KR20200041054A - Photosensitive resin composition, photosensitive resin film, pattern and method for manufacturing bump - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a photosensitive resin film, a pattern, and a manufacturing method of a bump. The photosensitive resin composition comprises: a first polymer; a photo-acid generator; an acid diffusion control agent; and a solvent, and may improve leaching properties of a plating solution.

Description

Manufacturing method of photosensitive resin composition, photosensitive resin film, pattern and bump {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN FILM, PATTERN AND METHOD FOR MANUFACTURING BUMP}

This specification relates to a method for producing a photosensitive resin composition, a photosensitive resin film, a pattern, and a bump.

The photosensitive resin composition is used for various purposes such as a photosensitive material for manufacturing color filters, an overcoat photosensitive material, and a column spacer. In general, a photosensitive resin refers to a polymer compound in which chemical changes of a molecular structure occur within a short period of time by light irradiation, resulting in changes in physical properties such as solubility, coloring, and curing in a specific solvent.

The use of photosensitive resins enables fine precision processing, significantly reduces energy and raw materials compared to thermal reaction processes, and enables quick and accurate work in a small installation space, leading to advanced printing fields, semiconductor production, and display production , Photo-curing surface coating materials, and various other applications in the precision electronic and information industries.

Specifically, the photosensitive resin composition is used for forming bumps or metal posts by a plating process.

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 having excellent mechanical properties and being able to form an ultra-fine pattern, and having excellent adhesion to a substrate.

Korean Patent Publication No. 2001-0009058

This specification is intended to provide a method for producing a photosensitive resin composition, a photosensitive resin film, a pattern and a bump.

One embodiment of the present specification includes a first polymer comprising one or more of the structures represented by the following Formulas 1 to 4; Photoacid generator; Acid diffusion control agents; And it provides a photosensitive resin composition comprising a solvent.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 1 to 4,

R1 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group, r15 is an integer from 0 to 8, L is a direct bond; Or a substituted or unsubstituted alkylene group.

Another embodiment of the present specification provides a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment of the present specification provides a pattern prepared using the photosensitive resin composition.

Another exemplary embodiment of the present specification is a step of coating the photosensitive resin composition on a semiconductor substrate to form a photosensitive resin film; A step of forming a pattern using the photosensitive resin film: and a method of manufacturing a bump to form a bump by electroplating.

When the photosensitive resin composition according to the present specification includes a first polymer including at least one of the structures represented by Chemical Formulas 1 to 4, the etchability of the plating solution may be improved.

In addition, in the photosensitive resin composition according to the present specification, the acrylate resin represented by the first polymer further includes the second polymer and the third polymer, or the fourth in the acrylate resin represented by the first polymer. When a polymer is further included, when forming a pattern on a semiconductor device using the photosensitive resin composition, stability with time increases at room temperature (25 ° C) and high temperature (40 ° C), and resistance to leaching during plating is improved. You can.

1 is a photograph measured by FE-SEM (field emission scanning electron microscope) for the pattern surface of Example 1.
Figure 2 is a photograph measured by FE-SEM (field emission scanning electron microscope) for the pattern surface of Comparative Example 1.

Hereinafter, the present specification will be described in more detail.

In this specification, when a member is said to be positioned “on” another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.

In the present specification, when a part “includes” a certain component, this means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

Means a site that is attached to another substituent or linkage.

In the present specification, a polymer means a compound composed of repeating molecules.

In the present specification, the basic unit may mean a monomer, and the unit may be included in a main chain in a polymer to constitute a polymer.

In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms may be 1 to 30, specifically 1 to 20, and more specifically 1 to 10. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. There are, but are not limited to these.

In the present specification, the alkylene group means that the alkane has two binding positions. The alkylene group may be straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkylene group is not particularly limited, but is, for example, 1 to 30 carbon atoms, specifically 1 to 20 carbon atoms, and more specifically 1 to 10 carbon atoms.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, indenyl group, phenanthrenyl group, pyrenyl group, perylene group, triphenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. These may be applied to the description of the aryl group described above, except that each is a divalent group.

In the present specification, the alkoxy group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but may be 1 to 30, specifically 1 to 20, and more specifically 1 to 10.

