KR101449563B1 - Photosensitive compound and method of manufacturing the same, and photosensitive composition comprising the same - Google Patents

Abstract

The photosensitive compound according to an embodiment of the present invention includes at least one naphthoquinone diazide sulfoxy group and at least two benzyl alcohol groups or alkoxymethyl groups having 12 to 20 carbon atoms in one molecule.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive compound, a photosensitive composition containing the photosensitive compound, and a photosensitive composition containing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a photosensitive compound for semiconductor processing, and more particularly, to a photosensitive compound capable of improving the perpendicularity and residual film ratio of a pattern in a semiconductor photolithography process and a photosensitive composition comprising the same, And a method for producing the same.

In general, sulfonic acid esters are used as photosensitive materials in compositions used in photolithography processes using visible light, ultraviolet light, electron beams, ion beams, and X-rays.

The photosensitive composition is prepared by mixing a resin (resin) which dissolves in a basic aqueous solution and a solvent and the sulfonic acid ester. The photosensitive composition is applied to a substrate or the like and then heated to a temperature of 50 to 150 DEG C so that the residual solvent can be easily removed. The film formed after heating is exposed using an exposure machine and then developed with a developing solution to obtain a pattern to be obtained. At this time, the sulfonic acid ester exposed to ultraviolet light is transformed into a carboxylic acid which can be dissolved in a basic developer solution. As described above, it is possible to obtain a pattern to be obtained by using the developing speed difference between the exposed portion and the non-exposed portion.

Recently, since the semiconductor process has become complicated and various film thicknesses are required, the kinds of sulfonic acid esters used as photosensitive compounds contained in the photosensitive resin composition have also been diversified. However, in general, since the ballast can not bind to the resin after curing, There is a problem of lowering.

The present invention has been proposed to overcome the above-mentioned problems, and an object of the present invention is to provide a photosensitive compound which is excellent in sensitivity at the time of exposure and can improve the residual film ratio and the vertical property of the pattern after curing.

Another object of the present invention is to provide a photosensitive resin composition capable of improving the vertical characteristics and residual film ratio of a pattern formed after a photolithography process in a semiconductor process.

It is still another object of the present invention to provide a production method capable of producing a photosensitive compound with high efficiency.

The photosensitive compound according to an embodiment of the present invention contains at least one naphthoquinone diazide sulfoxy group and at least two benzyl alcohol groups or alkoxymethyl groups having 12 to 20 carbon atoms in one molecule.

The molecule may be a sulfonic acid ester compound represented by the following formula (1).

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an ether group having 2 to 8 carbon atoms, An ester group of 3 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, a carbamate group of 1 to 8 carbon atoms, a thioether group of 2 to 8 carbon atoms, or a naphthoquinone diazide sulfoxy group (-ODNQ) Is at least one compound group selected from the group consisting of formulas (2) to (13).

(2) to (13)

In the above formulas (2) to (13), R ⁷ , R ⁸ And R ⁹ are each independently a divalent to hexavalent acyl group having at least 6 carbon atoms, and in the formula (10), R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms .

The photosensitive resin composition according to another embodiment of the present invention may contain at least one selected from the group consisting of novolac derivatives, polyhydroxystyrene derivatives, acrylic acid-containing polyacrylate derivatives, (meth) acrylic acid derivatives, styrene derivatives, polyamide derivatives, polyimide derivatives, At least one resin component selected from the group consisting of monovalent derivatives; And a photosensitive compound represented by the following formula (1), wherein a substituent group substituted by a naphthoquinone diazide sulfoxy group (-ODNQ) in 1 mole of the photosensitive compound with respect to 1 mole of the photosensitive compound present in the entire composition, At least two benzyl alcohol groups or an alkoxymethyl group substituted with 0.2 to 4.0 moles of a substituent.

[Chemical Formula 1]

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an ether group having 2 to 8 carbon atoms, An ester group of 3 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, a carbamate group of 1 to 8 carbon atoms, a thioether group of 2 to 8 carbon atoms, or a naphthoquinone diazide sulfoxy group (-ODNQ) Is at least one compound group selected from the group consisting of formulas (2) to (13).

