KR101184205B1 - Photo-sensitive compound, photo-sensitive polymer and chemically amplified photoresist composition including the same - Google Patents

Abstract

Disclosed are a photosensitive compound having excellent solubility and etching resistance by a developer even under short exposure wavelengths of 248 nm and 193 nm or less, improved line edge roughness, a photosensitive polymer resin, and a photoresist composition comprising the same. The photosensitive polymer resin includes a repeating unit represented by the following formula.

In the above formula, R ₁ is H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thio alkyl group, n is an integer of 1 or 2 and c is the photosensitive polymer resin It is 1-60 mol% as mol% of the said repeating unit with respect to all the repeating units.

Photosensitive compound, photosensitive polymer resin, photoresist, line edge roughness

Description

Photo-sensitive compound, photo-sensitive polymer and chemically amplified photoresist composition including the same}

1 to 8 are electron scanning micrographs of the photoresist patterns formed in Examples 17 to 24, respectively.

9 compares etch resistance to oxides and etch resistance to polysilicon of chemically amplified photoresist compositions.

The present invention relates to a photosensitive compound, a photosensitive polymer resin and a chemically amplified photoresist composition comprising the same, more particularly, excellent solubility and etching resistance by a developer even under an exposure source of 248 nm and 193 nm or shorter wavelength, The present invention relates to a photosensitive polymer resin having improved edge roughness and a photoresist composition comprising the same.

With the higher integration of semiconductor integrated circuit devices, the development of gigabit DRAMs with higher capacities than the dynamic random access memory (hereinafter referred to as DRAMs) with the conventional 256 megabit class storage capacity has been developed, and the conventional 0.25 µm line width such as 90 nm has been developed. There is a need to develop a photosensitive polymer resin and a chemically amplified photoresist composition capable of forming a finer photoresist pattern.

Generally, in the photolithography process, a chemically amplified photoresist composition used in photolithography processes under extreme ultraviolet exposure sources such as KrF (248 nm) and ArF (193 nm) excimer lasers, which are short wavelength exposure sources of less than 250 nm, is (i) exposed. In addition to excellent transparency to light, (ii) good adhesion to semiconductor circuit boards, (i) good etching resistance, and (i) line edge roughness in the photoresist pattern. edge roughness: pattern damage such as LER, top loss, and slope should not occur, and (iii) for conventional developer such as 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution. Development should be easy.

However, smaller wavelengths, such as Extreme UltraViolet Lithography (EUVL) and F2 (157 nm) light sources, allow finer size patterns, but these light sources have high light absorption and thus have a thin thickness. In the case of emulsion lithography using an ArF (193 nm) light source or filling the space between the transmission lens and the wiper with water, the adhesion area to the semiconductor circuit board is reduced by miniaturization of the photoresist pattern. As a result, there is a problem in that the resist pattern collapses due to the decrease, and when the thickness of the resist film is reduced to compensate for this problem, the resistance in the etching process is reduced.

Accordingly, although a bulk photosensitive compound is introduced to enhance etching resistance, which is the biggest problem of resists having a thin film thickness, the photoresist composition including the bulk photosensitive compound improves etching resistance while dissolving by a developer. There is another problem that is reduced, resulting in poor line edge roughness.

Accordingly, an object of the present invention is to provide a photosensitive polymer resin having excellent etching resistance, adhesion to a semiconductor substrate, and line edge roughness even under short exposure wavelengths of 248 nm and 193 nm, and a chemically amplified photoresist composition comprising the same. will be.

Still another object of the present invention is to provide a method of preparing the photosensitive polymer resin and a method of forming a photoresist pattern using the chemically amplified photoresist composition.

In order to achieve the above object, the present invention provides a photosensitive compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thio alkyl group, and n is an integer of 1 or 2.

The present invention also provides a photosensitive polymer resin comprising a repeating unit represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ , R ₂ , R ₃ , n are as defined in Formula 1, c is a mole% of the repeating unit to the total repeating units constituting the photosensitive polymer resin, 1 ~ 60 mol% to be.

The present invention also provides a photoresist composition comprising a repeating unit represented by Formula 2 and a method of forming a photoresist pattern using the photoresist composition.

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

The photosensitive compound according to the present invention is for preparing the photosensitive polymer resin, and is represented by the following Chemical Formula 1.

In Formula 1, R ₁ is H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thioalkyl group, and n is an integer of 1 or 2.

