KR20120068460A - Positive photoresist composition - Google Patents

Abstract

PURPOSE: A positive photo-resist composition is provided to overcome problems occurring in a reflow phenomenon after a hard baking process by forming patterns of constant shapes after a baking process. CONSTITUTION: A positive photo-resist composition includes an alkali soluble resin, a dissolution inhibitor, a compound represented by chemical formula 1, and a solvent. In chemical formula 1, A is an oxygen atom or a sulfur atom; R1 is selected from a group including a hydrogen atom, a halogen atom, a C1 to C6 linear or branched alkyl group, a C1 to C5 fluoroalkyl group, a C6 to C18 aryl group, a C4 to C18 heteroaryl group; R2 is a hydrogen atom, a C1 to C6 linear or branched alkyl group, a C2 to C6 linear or branched alkenyl group, a C6 to C18 aryl group, C4 to C18 heteroaryl group, C2 to C6 alkylcarbonyl group, C2 to C6 alkoxylcarbonyl group, or a C2 to C6 N-alkylcarbamoyl group; and n is 1 to 5.

Description

Positive photoresist composition

The present invention relates to a positive photoresist composition, and more particularly, to a positive photoresist composition excellent in thermal stability, sensitivity and pattern development.

Generally, as a positive photoresist composition, a composition containing a binder resin soluble in an alkaline developer such as a resol or cresol novolak resin and a dissolution inhibitor having a quinonediazide group is suitable. Such compositions are widely used in lithography using g-rays, i-rays, and the like.

Such lithography technology is widely used in the field of semiconductor and liquid crystal display device manufacturing in that it is relatively inexpensive and can form a pattern of resist having excellent resolution and shape.

However, in the four-mask process, the photoresist composition currently used has a problem that the channel portion is narrowed by forming a low angle profile when the heat is applied to 125 ° C. or higher during the baking process.

In order to overcome the above problems, there is a general method of introducing a high molecular weight resin or adding a high heat resistant material as a method of enhancing heat resistance to a resist. There is also a method of adding a resin in which carboxylic acids are introduced in order to maintain the dissolution rate of the resin in the developer. However, these methods are a good way to enhance the heat resistance and thermal stability of the positive photoresist, but they slow down the sensitivity of the photoresist and additionally reduce the development speed of the non-exposed areas where the pattern remains, so that they are not easily dissolved in the developer and the residues remain. This remains a problem that it is difficult to obtain a pattern capable of processing.

In order to solve the conventional problems as described above, an object of the present invention is to provide a positive photoresist composition that is excellent in the pattern shape during the LCD micropattern process, and can improve thermal stability, high sensitivity, chemical resistance, strip characteristics and the like. It is done.

In order to achieve the above object, the present invention (A) alkali-soluble resin; (B) dissolution inhibitors; (C) 0.1 to 10% by weight of the compound represented by Formula 1 based on the total weight of the composition; And (D) a solvent, wherein the positive photoresist composition is provided:

[Formula 1]

In Chemical Formula 1,

A is O or S;

R ₁ is selected from the group consisting of H, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 4 to 18 carbon atoms; ;

R ₂ is H, a linear or branched alkyl group of 1 to 6 carbon atoms, a linear or branched alkenyl group of 2 to 6 carbon atoms, an aryl group of 6 to 18 carbon atoms, a heteroaryl group of 4 to 18 carbon atoms, a 2 to 6 carbon atoms An alkylcarbonyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms,

n is 1-5.

When using the positive photoresist composition according to the present invention, it is possible to achieve high sensitivity due to the excellent pattern shape in the LCD micropattern process, and may occur in the reflow phenomenon after the hard bake by forming a certain pattern shape after the baking process In order to solve the problem, a thermally stable dispersion can be achieved, thereby reducing the defect rate, and improving the adhesion with the lower substrate, the high sensitivity, the chemical resistance, and the strip characteristics.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention (A) alkali soluble resin; (B) dissolution inhibitors; (C) 0.1 to 10% by weight of the compound represented by Formula 1, based on the total weight of the composition; And (D) provides a positive photoresist composition comprising a solvent.

More specifically, based on the total weight of the composition, (A) 10 to 25% by weight alkali-soluble resin; (B) 1 to 10% by weight dissolution inhibitor; (C) 0.1 to 10% by weight of the compound represented by Formula 1; And (D) a residual amount of the solvent such that the total weight of the composition is 100% by weight.