(2) to (13)

In the above formulas (2) to (13), R ⁷ , R ⁸ And R ⁹ are each independently a divalent to hexavalent acyl group having at least 6 carbon atoms, and in the formula (10), R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms .

In the above formulas (2) to (13), R ⁷ , R ⁸ And R ⁹ are each independently a divalent to hexavalent acyl group having at least 6 carbon atoms, and in the formula (10), R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms .

The photosensitive compound may have a content of 1 to 30% by weight in the total composition, and may include a plurality of photosensitive compounds having different substitution ratios of naphthoquinone diazide sulfoxide group (-ODNQ) and benzyl alcohol.

According to another embodiment of the present invention, there is provided a method of preparing a photosensitive compound, comprising: reacting a phenol group containing at least two benzyl alcohol groups or alkoxymethyl groups under a first basic catalyst to produce a first reactant; And cooling the reaction solution containing naphthoquinonediazide sulfonyl chloride (-DNQ-Cl) to the first reactant and reacting the first reactant under a second basic catalyst to produce a second reactant.

The first basic catalyst and the second basic catalyst may each be a tertiary amine catalyst.

The photoresist photosensitive resin composition containing the photosensitive compound according to an embodiment of the present invention is excellent in sensitivity and can be easily crosslinked during a semiconductor process. In addition, the thermally decomposed sulfonic acid ester acts as a crosslinking agent, so that the vertical characteristic and the residual film ratio of the pattern can be improved.

In addition, the photoresist photosensitive resin composition containing the photosensitive compound according to an embodiment of the present invention can be used as an insulating film of various semiconductor devices or display devices after curing and patterning.

Hereinafter, the photosensitive compound and the photosensitive resin composition according to the present invention will be described in detail. However, the following description is only an exemplary description of the present invention, and the technical idea of the present invention is not limited by the following description, and the technical idea of the present invention is defined by the claims that follow.

The photosensitive compound according to one embodiment of the present invention includes naphthoquinonediazidesulfonic acid ester (hereinafter referred to as "DNQ-esterase"). The DNQ-ester can be obtained by reacting a compound having at least one benzyl alcohol group or alkoxymethylbenzene group with naphthoquinonediazide sulfonyl chloride (DNQ-Cl) in the presence of a basic catalyst. For example, a DNQ-ester can be formed through a reaction such as the following reaction formula (1) or the following reaction formula (2).

[Reaction Scheme 1]

[Reaction Scheme 2]

In the above reaction formula (1), the amount of the DNQ group and the alkylcarbonyl or arylcarbonyl group may be arbitrarily controlled. However, when the DNQ group is substituted by 1 mole or less and the alkyl group or the arylcarbonyl group is substituted by 2 mole or more, the dissolution rate for the basic developer may be lowered and the film may not be developed to the bottom due to the high film thickness. If the DNQ group is substituted by 4 moles or more and the alkyl group or the aryl group is substituted by 0.2 mole or less, a disadvantage may occur that the residue may remain on the substrate after development. The proper amount of substitution in the DNQ group is most suitable from 1.0 mole to 3.5 mole. The substitution amount of DNQ can be suitably adjusted in consideration of the thickness and exposure energy of the film using the composition. When DNQ 4 moles is substituted, the solubility rate can be controlled by replacing the alcohol with an alkyl group when the residual ratio is low. Specifically, the primary alcohol is substituted with primary alcohol having from 1 to 3 carbon atoms. The higher the polarity of the resin in the mixture, the higher the residual film ratio than when the hydroxyl groups were replaced with anhydrides.

The synthesis of the sulfonic acid ester can be carried out in a similar manner to the introduction of a DNQ group into a compound having two or more phenol-type hydroxy groups. Depending on the case, the first reaction and the second reaction may be separated or reacted simultaneously. In the general reaction, a compound having two or more phenolic hydroxy groups and DNQ-Cl are dissolved in a solvent, the mixture is cooled to 10 ° C or lower, and then the basic catalyst is slowly added dropwise. After the dropwise addition, the mixture is stirred at room temperature for a sufficient period of time, and then the alkyl group or the aryl anhydride is added dropwise, followed by gradually dropping the basic catalyst at 10 ° C. After completion of the dropwise addition, the mixture is stirred at room temperature for a sufficient time, and then the reaction mixture is added dropwise to an excessive amount of distilled water to obtain a product as a precipitate. At this time, the obtained product is vacuum-dried at 40 DEG C or lower to be used for the preparation of a composition.