Preferred examples of the photosensitive compound represented by Chemical Formula 1 according to the present invention are the photosensitive compounds represented by the following Chemical Formulas 1a to 1h.

The photosensitive compound represented by Chemical Formula 1 according to the present invention may be prepared by a conventional method for preparing an organic compound, and the photosensitive compound represented by Chemical Formula 1a, which is a preferred example of the photosensitive compound of Chemical Formula 1, may be represented by the following Scheme 1. Can be synthesized as shown. First, a mononorbornene compound (a) is obtained by reacting cyclopentadiene with maleic anhydride (Diels-Alder) to obtain a mononorbornene compound (a). A Dinorbornene compound (b) is prepared by a Diels-Alder reaction. Next, the prepared dinorbornene compound (b) is reacted with a reducing agent such as LiAlH ₄ or NaBH ₄ in a nonpolar solvent to obtain a lactone compound (c), and the obtained lactone compound (c) is peracetic acid (peracetic) An epoxide compound (d) is obtained by reacting with a peroxide such as acid and CH ₃ CO ₃ H) to oxidize the double bond of norbornene. By reacting the obtained epoxide compound (d) with a reagent such as water, alcohol or thiol under acidic conditions, and ring-opening addition reaction of the epoxy group, a compound (e) having a hydroxyl group is obtained, and the compound having a hydroxyl group (e) is obtained. ) Is esterified with isopropenyl chloridecarbonate to prepare a photosensitive compound represented by Chemical Formula 1a. In addition, a photosensitive compound represented by Chemical Formulas 1b to 1h may be prepared by the same method as described above.

Formula 1a prepared according to Scheme 1 increases the solubility by the developer because the functional groups are easily deprotected by the generated acid, as shown in Scheme 2 below.

The photosensitive polymer resin according to the present invention includes a repeating unit represented by Formula 2 below.

In Formula 2, R ₁ , R ₂ , R ₃ , n are as defined in Formula 1, c is a mole% of the repeating unit to the total repeating units constituting the photosensitive polymer resin, 1 ~ 60 mol% to be.

The remaining repeating units constituting the photosensitive polymer resin according to the present invention together with the repeating unit represented by Formula 2 may be preferably repeating units having a protecting group sensitive to acid, and the protecting group sensitive to the acid may be a side chain of the photosensitive polymer resin. As a dissolution inhibiting group which is bound to and can be detached by an acid, in the non-exposed part, the dissolution of the photoresist composition into the alkaline developer is suppressed, and in the exposed part, the dissolution is suppressed by the acid generated from the photoacid generator. It protects and increases the solubility with respect to general alkali developing solution, and plays a role which enlarges the solubility difference of an exposure part and a non-exposure part. That is, when an acid-sensitive protecting group is attached, the photoresist material is inhibited from being dissolved by the alkaline developer, but when the acid-sensitive protecting group is desorbed by the acid generated from the photoacid generator, the photoresist material is developed. Can be dissolved in. The acid-sensitive protecting group can be anything as long as it can play such a role, preferably t-butyl, tetrahydropyran-2-yl, 2-methyl tetrahydropyran-2-yl, tetrahydrofuran 2-yl, 2-methyl tetrahydrofuran-2-yl, 1-methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1- Methoxyethyl, 1-ethoxyethyl, t-butoxyethyl, 1-isobutoxyethyl, 2-acetylment-1-yl and the like can be used.

Preferred examples of the photosensitive polymer resin according to the present invention are the photosensitive polymer resins represented by the following formula (3), and more preferred examples are the photosensitive polymer resins represented by the following formulas (3a to 3h).

In Formula 3, R ₁ is each independently H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thio alkyl group, and R ₄ is an alkyl group having 1 to 20 carbon atoms or carbon atoms A cycloalkyl group having 5 to 40 carbon atoms, R ₅ is a cycloalkyl group having 5 to 10 carbon atoms including a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms having a halogen substituent, an ether group or an ester group, and n Is an integer of 1 or 2, and a, b and c are mole% of each repeating unit with respect to the entire photosensitive compound constituting the photosensitive polymer resin, and each 1 to 60 mole%: 1 to 60 mole%: 1 to 60 mole %to be.

In Chemical Formulas 3a to 3h, a, b, and c are as defined in Chemical Formula 3.