Positive Photoresist Composition

(A) alkali-soluble resin

The alkali-soluble resin (A) included in the positive photoresist composition of the present invention is not particularly limited, and those known in the art can be used, but preferably novolak resins can be used. In this case, the novolak resin may be obtained by addition condensation reaction between a phenol compound and an aldehyde compound.

The phenolic compound is not particularly limited, and specific examples thereof include phenol, o-, m- and p-cresol, 2,5-xylenol, 3,4-xylenol 3,5-xylenol, 2, 3,5-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 3-methyl-6-t -Butylphenol, 4-methyl-2-t-butylphenol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and the like. These can be used 1 type or in mixture of 2 or more types.

The aldehyde-based compound is not particularly limited, and specific examples thereof include formaldehyde, p-formaldehyde, acetaldehyde, propylaldehyde, phenylaldehyde, α- and β-phenylpropylaldehyde, benzaldehyde, o-, m- and p-aldehyde. Hydroxybenzaldehyde, o- and p-methylbenzaldehyde, glutaraldehyde, glyoxal and the like. These may be used alone or in combination of two or more thereof.

The addition condensation reaction between the phenolic compound and the aldehyde compound may be carried out by a conventional method in the presence of an acid catalyst. Examples of the reaction conditions may include a temperature of 60 ° C. to 250 ° C. and a reaction time of 2 to 30 hours.

Examples of the acid catalyst include organic acids such as oxalic acid, formic acid, trichloroacetic acid, p-toluenesulfonic acid, and the like; Inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, and the like; Divalent metal salts, such as zinc acetate and magnesium acetate, etc. can be used 1 type or in mixture of 2 or more types.

The addition condensation reaction may be carried out under a suitable solvent or in a bulk phase, and the alkali-soluble resin produced by such addition condensation reaction preferably has a weight average molecular weight of 2,000 to 50,000 in terms of polystyrene. It is not.

The alkali-soluble resin is preferably included in 10 to 25% by weight, more preferably in 10 to 20% by weight relative to the total weight of the composition. If the above range is satisfied, there is an advantage in coatability and proper pattern formation according to the process conditions.

(B) dissolution inhibitor

The dissolution inhibitor (B) contained in the positive photoresist composition of the present invention is not particularly limited and may be one known in the art, but preferably a phenolic compound having a hydroxyl group and a quinonediazide sulfonic acid compound Ester compounds can be used.

The phenolic compound having the hydroxyl group is not particularly limited, and specific examples thereof include phenol, o-, m- and p-cresol, 2,5-xylenol, 3,4-xylenol 3,5-k Silenol, 2,3,5-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 3- Methyl-6-t-butylphenol, 4-methyl-2-t-butylphenol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene These etc. are mentioned, These can be used 1 type or in mixture of 2 or more types.

The quinonediazide sulfonic acid compound is not particularly limited, and specific examples thereof include an o-quinonediazide sulfonic acid compound.

Specific examples of the ester compound include phenolic polyhydroxy compounds having at least three hydroxyl groups, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, or 1 And ester compounds of, 2-benzoquinonediazide-4-sulfonic acid.

The ester compound can be obtained by reacting the phenolic compound having a hydroxyl group with o-quinonediazide sulfonyl halide in the presence of triethylamine base in a suitable solvent. Thereafter, suitable workup may be performed to separate the desired quinonediazide sulfonic acid ester.

Such post-treatment includes, for example, a method of mixing a reactant with water to precipitate a desired compound, filtration and drying to obtain a powdery product; The reaction is treated with a resist solvent such as 2-heptanone, washed with water, phase separated, and the solvent is removed by distillation or equilibrium flash distillation to obtain the product in the form of a solution in the resist solvent. In this case, the equilibrium flash distillation refers to a kind of continuous distillation which distills a part of the liquid mixture and separates the vapor into the liquid phase when equilibrium is achieved by sufficiently contacting the generated vapor with the liquid phase. This method is suitable for the concentration of the thermosensitive material because it has a very good vaporization rate, vaporization takes place in an instant, and the equilibrium between vapor and liquid phase is rapid.