The solvent used in this reaction is not particularly limited, but any solvent that does not participate in the reaction while being a solvent that dissolves compounds such as dioxane, tetrahydrofuran, dichloromethane, and chloroform may be used. The reaction time varies slightly depending on the structure of the compound, but it progresses more than 90% at room temperature for 5 hours or more. As the basic catalyst, any of tertiary amines or pyridines generally used may be used, but tertiary amines have a merit that the reaction rate is slightly faster than that of pyridine. Other basic catalysts should not react directly with DNQ-Cl. However, it is troublesome to completely remove the metal component after the reaction. The resulting product is used in the form of a mixture of different amounts of substitution. The degree of reaction can be confirmed by HPLC or ¹ H-NMR. In the above reaction scheme (2), the methoxy group is composed of a crosslinkable reactor and the phenol group is substituted with DNQ. Reaction formula (2) shows higher degree of crosslinking because of better reactivity of methoxy group.

The photosensitive compound according to an embodiment of the present invention includes at least one naphthoquinone diazide sulfoxy group (-ODNQ) in one molecule and at least two benzoyl alcohol groups or alkoxymethyl groups having 12 to 20 carbon atoms Quinone diazide sulfonic acid ester compound.

Meanwhile, the photosensitive composition according to an embodiment of the present invention may include a novolak derivative, a polyhydroxystyrene derivative, an acrylic acid-containing polyacrylate derivative, an acrylic acid derivative, a styrene derivative, a polyamide derivative, a polyimide derivative and a polyvinylpyrrolidone derivative , And a photosensitive compound represented by the following chemical formula (1).

Within 1 mole of the photosensitive compound, a substituent group substituted with a naphthoquinone diazide sulfoxide group (-ODNQ) and a substituent group substituted with a methoxy group are present in a distribution of 0.2 to 4.0 moles, respectively.

[Chemical Formula 1]

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an ether group having 2 to 8 carbon atoms, An ester group of 3 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, a carbamate group of 1 to 8 carbon atoms, a thioether group of 2 to 8 carbon atoms, or a naphthoquinone diazide sulfoxy group (-ODNQ) Is at least one compound group selected from the group consisting of formulas (2) to (13).

(2) to (13)

In the above formulas (2) to (13), R ⁷ , R ⁸ And R ⁹ are each independently a divalent to hexavalent acyl group having at least 6 carbon atoms, and in the formula (10), R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms .

The photosensitive compound may be produced by substituting both a DNQ group and a carboxy group or an alkoxy group for a phenol-type hydroxy or benzyl alcohol group in order to maximize the dissolution inhibiting effect while minimizing the thickness reduction after development. In general, the DNQ group receives ultraviolet rays and is deformed as shown in the following reaction formula to improve the transmittance to ultraviolet rays. However, the transmittance of the DNQ group is lower than that of the DNQ group.

[Reaction Scheme 3]

In the above reaction formula (3), R is an alkyl group or an aryl group having 1 to 8 carbon atoms. The above reaction formula (3) illustrates the reaction of replacing the hydroxyl group of methoxymethylbenzene with an anhydride.

The amount of the DNQ group, the benzyl alcohol and the methoxymethylbenzene group in the above reaction scheme can be arbitrarily controlled. However, if the DNQ group is substituted by 3.5 mol or more, the dissolution rate for the basic developer may be lowered. If the DNQ group is substituted by 2.5 mole or more and the alkyl group or aryl group is substituted by 0.2 mole or less, there may be a disadvantage that the residue may remain on the substrate after development. The appropriate amount of substitution of the DNQ group is preferably 1.0 to 2.5 moles. The substitution amount of DNQ can be suitably adjusted in consideration of the thickness and exposure energy of the film using the composition.

