimide resin.

At this time , the polyimide production peak was confirmed through IR, and the weight average molecular weight of the obtained polyimide resin was 40,000 and the polydispersity index was 1.7 through GPC.

Synthesis Example 2 : Of polyamic acid (Mw.45,000)  Synthesis (P-1)

7.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1 g of 3,4-diphenyl ether, 1.2 g of 4,4'-dithiodianiline and gamma in a 100 mL round bottom flask 40 g of butyrolactone were added sequentially and slowly stirred to dissolve completely, followed by 3,3 ', 4,4'-oxydiphthalic dianhydride (3,3,4,4) while maintaining the jacket temperature of the reactor at 10 ° C. Oxydiphthalic anhydride 9.3 g was added slowly and stirred. After the mixture solution was stirred at room temperature for 16 hours, 7 g of toluene was added thereto, and the mixture solution was installed to remove water through a dean stark distillation and refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and then dried in a 40 ° C. vacuum drying oven for one day to obtain 14 g of polyimide resin.

At this time, the polyamic acid production peak was confirmed through IR, and the weight average molecular weight of the obtained polyimide resin was 40,000 and the polydispersity index was 1.7 through GPC.

Comparative Synthesis Example 1 : Of polyamic acid (Mw.45,000)  Synthesis (P-1)

11 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 40 g of gamma-butyrolactone were sequentially added to a 100 mL round bottom flask and slowly stirred to complete dissolution. 9.3 g of 3,3 ', 4,4'-oxydiphthalic dianhydride (3,3', 4,4'-Oxydiphthalic anhydride) was slowly added while stirring. After stirring the mixed solution at room temperature for 16 hours, 7 g of toluene was added thereto, and the mixture solution was installed to remove water through a dean stark distillation and refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and then dried in a 40 ° C. vacuum drying oven for one day to obtain 14 g of polyimide resin.

At this time, the polyimide production peak was confirmed through IR, and the weight average molecular weight of the obtained polyimide resin was 40,000 and the polydispersity index was 1.7 through GPC.

< Example  And Comparative example : Production of Photosensitive Resin Composition>

Example 1 : Preparation of Polyimide Resin Composition

0.5 g of diazonaphthoquinone ester compound (TPPA 320: OD / (OD + OH) = 2/3 is selectively given as the photoactive compound to 1.6 g of the polyimide of Synthesis Example 1). 4 g of gamma-butyrolactone (GBL) was added thereto, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive resin composition.

Example 2 : Polyamide Of Novolak Resin Blending  Preparation of resin composition

2.0 g of the polyimide of Synthesis Example 1 and 0.5 g of a novolac resin (m-Cresol: p-Cresol = 6: 4) having a molecular weight of 6,000 were mixed, and 0.5 g of a diazonaptoquinone ester compound was added thereto as a photoactive compound. TPPA 320: OD / (OD + OH) = 2/3, optionally given between OH and OD), 5.5 g of gamma-butyrolactone (GBL) was added and stirred for 1 hour at room temperature. A photosensitive resin composition was prepared by filtration with a filter having a pore size of 1 μm.

Comparative Example 1 : Preparation of Polyimide Resin Composition

0.5 g of diazonaptoquinone ester compound (TPPA 320: OD / (OD + OH) = 2/3 as a photoactive compound in 1.6 g of the dissolved polyimide synthesized in Comparative Synthesis Example 1 was selected from OH and OD) 4 g of gamma-butyrolactone was added thereto, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive resin composition.

< Experimental Example >

Experimental Example 1 : Resolution evaluation

The photosensitive resin composition prepared in Examples and Comparative Examples was spin coated on a 4 inch silicon wafer, and heated at 120 ° C. for 2 minutes on a hot plate to form a 15 μm thick photosensitive resin layer. After the vacuum-processed silicon wafer was brought into close contact with the photomask, the G-line stepper Nikon NSB 1505 G4 was sequentially exposed from 20 mJ / cm 2 to 600 mJ / cm 2 at 5 mJ / cm 2 intervals. Thereafter, the solution was developed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 80 seconds, washed with ultrapure water for 60 seconds, and dried to obtain a pattern in which the non-exposed part remained clear. The patterned silicon wafer was heat-treated for 30 minutes using a hot plate under nitrogen stream to raise the temperature to 180 ° C.

The films completed from the compositions of Examples 1 and 2 and Comparative Example 1 had a thickness of 10 μm and the initial line width of the pattern was 3 μm. As shown in FIG. 1, it was confirmed that by using the photosensitive resin composition of Example 1, it was possible to form a 3 um hole pattern with excellent resolution.

Experimental Example 2 Photosensitive Resinous  Adhesion Evaluation

Forming an Au layer of 3 um thickness by electroplating method and spin-coating the photosensitive resin composition prepared in Example and Comparative Example on a 4 inch silicon wafer having a pattern formed thereon, and heated it at 120 ° C. for 2 minutes on a hot plate to have a thickness of 10 um The photosensitive resin layer of was formed. An image of the Au electroplating pattern is shown in FIG. 2.