One embodiment of the present specification includes a first polymer comprising one or more of the structures represented by the following Formulas 1 to 4; Photoacid generator; Acid diffusion control agents; And it provides a photosensitive resin composition comprising a solvent.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4, R1 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group, r15 is an integer from 0 to 8, L is a direct bond; Or a substituted or unsubstituted alkylene group.

A photosensitive resin composition according to an exemplary embodiment of the present specification includes a first polymer including at least one of the structures represented by Chemical Formulas 1 to 4, and thus includes a hydrophobic group and a rigid group to form a plating solution. The leaching property for can be improved.

The meaning of good etchability with respect to the plating solution means that the phenomenon that the photosensitive resin composition dissolves in the plating solution is reduced when electroplating is performed after forming a pattern using the photosensitive resin composition according to the present specification.

In addition, an exemplary embodiment of the present specification includes a second polymer including a structure represented by Formula 5 and Formula 6 below; And it provides a photosensitive resin composition that further comprises a third polymer comprising a structure represented by the following formula (5) and the formula (7), or a fourth polymer comprising a structure represented by the formula (5) to (7) .

[Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 5 to 7, X1 to X9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group.

A second polymer comprising a structure represented by the formula (5) and the formula (6) in the photosensitive resin composition according to one embodiment of the present specification; And a third polymer comprising a structure represented by Chemical Formula 5 and Chemical Formula 7, or a fourth polymer comprising a structure represented by Chemical Formulas 5 to 7, further comprising the photosensitive resin composition. Thus, when a pattern is formed on a semiconductor device, stability with time increases at room temperature (25 ° C.) and high temperature (40 ° C.), and resistance to leaching may increase when plating.

When the photosensitive resin composition includes the second polymer, there is a problem of poor stability over time, but further includes the third polymer, or the fourth polymer instead of the second polymer and the third polymer, Stability with time is increased, and resistance to leaching during plating can be improved.

In one embodiment of the present specification, R1 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R1 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R1 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

In one embodiment of the present specification, R1 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; Or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R1 to R15 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted methyl group; A substituted or unsubstituted tert-butyl group; Or a substituted or unsubstituted methoxy group.

In one embodiment of the present specification, R1 to R15 are the same as or different from each other, and each independently hydrogen; Methyl group; tert-butyl group; Or a methoxy group.

In one embodiment of the present specification, R1, R3, R5, R7, R8, R10, R12, R14 and R15 are hydrogen.

In one embodiment of the present specification, R2, R6, R9, and R13 are methyl groups.

In one embodiment of the present specification, R4 is a tert-butyl group.

In one embodiment of the present specification, R11 is a methoxy group.

In one embodiment of the present specification, r15 is an integer from 0 to 8.

In one embodiment of the present specification, L is a direct bond; Or a substituted or unsubstituted alkylene group.

In one embodiment of the present specification, L is a direct bond; Or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.

In one embodiment of the present specification, L is a direct bond; Or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

In one embodiment of the present specification, L is a direct bond; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

In one embodiment of the present specification, L is a substituted or unsubstituted ethylene group.

In one embodiment of the present specification, L is an ethylene group.

In one embodiment of the present specification, the second polymer may include a structure represented by Formula B below.

[Formula B]

In Formula B, m is an integer from 50 to 90, and n is an integer from 10 to 50.

In one embodiment of the present specification, m is 70 and n is 30.

The m and n mean each molar ratio (mol%) of the basic unit included in the second polymer represented by the formula (B).

In one embodiment of the present specification, the third polymer may include a structure represented by Formula C below.

[Chemical Formula C]

In Chemical Formula C, m is an integer from 50 to 90, and l is an integer from 10 to 50.

In one embodiment of the present specification, m is 70 and l is 30.

The m and l mean each molar ratio (mol%) of the basic unit included in the third polymer represented by the formula (C).

In one embodiment of the present specification, the fourth polymer may include a structure represented by Formula D below.

[Formula D]

In the above formula (D), m 'is an integer from 50 to 90, n' is an integer from 5 to 45, and l 'is an integer from 5 to 45.

In one embodiment of the present specification, m 'is 70, n' is 10, and l 'is 20.

In one embodiment of the present specification, m 'is 50, n' is 20, and l 'is 30.

The m ', n' and l 'mean each molar ratio (mol%) of the basic unit included in the fourth polymer represented by the formula (D).

In one embodiment of the present specification, the first polymer may include the structures represented by Chemical Formulas 1 to 4 in a random arrangement.