The solvent used in this reaction is not particularly limited, but may be a solvent which dissolves compounds such as dioxane, tetrahydrofuran, dichloromethane, chloroform and the like but does not participate in the reaction. The reaction time varies slightly depending on the structure of the compound, but it is more than 90% at room temperature for more than 10 hours. As the basic catalyst, any of the commonly used tertiary amines or metal catalysts may be used. Other basic catalysts should not react directly with DNQ-Cl. However, it is troublesome to completely remove the metal component after the reaction. The resulting product is used in the form of a mixture of different amounts of substitution. The degree of reaction can be confirmed by HPLC or ¹ H-NMR.

The photosensitive composition can be prepared by dissolving a resin soluble in a basic developer, a DNQ-ester compound and some additives in a solvent. If the rate of dissolution of the resin in the basic developer is fast, increasing the amount of sulfonate ester can reduce the amount of film loss at the unexposed area after development. In general, when the amount of the sulfonic acid ester compound is increased, the transparency of the film is decreased and the formed pattern becomes less vertical or a residue remains on the substrate. The photosensitive compound according to an embodiment of the present invention is characterized in that the degree of perpendicularity of the pattern during curing is prevented by the crosslinking of the ballast and the loss of the final film thickness after coating is small.

The dissolution rate of the resin in the basic developer may vary depending on the application of the composition. Generally used resins are resins which are soluble in basic developers such as novolak resins, polyhydroxy styrenes, polyacrylates containing acrylic acid or copolymers with styrene, polyamides, polyimides, polyvinylpyrrolidone and the like. I do not. Examples of the solvent to be used include propylene glycol methyl ether acetate, gamma-butyrolactone, 2-heptanone, cyclohexanone, methoxyacetoxypropane, ethylcellosolve acetate, butyl acetate, ethyl lactate, ethyl ethoxypropionate, methyl Methoxypropionate, and xylene. However, if the volatility is too high, the coating flatness is lowered. If the volatility is too low, there is a disadvantage that the residual solvent is large in the film. Depending on the intended thickness and application of the film, one or more of them can be selected and used.

The total solids content used in the composition depends on the required film thickness. The amount of sulfonic acid ester used can be from 5% to 50% based on the resin. The amount can vary depending on the dissolution rate of the resin in the basic developer. If the dissolution rate for the developer is good, increasing the content of the sulfonic acid ester can prevent film loss at the non-exposed portion. As the components used in other compositions, a UV sensitizer, a plasticizer for preventing cracking, a surfactant for improving flatness, and a small amount of additives for controlling the sensitivity are used. As additives for improving the developing speed, pyridine containing a carboxylic acid or a low-molecular compound having a phenol-type hardoxy group is used.

The prepared composition can form a film on the substrate to a certain thickness by a method such as rotation chart, spray coating, slit coating, etc. regardless of the substrate. The formed film is heated at 60 to 160 DEG C for 30 to 300 seconds to remove residual solvent. The film from which the solvent has been removed can be obtained by exposure to ultraviolet rays passing through the mask. The film exposed to ultraviolet rays may be subjected to a heating process again in order to optimize the pattern shape as the case may be. The film thus treated is developed with a basic developer and washed with deionized water to obtain a clean pattern. The basic developer is mainly a tetramethylammonium hydroxide solution, but it can be selected depending on the pattern size and working environment such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, amines and pyridines.

The photosensitive resin composition of the present invention shows the final film thickness of the final high thickness while maintaining the pattern upon curing after development.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the technical idea of the present invention is not limited by the following embodiments.

Synthetic example

[ Synthetic example  One: Novolac  Resin Synthesis (Resin A)]

70 g of m-cresol, 60 g of p-cresol and 15 g of 2,5-xylenol were placed in a round flask, and 5 g of oxalic acid and 0.3 g of an aqueous hydrochloric acid solution (35%) were added as a reaction catalyst, followed by stirring at room temperature for 10 minutes. 15 g of acetaldehyde and 60 g of formaldehyde aqueous solution (37%) were slowly added dropwise, followed by stirring at 90 ° C for 8 hours. After the reaction was partially advanced, the internal temperature was raised to 180 ° C to remove the mixed water. If the water was no longer removed, the temperature was raised to 195 ° C to remove unreacted monomers. At this time, the degree of vacuum was maximized to remove the low molecular weight and monomers contained in the novolac resin as much as possible. The obtained novolac resin (130 g) had a polystyrene-reduced molecular weight of 3,800 and a degree of dispersion of 2.8.