The photosensitive polymer resin incorporating the photosensitive compound according to the present invention introduces a bulky aliphatic cyclic hydrocarbon, dynobornene group to enhance etching resistance, and improves adhesion to a semiconductor circuit board using a lactone group. By introducing a functional group which is deprotected by the above, the contrast, which is the difference in solubility due to the development of the exposed portion and the non-exposed portion, is increased to improve the line edge roughness.

 Method for producing a photosensitive polymer resin according to the present invention is a) a photosensitive compound represented by the formula (1), and the photosensitive compound represented by the following formulas (4), 5, if necessary in a polymerization solvent, b) polymerization in the mixture solution The initiator may be added, and c) the mixture solution to which the initiator is added may be prepared by reacting at a temperature of 60 to 70 ° C. for 4 to 24 hours under a nitrogen or argon atmosphere. Preferably, the polymerization may be carried out by radical polymerization, solution polymerization, bulk polymerization or polymerization using a metal catalyst. In addition, the preparation method may include the step of purifying the reaction product using a lower alcohol containing diethyl ether, hexane, petroleum ether, methanol, ethanol or isopropanol, water, a mixture thereof, and the like. It may also include.

R ₁ in Formulas 4 and 5, R ₄ , and R ₅ are as defined in the formula (3).

As the polymerization solvent of the polymerization reaction, a polymerization solvent commonly known in the art can be used in a wide range, and without limitation, cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane , Methylethylketone, benzene, toluene and xylene or mixtures thereof may be used, and the polymerization initiator may also be widely used polymerization initiators commonly known in the art, but are not limited to benzoyl peroxide, 2,2 '-Azobisisobutyronitrile (AIBN), acetylperoxide, lauryl peroxide, t-butylperacetate, t-butylhydroperoxide and di-t-butylperoxide or mixtures thereof can be used.

The photoresist composition according to the present invention includes a photosensitive polymer resin including a repeating unit represented by Formula 3, a photoacid generator for generating an acid and an organic solvent, and may further include various additives as necessary. The photosensitive polymer resin of Chemical Formula 3 may have a weight average molecular weight of 3,000 to 100,000, and a dispersion degree of 1.0 to 5.0. When the weight average molecular weight and the dispersion degree are outside the above ranges, the physical properties of the photoresist film may be reduced, or the formation of the photoresist film may be difficult, and the contrast of the pattern may be lowered.

The photoacid generator generates an acid component such as H ⁺ by exposure to induce chemical amplification, and may be any compound that can generate an acid by light, and preferably, sulfide salts such as eutechonic acid. Onium salt type compounds, such as a type | system | group compound and an onium salt, and its mixture can be used. Non-limiting examples of photoacid generators include phthalimidotrifluoromethanesulfonate, dinitrobenzyltosylate, n-decyldisulfone, naphthylimidotrifluoromethanesulfonate, diphenyl having low absorbance at 157 nm and 193 nm. Urethritis hexafluorophosphate, Diphenyluredo salt hexafluoro arsenate, Diphenyluredo salt hexafluoro antimonate, Diphenylparamethoxyphenylsulfonium triflate, Diphenylparatoluenylsulfonium triflate, Diphenylpara Isobutylphenylsulfonium triflate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate and mixtures thereof can do. The content of the photoacid generator is preferably 0.1 to 20% by weight based on the photosensitive polymer resin. If it is less than 0.1% by weight, the sensitivity of the photoresist composition to light may decrease, which may make it difficult to deprotect the protective group. If it exceeds 20% by weight, a large amount of acid may be generated in the photoacid generator, resulting in poor cross-section of the resist pattern. There is concern.

As the organic solvent constituting the remaining components of the photoresist composition according to the present invention can be used a wide variety of organic solvents commonly used in the preparation of the photoresist composition, non-limiting examples include ethylene glycol monomethyl ethyl, ethylene glycol Monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA), toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-hydroxypropionethyl, 2-hydroxy 2-methyl ethyl propionate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2-hydroxy methyl methyl butyrate, 3-methoxy 2-methyl methyl propionate, 3-ethoxy propionate, 3-methoxy 2- Ethyl methyl propionate, ethyl acetate, butyl acetate, and mixtures thereof can be illustrated.

In addition, the photoresist composition according to the present invention may further include an organic base as needed, non-limiting examples of the organic base is triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanol Amines and mixtures thereof can be exemplified. The content of the organic base is preferably 0.01 to 10.00% by weight based on the total photoresist composition. If the content of the organic base is less than 0.01% by weight, there is a possibility that a t-top phenomenon occurs in the resist pattern, and if the content is more than 10.00% by weight, the sensitivity of the photoresist composition may decrease and the process progress may be lowered. have.