The dissolution inhibitor is preferably included in 1 to 10% by weight, more preferably in 1 to 5% by weight based on the total weight of the composition. When the above range is satisfied, there are advantages such as contrast improvement and residual film ratio improvement of the resist.

(C) a compound represented by the following formula (1)

The compound represented by the following Chemical Formula 1 included in the positive photoresist composition of the present invention is an oxetane compound, which provides a high thermal sensitivity and a constant thermal stability after the hard bake process.

[Formula 1]

In Chemical Formula 1,

A is O or S;

R ₁ is selected from the group consisting of H, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 4 to 18 carbon atoms; ;

R ₂ is H, a linear or branched alkyl group of 1 to 6 carbon atoms, a linear or branched alkenyl group of 2 to 6 carbon atoms, an aryl group of 6 to 18 carbon atoms, a heteroaryl group of 4 to 18 carbon atoms, a 2 to 6 carbon atoms An alkylcarbonyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms,

n is 1-5.

Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in R ₁ of Chemical Formula 1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and the like, but are not limited thereto.

Examples of the fluoroalkyl group having 1 to 6 carbon atoms in R ₁ of Formula 1 include, but are not limited to, trifluoromethyl group, pafluoromethyl group, pafluorotoethyl group, and pafluoropropyl group.

The halogen atom in R ₁ of Formula 1 is preferably a fluorine atom, but is not limited thereto.

Examples of the aryl group having 6 to 18 carbon atoms in R ₁ of Formula 1 include a phenyl group and a naphthal group, but are not limited thereto.

Examples of the heteroaryl group having 4 to 18 carbon atoms in R ₁ of Formula 1 include a furyl group, a thienyl group, and the like, but are not limited thereto.

Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in R ₂ of Formula 1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like, but are not limited thereto.

Examples of the linear or branched alkenyl group having 2 to 6 carbon atoms in R ₂ of Formula 1 include 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, and 1- Butenyl group, 2-butenyl group, 3-butenyl group, and the like, but are not limited thereto.

Examples of the aryl group having 6 to 18 carbon atoms in R ₂ of Formula 1 include a benzyl group, a fluorobenzyl group, a methoxybenzyl group, a phenethyl group, a styryl group, cinnamil group, an ethoxybenzyl group, and the like. Do not.

Examples of the heteroaryl group having 4 to 18 carbon atoms in R ₂ of Formula 1 include an aryloxyalkyl group such as a phenoxymethyl group and a phenoxyethyl group, but are not limited thereto.

Examples of the alkyl carbonyl group having 2 to 6 carbon atoms in R ₂ of Formula 1 include an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group, but are not limited thereto.

Examples of the alkoxycarbonyl group having 2 to 6 carbon atoms in R ₂ of Formula 1 include an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, and the like, but are not limited thereto.

Examples of the N-alkylcarbamoyl group having 2 to 6 carbon atoms in R ₂ of Formula 1 include an ethyl carbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, a pentylcarbamoyl group, and the like, but are not limited thereto. .

In addition, in Formula 1, R ₁ and R ₂ may be a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and 6 to 6 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an aryl group of 18 and a heteroaryl group having 6 to 18 carbon atoms.

N is 1-5, Preferably it is 1-3, More preferably, it is 1.

More specific examples of the compound represented by Formula 1 include 3-ethyl-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, and (3-ethyl-3-oxetanylmethoxy) methylbenzene , 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [ 1- (3-ethyl-3-oxetanylmethoxy) ethylphenyl ether, isobutoxymethyl (3-ethyl-3 oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl Ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-oxetanyl Methyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylethyl (3- To ethyl-3-oxetanylmethyl) ether and tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) Ter, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl -3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether , 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanyl Methyl) ether, pentabormophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like, and these may be used alone or in combination of two or more thereof. It can be mixed and used.

Preferably, the compound represented by the formula (1) is 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, 3-propyl-3-((2-ethylhexyloxy) methyl) jade Cetane, 3-ethyl-3-((2-ethylheptyloxy) methyl) oxetane, 3-propyl-3-((2-ethylheptyloxy) methyl) oxetane, 3,3'-oxybis (methylene) Bis (3-ethyloxetane), 3,3'-oxybis (ethylene) bis (3-ethyloxetane) can be used, more preferably (3-ethyloxetan-3-yl) methanol, ( 3-ethyloxetan-3-yl) ethanol, (3-propyloxetan-3-yl) methanol, (3-propyloxetan-3-yl) ethanol and the like can be used.