 [ Synthetic example  2: Synthesis of Benzyl Ether Resin (Resin B)]

In a round flask, 130 g of 4-methoxymethylphenol was added, and 7 g of oxalic acid and 0.3 g of an aqueous hydrochloric acid solution (35%) were added as a reaction catalyst, followed by stirring at room temperature for 10 minutes. After the reaction mixture was thoroughly mixed, 15 g of acetaldehyde and 60 g of an aqueous formalin solution (37%) were slowly added dropwise, and the mixture was stirred at 90 ° C for 8 hours. After the reaction was partially advanced, the internal temperature was raised to 180 ° C to remove the mixed water. If the water was no longer removed, the temperature was raised to 195 ° C to remove unreacted monomers. At this time, the degree of vacuum was maximized to remove the low molecular weight and monomers contained in the benzyl ether type phenolic resin as much as possible. The obtained benzyl ether-type phenol resin had a molecular weight of 3,400 in terms of polystyrene and a dispersion degree of 3.1.

 [ Synthetic example  3: Polyvinylphenol  Derivative Synthesis (Resin C)]

In a round flask, 50 g of polyvinyl phenol having a molecular weight of 8,000 and a dispersion degree of 1.1 was dissolved in 250 g of acetone. 10 g of acetic anhydride was added thereto, and 12 g of triethylamine was slowly added dropwise at room temperature. The solution was stirred at the same temperature for 5 hours, then slowly added dropwise to excess deionized water containing 1% hydrochloric acid to form a precipitate. The precipitate formed was vacuum dried to obtain 52 g of a resin in which the hydroxy group of the polyvinyl phenol was partially substituted with an acetyl group. The molecular weight of this resin in terms of polystyrene was 8,900 and the dispersion degree was 1.1.

 [ Synthetic example  4: Polyacrylate  Synthetic (Resin D)]

5 g of styrene, 3 g of 2-hydroxyethyl methacrylate, 10 g of isobornyl methacrylate and 2 g of methacrylic acid were dissolved in 30 g of isopropanol, and 3 g of AIBN, which is a radical initiator, was added to the round flask, and the flask was heated did. After stirring at the same temperature for 5 hours, the reaction mixture was cooled to room temperature and gradually added dropwise to an excess amount of hexane to form a white precipitate. The precipitate was filtered and vacuum dried to obtain 18 g of a polyacrylate resin having a polystyrene reduced molecular weight of 16,000 and a dispersion degree of 2.2.

[ Synthetic example  5: 4,4'- Oxybisbenzoyl  Chloride synthesis]

60 g (0.2324 mol) of 4,4'-oxybisbenzoic acid was added to 240 g of N-methylpyrrolidone (NMP) in a 0.5 L flask equipped with a stirrer and a thermometer and dissolved by stirring. 110 g (0.9246 mol) of thionyl chloride was added dropwise and reacted for 1 hour to obtain a 4,4'-oxybisbenzoyl chloride solution.

 [ Synthetic example  6: Synthesis of polyamide (resin E)]

400 g of N-methylpyrrolidone (NMP) was placed in a 1 L flask equipped with a stirrer and a thermometer, and 85 g (0.2321 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added thereto, While melting. 39 g (0.4930 mol) of pyridine was then added, and 8 g (0.0487 mol) of 5-norbornene-2,3-dicarboxylic anhydride and 4,4'-oxybisbenzoyl chloride synthesized in Synthesis Example 5 After the dropwise addition, the mixture was stirred at room temperature for 1 hour. The resulting solution was added to 3 liters of water, and the resulting precipitate was filtered, washed, and vacuum-dried to obtain 110 g of a polyamide. The polyamide thus obtained had an average molecular weight in terms of polystyrene of 18,500 and a degree of dispersion of 1.9.