The random (random) arrangement means that the structures represented by Formulas 1 to 4 are linearly and irregularly arranged.

In addition, in one embodiment of the present specification, the first polymer may include a structure represented by Formula A below.

[Formula A]

In Chemical Formula A,

R1 to R15, r15 and L are as defined above, a and c are integers from 10 to 60, and b and d are integers from 10 to 50.

The a, b, c and d means each molar ratio (mol%) of the basic unit included in the first polymer represented by the formula (A).

In one embodiment of the present specification, a may be 30.

In one embodiment of the present specification, b may be 20.

In one embodiment of the present specification, c may be 30.

In one embodiment of the present specification, d may be 20.

In one embodiment of the present specification, Chemical Formula A may be represented by Chemical Formula A-1.

[Formula A-1]

In one embodiment of the present specification, the weight average molecular weight of the first polymer is 5,000 to 200,000 g / mol.

When the weight average molecular weight of the first polymer satisfies the above range, when a pattern is prepared using a photosensitive resin composition containing the first polymer, excellent pattern shape can be obtained.

The weight-average molecular weight is a value obtained by averaging the molecular weights of the molecular weights of the component molecular species of the polymer compound having a molecular weight distribution as one of the average molecular weights in which the molecular weight is not uniform and the molecular weight of a certain polymer material is used as a standard.

In one embodiment of the present specification, the polydispersity index (PDI) of the first polymer may be 1 to 5, and preferably 1 to 3.

The polydispersity index (PDI) means a value obtained by dividing a weight average molecular weight value by a number average molecular weight.

The weight average molecular weight and number average molecular weight can be measured through gel permeation chromatography (Gel Permeation Chromatography; GPC) analysis.

In one embodiment of the present specification, the weight average molecular weights of the second to fourth polymers are the same as or different from each other, and each independently is 3,000 to 7,000 g / mol.

When the weight average molecular weights of the second to fourth polymers satisfy the above range, when a pattern is prepared using a photosensitive resin composition, excellent pattern shape can be obtained.

In one embodiment of the present specification, the polydispersity index (PDI) of the second polymer to the fourth polymer is the same as or different from each other, and may be independently 1 to 5, and preferably 1 to 3.

In one embodiment of the present specification, the acid value of the first polymer may be 0 to 30 KOH mg / g.

When the acid value of the first polymer satisfies the above range, the developability of the photosensitive resin composition containing the first polymer may be improved by maintaining an appropriate acid value.

The acid value can be measured by titration with a 0.1 N concentration of potassium hydroxide (KOH) methanol solution.

In one embodiment of the present specification, the photosensitive resin composition may further include a surfactant.

The surfactant may be applied without limitation, as long as it can be used conventionally in the photosensitive resin composition in the art.

An exemplary embodiment of the present specification, based on the total weight of the photosensitive resin composition, the content of the first polymer is 10 to 40% by weight, the content of the second polymer and the third polymer or the fourth polymer is 5 to 30 Weight%, the photoacid generator content is 0.1 to 2% by weight, the acid diffusion control agent content is from 0.01 to 0.5% by weight and the solvent is 30 to 80% by weight to provide a photosensitive resin composition.

When each component of the photosensitive resin composition satisfies the weight range, a desired pattern can be easily obtained when preparing a pattern using the photosensitive resin composition.

In one embodiment of the present specification, the photosensitive resin composition may be positive.

The photosensitive resin composition can be divided into a negative type and a positive type according to the development method. The positive type has better resolution than the negative type, has a low light generation area and has a low defect rate, and uses an alkaline aqueous solution as a developer. It is advantageous in terms of wastewater treatment and environmental aspects. The pattern formation through the positive photosensitive composition is based on a photolithography method. The positive photosensitive composition is originally insoluble in alkali or changed to alkali solubility when exposed to light, and has the property of dissolving the exposed portion when developing with an aqueous alkali solution.

The photosensitive resin composition according to one embodiment of the present specification is a chemically amplified photoresist containing a photoacid generator. In the chemically amplified photoresist, acid is generated as a photoacid generator by irradiation (exposure), and the generation of acid is accelerated by heat treatment after exposure, causing an acid catalytic reaction to the base resin or the like in the photosensitive resin composition, and alkali solubility thereof. Is to change.