Since the oxetane compound represented by the formula (1) according to the present invention is heat stable and low molecular weight, it shows a flowability that maintains a stable shape stably during the heating process, thereby causing a problem of temperature variation by position in a large area substrate. It is possible to solve the problem, to exhibit excellent thermal stability, high sensitivity, and excellent resolution, and to form the same wiring in a later process.

The compound represented by Formula 1 is preferably included in 0.1 to 10% by weight, more preferably in 0.1 to 5% by weight relative to the total weight of the composition. When in the above range, there is an advantage that the reduction in resolution at high sensitivity is suppressed.

Meanwhile, the positive photoresist composition of the present invention may further include a low molecular weight phenolic compound and / or a surfactant as an additive in addition to the compound represented by Chemical Formula 1.

The low molecular weight phenolic compound is not particularly limited, and specific examples thereof include 4,4 '-(2-hydroxybenzylidene) di-2,6-xylenol), 4,4'-(3-hydroxybenzyl Lidene) di-2,6-xylenol), 4,4 '-(4-hydroxybenzylidene) di-2,6-xylenol), 4,4'-(2-methylbenzylidene) di -2,6-xylenol), 4,4 '-(3-ethylbenzylidene) di-2,6-xylenol), 4,4'-(3-methylbenzylidene) di-2,6 -Xyllenol), 4,4 '-(4-methylcybenzylidene) di-2,6-xylenol), 4- (2-hydroxybenzylidene) -2,6-xylenol), 3- (2-hydroxybenzylidene) -2,6-xylenol), 4,4 '-(2-hydroxybenzylidene) di-2,6-xylenol), 4,4'-( 2-hydroxybenzylidene) di-2-methylphenol), 4,4 '-(2-hydroxybenzylidene) di-3-methylphenol), etc. are mentioned. Preferably 4,4 '-(2-hydroxybenzylidene) di-2,6-xylenol), 4,4'-(3-hydroxybenzylidene) di-2,6-xylenol) , 4,4 '-(4-hydroxybenzylidene) di-2,6-xylenol) and the like, and more preferably 4,4'-(2-hydroxybenzylidene) di-2 , 6-xylenol) can be used. The low molecular weight phenolic compound is preferably used in 0.001 to 10% by weight based on the total weight of the composition, because there is an advantage that the shape of the residue and pattern within the above range is good.

In addition, the surfactant can be used without any particular limitation known in the art, for example, a silicone-based surfactant, a fluorine-based surfactant may be used alone or in combination of two or more. The surfactant is preferably used in 0.001 to 10% by weight relative to the total weight of the composition in terms of planarization.

(D) solvent

The solvent (D) included in the positive resist composition of the present invention dissolves the (A) alkali-soluble resin, (B) dissolution inhibitor, and (C) the compound represented by the formula (1), and the solution of the positive photoresist composition of the present invention It exists in the form of. The solvent is preferably contained in the remaining amount so that the total weight of the composition is 100%.

The solvent is not particularly limited as long as it is capable of dissolving the components of the present invention, has a suitable drying speed, and can form a uniform and smooth coating film after evaporation of the solvent.

Examples of the solvent include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol and monoethyl ether acetate; Glycol ethers such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Esters such as ethyl acetate, butyl acetate, amyl acetate ethyl pyruvate and ethyl lactate; Ketones such as acetone, methyl isobutyl ketone, 2-heptone and cyclohexanone; And cyclic ester, such as (gamma) -butyrol acetone, etc. are mentioned, These can be used individually or in combination of 2 or more types.

<Pattern Forming Method Using Positive Photoresist Composition>

The positive photoresist composition of the present invention may be applied to a substrate in conventional manner, including dipping, spraying, spinning and spin coating. For example, in the case of spin coating, a coating having a desired thickness can be formed by appropriately changing the solids content of the photoresist solution according to the type and method of the spinning apparatus.

The substrate includes silicon, aluminum, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramics, aluminum / copper mixtures, and various polymerizable resins.

The coated positive photoresist composition may be soft baked at a temperature of 20 ° C to 110 ° C. The soft bake is to evaporate the solvent without pyrolyzing the solid component in the photoresist composition. In general, it is desirable to minimize the concentration of the solvent through a soft bake process, so this treatment is performed until most of the solvent has evaporated leaving a thin coating of photoresist composition on the substrate.