 [ Synthetic example  7: Dimethyl-3,3 ', 4,4'- Diphenyl ether - Tetracarboxylate Dichloride  synthesis]

12.5 g (0.3901 mol) of methyl alcohol, 2 g (0.0198 mol) of triethylamine, and 120 g of N-methylpyrrolidone (0.1934 mol) (NMP) was added to a 1 L flask equipped with a stirrer and a thermometer, and stirred at room temperature for 4 hours and reacted to prepare a solution of di-n-methyl-3,3 ', 4,4'-diphenyl ether-tetracarboxylate The back flask was cooled to 0 占 폚. Thereafter, 70 g (0.5884 mol) of thionyl chloride was added dropwise thereto and the reaction was carried out for 2 hours to obtain a solution of dimethyl-3,3 ', 4,4'-diphenyl ether-tetracarboxylate dichloride.

 [ Synthetic example  8: Polyamidate  Synthetic (Resin F)]

(NMP) was added to a 1 L flask equipped with a stirrer and a thermometer and 65 g (0.1775 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) And dissolved with stirring. After adding 35 g (0.4425 mol) of pyridine, the solution of dimethyl-3,3 ', 4,4'-diphenyl ether-tetracarboxylate dichloride synthesized in Synthesis Example 7 was slowly added dropwise over 30 minutes, Lt; / RTI > for 1 hour. 3 L of water was added to the resulting solution, and the resulting precipitate was filtered, washed and vacuum-dried to obtain 128 g of polyamidate. The polyamidate thus obtained had an average molecular weight in terms of polystyrene of 19,200 and a degree of dispersion of 1.7.

 [ Synthetic example  9: Synthesis of sulfonic acid ester PAC  A)]

100 mg of 3,3,5,5-tetrakis (hydroxymethyl) biphenyl-4,4-diol was placed in 1000 ml of ethyl acetate, and thionyl chloride was reacted at room temperature for 30 minutes. Recrystallization from ethyl acetate and hexane gave 55 g. The obtained 3,3,5,5-tetrakis (chloromethyl) biphenyl-4,4-diol was reacted with 10 g of methanol at room temperature to obtain a final product, 3,3,5,5-tetrakis (methoxymethyl) Phenyl-4, 4-diol. 80 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride was dissolved in 800 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution was added dropwise to deionized water to form a precipitate. The precipitate formed was filtered and washed and dried under vacuum at 40 캜 for 48 hours to obtain 104 g of sulfonic acid ester (PAC A).

[ Synthetic example  10: Synthesis of sulfonic acid ester PAC  B)]

In a round flask, 50 g of bis-3,5-bis (hydroxymethyl) -4-hydroxyphenylmethane and 10 g of iodomethane were reacted at 40 ° C. in methanol and water for 12 hours. This was recrystallized to obtain 51 g. 103 g (3.5 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride was dissolved in 900 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution was added dropwise to deionized water to form a precipitate. The precipitate formed was filtered and washed, and vacuum dried at 40 DEG C for 48 hours to obtain 118 g of sulfonic acid ester (PAC B).

[ Synthetic example  11: Synthesis of sulfonic acid ester PAC  C-1)]

In a round flask, 50 g of 4,4- (1-trifluoromethyl-2-trifluoroethylidene) bis (3,5-dihydroxymethylphenol) and 50 g of 1,2-naphthoquinonediazide- 103 g (3.5 mol) of sulfonyl chloride was dissolved in 900 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution was added dropwise to deionized water to form a precipitate. Filtration of the precipitate formed. Washed and vacuum-dried at 40 DEG C for 48 hours to obtain 118 g of sulfonic acid ester (PAC C-1).

[ Synthetic example  12: Synthesis of sulfonic acid ester PAC  C-2)]

In a round flask, 50 g of 4,4- (1-trifluoromethyl-2-trifluoroethylidene) bis (3,5-dihydroxymethylphenol) and 50 g of 1,2-naphthoquinonediazide- 103 g (3.5 mol) of sulfonyl chloride and 11.2 g of acetic anhydride were dissolved in 900 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution was added dropwise to deionized water to form a precipitate. The precipitate formed was filtered and washed and dried under vacuum at 40 DEG C for 48 hours to obtain 118 g of sulfonic acid ester (PAC C-2).