The photoacid generator is a compound that generates an acid by light in the photosensitive resin composition, and can be used without limitation as long as it can be commonly used in the photosensitive resin composition. Commonly used photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivatives, nitrobenzyl compounds, benzoincylate compounds, and iron arene complexes. , Halogen-containing triazine compounds, acetphenone derivative compounds, and cyano group-containing oxime sulfonate compounds, and may be specifically, azonaphthoquinone sulfonate (DNQ), but is not limited thereto.

In one embodiment of the present specification, the photoacid generator may be NAI-105 (manufactured by Midori Kagaku Co. Ltd.).

The acid diffusion control agent (Quencher) is used to control the diffusion of the acid in the photosensitive resin film. This can lower the environmental dependence and control the change in sensitivity after exposure. As the acid diffusion control agent, a basic compound is mainly used, and specific examples include triethylamine, tripropyl amine, tribenzyl amine, trihydroxyethyl amine, and trihexylamine (Trihexyl amine) and ethylene diamine (ethylene diamine) may be one or two or more selected from the group consisting of, but is not limited thereto.

In one embodiment of the present specification, the acid diffusion control agent may be trihexyl amine (manufactured by Sigma-aldrich).

The solvent may include a solvent known in the art. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, Propylene glycol methyl ether acetate, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1- Trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl Ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol monomethyl ether, and gamma-butyrolactone, etc. It is preferable to use one or more selected from the group consisting of, but not limited to these, a solvent known in the art may be used.

In one embodiment of the present specification, the solvent may be propylene glycol methyl ether acetate (PGMEA).

In addition, the photosensitive resin composition may further include one or more additives selected from the group consisting of radiation-sensitive compounds and other additives.

One embodiment of the present specification provides a photosensitive resin film prepared using the photosensitive resin composition.

The photosensitive resin composition according to the present specification may be coated on a support by an appropriate method and cured to form the photosensitive resin film.

The support is not limited, and known ones known in the art may be used. For example, a substrate for an electronic component and a predetermined wiring pattern formed thereon can be exemplified. Examples of the substrate include metal substrates such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold, and nickel, and glass substrates. As the material of the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, and the like may be used, but is not limited thereto.

According to an example, the support may be copper (Cu) deposited on a silicon substrate. In addition, the support may be deposited after depositing titanium (Ti) on a silicon wafer, and then copper (Cu).

Although the coating method is not particularly limited, a spray method, a roll coating method, a spin coating method, or the like can be used, and the spin coating method is generally widely used. In addition, after forming the coating film, in some cases, the residual solvent may be partially removed under reduced pressure.

Examples of the light source for curing include, but are not limited to, mercury vapor arcs, carbon arcs, Xe arcs, etc., which emit light having a wavelength of 250 nm to 450 nm.

One embodiment of the present specification provides a pattern prepared using the photosensitive resin composition.

The pattern may be a resist pattern or a photoresist pattern formed using a photosensitive resin film prepared using the photosensitive resin composition.

An exemplary embodiment of the present specification is a step of applying a photosensitive resin composition on a semiconductor substrate to form a photosensitive resin film; A step of forming a pattern using the photosensitive resin film: and a method of manufacturing a bump to form a bump by electroplating.

The step of forming the photosensitive resin film by applying the photosensitive resin composition on the substrate may be applied to the above-described coating method and curing.

In the step of forming a pattern using the photosensitive resin film, the pre-baked coating film is irradiated with ultraviolet light through a predetermined pattern mask, and post exposure baking is performed using a heating device such as a hot plate or oven. The pattern can be formed through post exposure-bake) and developed by an aqueous alkali solution to remove unnecessary parts.

At this time, as the developing method, a dipping method, a shower method, or the like can be applied without limitation. The development time is usually about 30 to 180 seconds. Examples of the developer used for the above development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, sodium methsilicate, and ammonia as an aqueous alkali solution; Primary amines such as ethylamine and N-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimenylamine, methyldiethylamine, and dimethylethylamine; Tertiary alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; Pyrrole, piperidine, n-methylpiperidine, n-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Cyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, corizine, rutidine, and Quiroline; Aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used.

In one embodiment of the present specification, a pattern may be formed by performing water washing after development for about 30 to 90 seconds and drying with air or nitrogen.

To form the bumps by electroplating, the substrate patterned by development may be immersed in various plating solutions for electroplating at the same temperature and time as the plating conditions to perform electroplating. The plating method is not particularly limited, and a method employed in the art may be applied.