Next, the substrate on which the photoresist film is formed is exposed using a suitable mask or template. At this time, it is preferable to expose with a short wavelength high energy ray, X-ray, or an electron beam of wavelength 500nm or less.

The substrate including the exposed photoresist film is sufficiently immersed in an alkaline developing aqueous solution, and then left until all or almost all of the exposed photoresist film is dissolved. Although it does not specifically limit as said alkaline developing aqueous solution, The aqueous solution containing alkali hydroxide, ammonium hydroxide, tetramethylammonium hydroxide (TMAH), (2-hydroxyethyl) trimethyl ammonium hydroxide (also called "choline") Can be used.

After the exposed portion is dissolved and removed, the substrate on which the photoresist pattern is formed may be taken out of the developer, and then a hard bake process may be performed to enhance adhesion and chemical resistance of the photoresist film. The hard bake process is preferably performed at a temperature below the softening point of the photoresist film, and more preferably at a temperature of about 100 ℃ to 150 ℃.

Subsequently, the substrate on which the photoresist pattern is formed is etched using wet etching using an etching solution or dry etching using a gas plasma. At this time, the substrate located below the photoresist pattern is protected. After the substrate is treated in this manner, a fine circuit pattern is formed on the substrate by removing the photoresist pattern with an appropriate stripper.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

In the following, the percentages, parts and ratios indicating the content or amount used are all by weight unless otherwise indicated. The weight average molecular weight is a value measured by GPC using polystyrene as a standard.

Synthesis Example 1 : Novolac  Preparation of Resin A-1

m-cresol and p-cresol were mixed at a weight ratio of 60:40, formalin was added thereto, and condensed by a conventional method using an oxalic acid catalyst to obtain a cresol novolak resin. This resin was fractionated and cut except for the polymer region and the low molecular region to obtain a novolak resin having a weight average molecular weight of 15,000. Hereinafter, this novolak resin is called A-1.

Synthesis Example 2 : Novolac  Preparation of Resin A-2

m-cresol and p-cresol were mixed at a weight ratio of 50:50, formalin was added thereto, and condensed by a conventional method using an oxalic acid catalyst to obtain a cresol novolak resin. This resin was fractionated and cut except for the polymer region and the low molecular region to obtain a novolak resin having a weight average molecular weight of 16,000. Hereinafter, this novolak resin is called A-2.

Example  1 to 4 and Comparative example  1 to 5: positive Photoresist  Composition manufacturing

The additives of the novolak resin and cationic initiator shown in Table 1 were premixed according to the composition ratios shown in Table 1 below. Thereafter, the premixed novolak resin and the oxetane compound shown in Table 1 were mixed with a solvent together with a dissolution inhibitor, a low molecular weight phenolic compound, and a surfactant to prepare a positive photoresist composition. At this time, the content of the constituents excluding the surfactant and the solvent is based on the content converted into solids.

A-1: the novolak resin manufactured by the synthesis example 1

A-2: the novolak resin manufactured by the synthesis example 2

B: 2,6-bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol with a reaction molar ratio of 1: 2.2, 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (powder form)

C-1: (3-ethyloxetan-3-yl) methanol

C-2: 3-ethyl-3 ((2-ethylhexyloxy) methyl) oxetane

C-3: 3,3'-oxybis (methylene) bis (3-ethyl oxetane)

D: 4,4 '-(2-hydroxybenzylidene) di-2,6-xylenol

E: fluorine-based surfactant

F: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

Test Example Positive Photoresist  Evaluation of the properties of the composition

The photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were filtered through a fluorine resin filter to obtain a resist solution. The resist solutions were spin coated onto a silicon wafer treated with hexamethyldisilazane and pre-baked at 110 ° C. for 130 seconds directly on a hot plate to form a resist film having a thickness of 1.50 μm.

The line-and-space pattern was formed on the wafer having the resist film using an i-line stepper ("NSR-2005 i9C", manufactured by Nikon Co., Ltd., NA = 0.57, sigma = 0.60) while gradually changing the exposure amount. It used for exposure process. Thereafter, a puddle development was performed for 60 seconds using an aqueous 2.38% tetramethylammonium hydroxide solution.