[ Synthetic example  13: Synthesis of sulfonic acid ester PAC  D)]

In a round flask, 50 g of 2,2-bis (4-hydroxyphenyl) propane was dissolved in 90 g of a 20% aqueous solution of potassium hydroxide, and the mixture was stirred at room temperature for 10 minutes. Then, 120 g of 35% formaldehyde aqueous solution was added dropwise at 50 캜 for 90 minutes. Thereafter, the mixture was stirred at the same temperature for 15 hours. This was neutralized with 16% sulfonic acid. Methyl ethyl ketone was added to dissolve the product, and the water layer and the layer were separated, and methyl ethyl ketone was distilled off. The final product was recrystallized from toluene and methanol to give 44 g. 103 g (3.5 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 11.2 g of acetic anhydride were dissolved in 900 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution was added dropwise to deionized water to form a precipitate. The precipitate formed was filtered and washed and dried in vacuo at 40 ° C for 48 hours to give 118 g of sulfonic acid ester (PAC D).

[ Synthetic example  14: Synthesis of sulfonic acid ester PAC  E)]

Sulfonic acid ester 44 g of the reaction product obtained in Synthesis D was dissolved in 500 g of ethyl acetate, and then 10 g of thionyl chloride and 18 g of methanol were reacted. After adding 15 g of triethylamine, the reaction product was recrystallized from hexane / ethyl acetate to obtain 40 g. 103 g (3.5 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 11.2 g of acetic anhydride were dissolved in 900 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution was added dropwise to deionized water to form a precipitate. The precipitate formed was filtered and washed and vacuum dried at 40 DEG C for 48 hours to obtain 118 g of sulfonic acid ester (PAC E).

[ Synthetic example  15: Synthesis of sulfonic acid ester PAC  F)]

60 g of 1,1,1-tris (4-hydroxyphenyl) ethane and 90 g of 20% potassium hydroxide aqueous solution were dissolved in a round flask, and the mixture was stirred at room temperature for 10 minutes. Subsequently, 120 g of a 35% formaldehyde aqueous solution was added dropwise at 50 캜 for 1.5 hours. Thereafter, the mixture was stirred at the same temperature for 15 hours. This was neutralized with 16% sulfonic acid. Methyl ethyl ketone was added to dissolve the product, and the water layer and the layer were separated, and methyl ethyl ketone was distilled off. This was recrystallized from toluene and methanol and dried. This was reacted with 20 g of thionyl chloride and reacted again with 50 g of methanol. 45 g of 1,1,1-tris (3,5-bis (methoxymethyl) -4-hydroxyphenyl ethane) was finally obtained. 50 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride Was dissolved in 900 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution was added dropwise to deionized water to form a precipitate The resulting precipitate was filtered and washed and dried in vacuo at 40 ° C for 48 hours to give 118 g of sulfonic acid ester (PAC F).

[Chemical Formulas 14 to 19]

The ballast A to F represented by the above formulas (14) to (19) were synthesized in the sulfonate ester Synthesis Examples 1 to 6.

[compare Synthetic example  1: Sulfonic acid ester ( PAC  G)]

In a round flask, 50 g of tris (4-hydroxyphenyl) ethane and 132 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride were dissolved in 900 g of dioxane and then cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution is added to excess deionized water to form a precipitate. The precipitate formed was filtered and washed and vacuum dried at 40? For 48 hours to obtain 118 g of sulfonic acid ester (PAC G).

Example  1 to 14, and Comparative Example  1 and 2

10 g of the sulfonic acid ester compounds (PAC A to PAC F) synthesized in Synthesis Examples 9 to 15 and 100 g of the alkali-soluble resins (Resin A to Resin F) synthesized in Synthesis Examples 1 to 4, 6 and 8, 20 g of the cyclohexyl-4-methylbenzenesulfonate additive (A) (optional) and 300 ppm of a fluorinated surfactant were dissolved in 230 g of a solvent to improve the uniformity of the film. The resulting mixture was filtered using a filter having a pore size of 0.5 μm, Thereby obtaining a resist composition. The composition ratios of the compositions of Examples 1 to 14 and Comparative Examples 1 and 2 are shown in Table 1.