The plating solution may be, for example, a copper (Cu) plating solution, a nickel (Ni) plating solution, or a tin silver (SnAg) plating solution, but is not limited thereto.

If necessary, the non-exposed portion of the photosensitive resin film may be peeled after the electroplating. As the peeling method, the non-exposed portion of the photosensitive resin film can be peeled by immersing the electroplated substrate in a peeling liquid at 25 to 80 ° C for 1 to 10 minutes. As the peeling solution, one used in the art can be suitably employed.

An exemplary embodiment of the present specification provides a semiconductor device including a bump manufactured by the bump manufacturing method.

The semiconductor device may further include various components generally included in semiconductor devices, and may be used in semiconductor devices.

1 is a photograph measured by FE-SEM (field emission scanning electron microscope) for the pattern surface of Example 1 according to one embodiment of the present specification. 1, it can be seen that the pattern between the pattern and the plated tin silver (SnAg) filler is clean. That is, when the pattern is manufactured using the photosensitive resin composition according to the present specification, it can be confirmed that the degree of leaching resistance is improved.

Figure 2 is a photograph measured by FE-SEM (field emission scanning electron microscope) for the pattern surface of Comparative Example 1. In FIG. 2, it can be confirmed that there is a trace in which the photosensitive resin composition was melted between the pattern according to Comparative Example 1 and the plated tin silver (SnAg) filler. This can be confirmed that when the pattern is prepared by using the photosensitive resin composition according to Comparative Example 1, the etch resistance is low.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

<Synthesis example>

Synthesis Example of First Polymer

Based on the total weight of acrylate monomers, the total amount of acrylate monomers of 30 mol%, 20 mol%, 30 mol%, and 20 mol% of the basic units represented by A, B, C, and D in the following formula A-1 is 500 g After stirring 500 g of propylene glycol monomethyl ether acetate (PGMEA), the temperature was raised to 80 ° C., 5 g of azobisisobutyronitrile (AIBN) was added, and the temperature was maintained at 80 ° C. while stirring for 12 hours to obtain a polymerization solution. It was prepared.

After diluting the prepared polymerization solution with acetone, the precipitate was collected in hexane (Hexane) and filtered to obtain a white solid, from which a first polymer having a structure represented by the following Chemical Formula A-1 was obtained. (Weight average molecular weight (Mw) = 25,000 g / mol, polydispersity index (PDI) = 1.8)

[Formula A-1]

Synthesis Example of Second Polymer

In a round bottom flask, Maruzen PHS (M2VPM, sol.con 30wt% in PGMEA) 100g, Pyridinium p-toluenesulfonate (PPTS, 0.01eq) was added and an ice bath was installed. Ethyl vinyl ether / PGMEA solution was added dropwise using a dropping funnel at 0 ° C. and stirred at 25 ^° C. for 18 hours.

After the reaction was completed, extraction was performed three times with ethyl acetate and water, and then the solvent was removed with a rotary evaporator. After dissolving it in acetone, the precipitate was collected in hexane and filtered to obtain a white solid. As a result, a second polymer having a structure represented by the following Chemical Formula B, in which Ethyl vinyl ether (EE) group is 30 mol% substituted PHS (Polyhydroxy Styrene), was synthesized. (Weight average molecular weight (Mw) = 5,500 g / mol, polydispersity index (PDI) = 1.63)

[Formula B]

In the above formula B, m is 70 and n is 30.

Synthesis Example of Third Polymer

Maruzen PHS (M2VPM, sol.con 30wt% in PGMEA) 100g, Pyridinium p-toluenesulfonate (PPTS, 0.01eq) was put in a round bottom flask and an ice bath was installed. At 0 ° C., a 3,4-dihydro-2H-pyran (DHP) / PGMEA solution was added dropwise using a dropping funnel and stirred at 25 ^° C. for 18 hours.

After the reaction was completed, extraction was performed three times with ethyl acetate and water, and then the solvent was removed with a rotary evaporator. After dissolving it in acetone, the precipitate was collected in hexane and filtered to obtain a white solid. As a result, a third polymer having a structure represented by the following Chemical Formula C, which is a polyhydroxy styrene (PHS) in which 30 mol% of Tetrahydropyranyl (THP) groups are substituted, was synthesized. (Weight average molecular weight (Mw) = 5,400 g / mol, polydispersity index (PDI) = 1.62)

[Chemical Formula C]

In Chemical Formula C, m is 70 and l is 30.