In addition, the sensitivity, resolution, strip and thermal stability were evaluated for each pattern by the following method, and the results are shown in Table 2 below.

<Effectiveness>

The exposure amount when the cross section of the 3.0 μm line-and-space pattern is 1: 1 is shown.

<Resolution>

When exposed to effective sensitivity, it represents the smallest discrete line width of the line-and-space pattern.

<Strip>

The surface after the strip was observed using PRS2000 (manufacturer: Dongwoo Finechem).

<Thermal stability>

After treatment at 130 ° C. for 150 seconds on a hot plate, the results were evaluated by comparing the profiles with the results using the scanning electron microscope.

Effective sensitivity resolution strip Thermal stability Example 1 ○ ○ ○ ○ Example 2 ○ ○ ○ ○ Example 3 ◎ ○ ○ ○ Example 4 ◎ ○ ○ ○ Comparative Example 1 △ ○ ○ X Comparative Example 2 △ ○ ○ X Comparative Example 3 ○ X ○ ◎ Comparative Example 4 X △ ○ ○ Comparative Example 5 X △ ○ △

Effective sensitivity / Resolution / Strip: ◎: Very good, ○: Good, △: Normal, X: Bad

Thermal stability: ◎: Constant shape by position, ○: Small change, △: Normal, X: Poor

As described in Table 2, the positive photoresist composition according to the present invention is excellent in the profile and thermal stability of the pattern, it can be seen that the sensitivity characteristics and strip characteristics are improved. On the other hand, the positive photoresist compositions of Comparative Examples 1 and 2 did not have good thermal stability, and the positive photoresist compositions of Comparative Example 3 did not have good resolution as compared to the embodiments of the present invention. , Comparative Examples 4 and 5 can be seen that the effective sensitivity is not good.

Claims (9)

(A) alkali-soluble resins;
(B) dissolution inhibitors;
(C) 0.1 to 10% by weight of the compound represented by Formula 1 based on the total weight of the composition; And
(D) solvent
Positive photoresist composition comprising:
[Formula 1]

In Chemical Formula 1,
A is O or S;
R ₁ is selected from the group consisting of H, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 4 to 18 carbon atoms; ;
R ₂ is H, a linear or branched alkyl group of 1 to 6 carbon atoms, a linear or branched alkenyl group of 2 to 6 carbon atoms, an aryl group of 6 to 18 carbon atoms, a heteroaryl group of 4 to 18 carbon atoms, a 2 to 6 carbon atoms An alkylcarbonyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms,
n is 1-5.
The method according to claim 1,
(A) 10 to 25% by weight, based on the total weight of the composition; (B) 1 to 10% by weight dissolution inhibitor; (C) 0.1 to 10% by weight of the compound represented by Formula 1; And (D) a residual amount of solvent such that the total weight of the composition is 100% by weight.
The method according to claim 1,
The positive photoresist composition further comprises at least one of a low molecular weight phenolic compound and a surfactant.
The method according to claim 3,
The content of the low molecular weight phenolic compound is a positive photoresist composition, characterized in that 0.001 to 10% by weight based on the total weight of the composition.
The method according to claim 3,
The amount of the surfactant is positive photoresist composition, characterized in that 0.001 to 10% by weight relative to the total weight of the composition.
The method according to claim 1,
The compound represented by the formula (1) is 3-ethyl-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4- Fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- ( 3-ethyl-3-oxetanylmethoxy) ethylphenyl ether, isobutoxymethyl (3-ethyl-3 oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, Isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-oxetanylmethyl) ether , Dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylethyl (3-ethyl-3 -Oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl ( 3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl Ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl ( 3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabormo 1 or 2 or more types selected from the group consisting of phenyl (3-ethyl-3-oxetanylmethyl) ether and bornyl (3-ethyl-3-oxetanylmethyl) ether.
The method according to claim 1,
The alkali soluble resin is a novolak resin, characterized in that the positive photoresist composition.
The method according to claim 1,
The dissolution inhibitor is a positive photoresist composition, characterized in that the ester compound of the phenolic compound having a hydroxyl group and the quinone diazide sulfonic acid compound.
The method according to claim 1,
The solvent is a positive photoresist composition, characterized in that one or two or more selected from the group consisting of glycol ether esters, glycol ethers, esters, ketones and cyclic esters.