Composition Resin Sulfonic acid
ester menstruum Additive (A)
The presence or absence Example 1 A PACE PGMEA X Example 2 A PAC B GBL O Example 3 B PAC C-1 PGMEA O Example 4 B PAC D GBL X Example 5 C PAC B PGMEA O Example 6 C PAC D GBL O Example 7 D PAC E GBL O Example 8 D PAC F GBL O Example 9 E PAC E GBL X Example 10 E PAC F GBL O Example 11 F PAC E GBL O Example 12 F PAC F GBL X Example 13 D PAC C-1 GBL O Example 14 D PAC C-2 GBL O Comparative Example 1 E PAC G GBL O Comparative Example 2 F PAC G GBL O

- PGMEA: propofolene glycol monomethyl ether acetate, GBL: gamma-butyrolactone

Performance measurement and evaluation

The compositions prepared in Examples 1 to 14 and Comparative Examples 1 and 2 were spin coated and then dried by heating at 120 DEG C for 120 seconds to obtain a film having a thickness of 7 mu m. This was exposed using an i-line stepper and developed with 2.38 wt% TMAH (Tetramethyl ammonium hydroxide) to obtain a pattern.

The residual film ratio refers to a value obtained by dividing the thickness (initial film thickness) of the non-exposed portion after development by the thickness of the heat dried film (final film thickness) after spin coating. Sensitivity refers to the exposure energy value at which the pattern is formed. The pattern perpendicularity was observed with SEM. The results are shown in Table 2.

Remaining film ratio (%) Sensitivity (mJ / cm ² ) Pattern verticality Example 1 88 220 middle Example 2 90 250 good Example 3 84 200 middle Example 4 88 260 middle Example 5 83 290 middle Example 6 89 300 good Example 7 90 270 good Example 8 90 250 good Example 9 84 340 middle Example 10 88 320 good Example 11 82 360 good Example 12 84 380 good Example 13 85 270 good Example 14 90 250 good Comparative Example 1 67 420 Poor Comparative Example 2 70 400 Poor

Claims (7)

As a photosensitive compound synthesized through reaction of at least two compounds having at least two benzyl alcohol groups or at least two alkoxymethylbenzene groups in one molecule with at least two naphthoquinonediazide sulfonyl chlorides (-DNQ-Cl)
Wherein the photosensitive compound comprises at least two naphthoquinone diazidesulfoxymethylbenzene groups or at least two alkoxymethylbenzene groups.
The method according to claim 1,
Wherein the photosensitive compound is any one of compounds represented by the following formula (1) or (2).

(One)

(2)
At least one resin component selected from the group consisting of novolak derivatives, polyhydroxystyrene derivatives, acrylic acid-containing polyacrylate derivatives, (meth) acrylic acid derivatives, styrene derivatives, polyamide derivatives, polyimide derivatives and polyvinyl pyrrolidone derivatives ; And
As a photosensitive compound synthesized through the reaction of a compound having at least two benzyl alcohol groups or at least two alkoxymethylbenzene groups in a molecule with at least two naphthoquinonediazide sulfonyl chlorides (-DNQ-Cl), at least two Or a photosensitive compound comprising at least two alkoxymethylbenzene groups. 2. The photosensitive composition as claimed in claim 1, wherein the photosensitive compound is at least one compound selected from the group consisting of naphthoquinone diazide sulfoxymethylbenzene group and naphthoquinone diazide sulfoxymethylbenzene group.
The method of claim 3,
Wherein the photosensitive compound has a content of 1 to 30% by weight in the total composition.
The method of claim 3,
Wherein the photosensitive composition comprises a plurality of photosensitive compounds having different substitution ratios of naphthoquinone diazide sulfoxy group (-ODNQ).
Reacting a compound comprising at least two benzyl alcohol groups or at least two alkoxymethylbenzene groups under a first basic catalyst to produce a first reactant; And
Cooling the reaction solution containing naphthoquinonediazide sulfonyl chloride (-DNQ-Cl) to the first reaction product, and then reacting the first reaction product under a second basic catalyst to produce a second reaction product; Way.


delete