After cross-cutting the silicon cone wafer on which the photosensitive resin layer was formed as shown in FIG. 3, a first taping test was performed. In addition, after storage at 85 ° C. and 85% moisture for 24 hours under severe conditions corresponding to JEDEC standard level 1, a thermal reflow was performed three times at 260 ° C., followed by a second taping test. Adhesion was evaluated. The evaluation result is as follows.

 Adhesion evaluation result Example 1 Comparative Example 1 First taping test Figure 4 5 Second taping test Figure 6 7

As shown in Figures 4 and 6, the photosensitive resin layer formed using the composition of Example 1 has a high adhesion to the Au layer, and even after applying the conditions of high temperature, high humidity, the adhesion to the Au layer is kept constant It was confirmed.

On the contrary, the photosensitive resin layer formed by using the composition of Comparative Example 1 does not have good adhesion to Au due to peeling of a wide area even in the first taping test (FIG. 5), and even after applying the conditions of high temperature and high humidity. Peeling occurred in the substrate region (Fig. 7), and it was confirmed that it had a relatively low adhesive force as compared with Example 1.

Claims (17)

A polymer resin compound having at least one repeating unit selected from the group consisting of a repeating unit of Formula 1 and a repeating unit of Formula 2 and having excellent metal adhesion to a substrate:
[Chemical Formula 1]

(2)

In Chemical Formulas 1 and 2,
X ₁ , X ₂ , X ₃ and X ₄ are each a tetravalent organic group,
Y ₁ and Y ₃ are each a divalent organic group having a phenolic hydroxyl group represented by the following formula (31),
Y ₂ and Y ₄ comprise a divalent organic group derived from dithiodinaniline,
R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen or an alkyl group or silylalkyl group having 1 to 10 carbon atoms.
(31)

The method of claim 1,
X ₁ , X ₂ , X ₃ and X ₄ each represent a tetravalent organic group including an alicyclic ring or an aromatic ring having 4 to 40 carbon atoms; Or a tetravalent aliphatic (Aliphatic) organic group having 4 to 20 carbon atoms.
The method of claim 1,
X ₁ , X ₂ , X ₃ and X ₄ are each a polymer resin compound comprising one selected from the group consisting of organic groups of the formula 5 to 23.
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

delete delete The method of claim 1,
Alkali-soluble polymer resin compound.
The method of claim 1,
Polymer resin compound having a weight average molecular weight of 1,000 to 500,000.
The method of claim 1,
A polymer resin compound further comprising at least one repeating unit selected from the group consisting of a repeating unit of Formula 3 and a repeating unit of Formula 4 below:
[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,
X ₅ and X ₆ each represent a tetravalent organic group including an alicyclic or aromatic ring having 4 to 40 carbon atoms; Or a tetravalent aliphatic organic group having 4 to 20 carbon atoms,
Y ₅ and Y ₆ are each selected from the group consisting of divalent organic groups represented by Formulas 35 to 52,
R ₅ and R ₆ are each hydrogen or an alkyl group or silylalkyl group having 1 to 10 carbon atoms,
[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

*

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

*

Formula 46

[Formula 47]

[Formula 48]

[Formula 49]

[Formula 50]

[Formula 51]

In Formula 51, R ₁ is alkylene or arylene having 2 to 8 carbon atoms, R ₂ is alkylene having 2 to 8 carbon atoms, a and b are each 0 or 1, and c is an integer of 1 to 21, and ,
[Formula 52]

In Chemical Formula 52, d is an integer of 1 to 12.
The polymer resin compound according to any one of claims 1 to 3 and 6 to 8;
Photo-active compounds; And
Contains an organic solvent,
A photosensitive resin composition further comprising a novolac resin having a polystyrene-based weight average molecular weight of 2,500 to 15,000.
10. The method of claim 9,
The photoactive compound is a photosensitive resin composition comprising a diazonaphthoquinone-based compound.
10. The method of claim 9,
The photoactive compound is a photosensitive resin composition comprising one or more selected from diazonaptoquinone-based compounds of the formula 53 to 60.
[Formula 53]

(54)

(55)

(56)

[Formula 57]

(58)

[Chemical Formula 59]

[Formula 60]

In Formulas 53 to 60, D is a compound of Formula 61 or 62.
(61)

(62)

10. The method of claim 9,
The organic solvent is N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl Ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol A photosensitive resin composition comprising at least one member selected from the group consisting of 3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxy propionate.
delete 10. The method of claim 9,
Per 100 parts by weight of the polymer resin,
1 to 50 parts by weight of the photoactive compound; And
Photosensitive resin composition comprising 20 to 2000 parts by weight of the organic solvent.
10. The method of claim 9,
Positive photosensitive resin composition in which an exposure part is developed.
An electronic device comprising an organic insulating film or a photosensitive pattern formed from the photosensitive resin composition of claim 9.
17. The method of claim 16,
The organic insulating film includes an interlayer insulating film, a surface protective film, an electrode protective layer buffer coat film or a passivation film,
The electronic device includes a component of a semiconductor device or a display device.

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