Synthesis example of the fourth polymer

Maruzen PHS (M2VPM, sol.con 30wt% in PGMEA) 100g, Pyridinium p-toluenesulfonate (PPTS, 0.01eq) was put in a round bottom flask and an ice bath was installed. The solution of 3,4-Dihydro-2H-pyran / PGMEA was added dropwise using a dropping funnel at 0 ° C and stirred at 25 ° C for 6 hours.

The ice bath was installed again, and the Ethyl vinyl ether / PGMEA solution was dropped using a dropping funnel at 0 ° C (dropwise) and stirred at 25 ° C for 18 hours.

After the reaction was completed, extraction was performed three times with ethyl acetate and water, and then the solvent was removed with a rotary evaporator. After dissolving it in acetone, the precipitate was collected in hexane and filtered to obtain a white solid.

Thus, the Ethyl vinyl ether (EE) and Tetrahydropyranyl (THP) groups are 10 mol%: 20 mol%, 20 mol%: 30 mol% substituted PHS (Polyhydroxy Styrene) substituted PHS (Polyhydroxy Styrene), respectively. 4 Polymers were synthesized. (Weight average molecular weight (Mw) = 5,630 g / mol, polydispersity index (PDI) = 1.62)

[Formula D]

In Chemical Formula D, m 'is 70, n' is 10, l 'is 20, or m' is 50, n 'is 20, and l' is 30.

Comparative Synthesis Example 1

In the synthesis example of the first polymer, except that the molar ratio of A, B, C, D of the formula A-1 is changed to 30 mol%, 20 mol%, 50 mol% of A, B, C, respectively. In the same manner as the synthesis example of the first polymer, the polymer of Comparative Synthesis Example 1 including the structure represented by the following Chemical Formula A-2 was synthesized. (Weight average molecular weight (Mw) == 25,000 g / mol, polydispersity index (PDI) = 1.82)

[Formula A-2]

Comparative Synthesis Example 2

In the synthesis example of the first polymer, A, B, C, and D of Formula A-1 are changed to A, B, C, and E of Formula A-3, and the molar ratio of A, B, C, and E Comparative Synthesis Example comprising the structure represented by the following Chemical Formula A-3 in the same manner as the synthesis example of the first polymer, except that it was changed to 30 mol%, 20 mol%, 30 mol%, and 20 mol%, respectively. The polymer of 2 was synthesized. (Weight average molecular weight (Mw) = 26,300 g / mol, polydispersity index (PDI) = 1.78)

[Formula A-3]

<Examples and Comparative Examples: Preparation of photosensitive resin composition>

By mixing the components shown in Table 1 to prepare a photosensitive resin composition of each of Examples and Comparative Examples.

Specifically, based on the total weight of the photosensitive resin composition, 40% by weight of acrylic resin, 18% by weight of Resin 2, 0.9% by weight of the photoacid generator NAI-105 (manufactured by Midori Kagaku Co.Ltd.), Acid diffusion control agent (Quencher) A photosensitive resin composition was prepared by mixing 0.1% by weight of trihexyl amine (manufactured by Sigma-aldrich) and 41% by weight of propylene glycol methyl ether acetate (PGMEA) as a solvent.

In Table 1, the addition amount (wt%) described in the acrylic resin and Resin 2 means the weight percentage of the acrylic resin and Resin 2 included based on the total weight of the resin including the acrylic resin and Resin 2.

In addition, in Formula 1-1 of Table 1, the first polymer, PHS-EE means the second polymer, PHS-THP means the third polymer, and PHS-EE-THP means the fourth polymer, respectively.

In addition, the numerical value in parentheses described in Resin 2 means a molar ratio (mol%). For example, PHS (70) -EE (30) means that in the second polymer, PHS contains 70 mol% and EE contains 30 mol%.

<Experimental Example>

Experimental Example 1: Measurement of viscosity change

The photosensitive resin composition prepared in the above Examples and Comparative Examples was stored in an oven at room temperature (25 ^o C) and 40 ^o C, and the viscosity change was measured immediately after and a month later by a viscometer (Model: DV3TRVCJ0, AMETEK BROOKFIELD product). By measuring, the storage value of the photosensitive resin composition was evaluated by subtracting the viscosity value after a month from the viscosity value immediately after preparation, and dividing it by the viscosity value immediately after preparation as a percentage. Table 2 shows the results.

Experimental Example 2: Preparation of photosensitive resin film and pattern

On the copper (Cu) substrate, spin-coated the photosensitive resin composition prepared in Examples and Comparative Examples to have a film thickness of 30 μm, dried on a hot plate at 110 ° C. for 2 minutes, and then exposed to an i-line irradiator (about 10, After exposure to 250 mJ / cm ² using 20, 30, 40, and 50 μm sized hole masks), and further dried on a hot plate at 90 ° C. for 2 minutes, about 2.38% by weight of tetra A resist pattern was prepared by developing in an aqueous solution of methylmethylammonium hydroxide (tetramethylammonium hydroxide, TMAH) for 2 minutes.

Experimental Example 3: Evaluation of the leaching phenomenon during plating

After plating the resist pattern prepared in Experimental Example 2 with copper (Cu) plating solution, nickel (Ni) plating solution, and tin silver (SnAg) plating solution with 8 ASD, 8 ASD, and 4.5 ASD, respectively, the resist pattern surface was FE- Analysis was performed through SEM (field emission scanning electron microscope, Hitachi, S-4800) equipment to evaluate the leaching phenomenon during plating based on the presence or absence of deformation of the resist pattern.

The ASD (Ampere per Square Decimeter) means the plating speed, and the higher the value of ASD, the faster the plating speed.

-None: No deformation of the resist pattern

-Yes: There is a deformation of resist pattern

In Table 2, when the viscosity change value after one month is negative (-), it means that the viscosity is increased.

According to Table 2, Examples 1 to 5 can be confirmed that the viscosity change is not large after one month at 40 ° C. and 25 ^° C. conditions. On the other hand, Comparative Examples 1 and 2 can be confirmed that the viscosity change value after one month is greater than Examples 1 to 5. Thus, it was found that Examples 1 to 5 had higher stability of the photosensitive resin composition than Comparative Examples 1 and 2.

In addition, according to Table 2, Examples 1 to 5 can be confirmed that the etching phenomenon is "none" when plating, and Comparative Examples 1 to 4 can be confirmed that the etching phenomenon is "existing" when plating. This, it was confirmed that Examples 1 to 5 have improved resistance to leaching when plating than Comparative Examples 1 to 4.

Claims (8)

A first polymer comprising at least one of the structures represented by the following formulas 1 to 4; Photoacid generator; Acid diffusion control agents; And a photosensitive resin composition comprising a solvent:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 1 to 4,
R1 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group,
r15 is an integer from 0 to 8,
L is a direct bond; Or a substituted or unsubstituted alkylene group. The method according to claim 1,
A second polymer comprising a structure represented by the following Chemical Formula 5 and Chemical Formula 6; And a third polymer comprising a structure represented by the following Chemical Formula 5 and Chemical Formula 7, or
A photosensitive resin composition further comprising a fourth polymer comprising structures represented by the following Chemical Formulas 5 to 7:
[Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 5 to 7,
X1 to X9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group. The method according to claim 1, wherein the first polymer is a photosensitive resin composition comprising a structure represented by the formula (A):
[Formula A]

In Chemical Formula A,
R1 to R15, r15 and L are as defined in claim 1,
a and c are integers of 10 to 60, and b and d are integers of 10 to 50. The method according to claim 1, The first polymer has a weight average molecular weight of 5,000 to 200,000 g / mol photosensitive resin composition. The method according to claim 2, based on the total weight of the photosensitive resin composition,
The content of the first polymer is 10 to 40% by weight,
The content of the second polymer and the third polymer or the fourth polymer is 5 to 30% by weight,
The photoacid generator content is 0.1 to 2% by weight,
The acid diffusion control agent content is 0.01 to 0.5% by weight and
The solvent is 30 to 80% by weight of the photosensitive resin composition. A photosensitive resin film prepared using the photosensitive resin composition according to any one of claims 1 to 5. The pattern produced using the photosensitive resin composition according to any one of claims 1 to 5. Forming a photosensitive resin film by applying the photosensitive resin composition according to any one of claims 1 to 5 onto a semiconductor substrate;
Forming a pattern using the photosensitive resin film: And
A method for manufacturing bumps by electroplating to form bumps.

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