The chemically amplified photoresist composition according to the present invention contains the photosensitive polymer resin, the photoacid generator, the organic solvent and various additives as necessary, and preferably, the solid content concentration is 1 to 30 parts by weight based on 100 parts by weight of the total photoresist composition. Prepared to be in weight%. After manufacture, it uses by filtering with a 0.2 micrometer filter as needed.

Using the chemically amplified photoresist composition according to the present invention, a photoresist pattern may be formed by the following method.

First, a) a thin film is formed by applying the chemically amplified photoresist composition according to the present invention on a etched layer such as a silicon wafer or an aluminum substrate using a spin coater, and b) applying a short wavelength light source to the formed thin film. After exposure, c) the exposed photoresist film is heated as needed, and d) the heated resist film is developed to form a photoresist pattern.

The method of forming the photoresist pattern may further include a prebake process of heating the applied resist film after the a) coating process and b) before the exposure process, and the exposed photo of the prebaking process and c). It is preferable that the heating process of a resist consists of 70 degreeC-200 degreeC. When the heating temperature is less than 70 ° C, the organic solvent included in the photoresist composition may not be sufficiently evaporated. When the heating temperature exceeds 200 ° C, the photoresist composition may be thermally decomposed.

In the d) development process, the developer may be a developer commonly known in the art, preferably an alkaline developer, more preferably an aqueous tetramethylammonium hydroxide (TMAH) solution. The concentration of the developer is preferably 0.1 to 10% by weight. In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and a surfactant may be added to the developer.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples.

Example 1 Preparation of Photosensitive Compound (Formula 1a)

1) Cracking of dicyclopentadiene

450 g of dicyclopentadiene heated to 220 ° C. was stirred dropwise into paraffin oil, and 40 to 45 ° C. vapor from the stirred reaction product was cooled to 10 ° C. to obtain 390 g of cyclopentadiene.

2) Preparation of Dinorbornene Compounds

As shown in Scheme 1, 190 g of the cyclopentadiene obtained in 1) of Example 1 was added dropwise to a flask reactor to which maleic anhydride and 1.3 kg of benzene equally equivalent to cyclopentadiene were added, followed by stirring. The reaction was carried out. At this time, by cooling the reactor in a dry ice bath (bath), the temperature of the reactants is increased so that no gas is generated. After completion of the dropwise addition, the reaction mixture was allowed to stand and the temperature was raised to room temperature, and then the reaction was carried out while stirring at room temperature for 1 day to obtain a mono norbornene compound. Negative cyclopentadiene was added and carried out in the same manner as above to obtain the di-norbornene compound. {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.43 (CH ₂ , 2H), 1.44 (CH, 2H), 1.82 (CH ₂ , 2H), 2.06 (CH, 2H), 2.26 ( CH, 2H), 2.89 (CH, 2H), 5.60 (CH, 2H)}

3) Preparation of Lactone Compounds

As shown in Scheme 1, 0.5 mol (115.13 g) of the dinorbornene compound obtained in Example 1-2) was added to the reactor with stirring and adding 0.2 mol (7.58 g) of LiAlH ₄ and 500 ml of purified THF. The mixture was dissolved in anhydrous THF and added dropwise, and the reaction mixture was refluxed for 24 hours, cooled to room temperature, and water was added to carry out the reaction. After the reaction was completed, the reaction was filtered, washed with methanol, the solvent was evaporated under reduced pressure, the solvent was removed by column chromatography (Rf = 0.2) to give a lactone compound (yield: 97%). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.42 (CH, 1H), 1.43 (CH ₂ , 2H), 1.44 (CH, 3H), 1.82 (CH ₂ , 2H), 2.06 ( CH, 1H), 2.25 (CH, 1H), 2.65 (CH, 3H), 4.26 (CH ₂ , 2H), 5.60 (CH, 2H)}

4) Preparation of Compound Having Epoxide Compound and Hydroxyl Group

As shown in Scheme 1, 0.4 mol (86.52 g) of lactone compound and 1.0 mol (106 g) of sodium carbonate (Na ₂ CO ₃ ) obtained in Example 1.3 were dissolved in 700 ml of methylene chloride. 72 g (0.4 mol) of acetic acid was added dropwise to a mixed solution of 2 g of sodium acetate, and then the reacted solution was mixed for 30 to 45 minutes while maintaining the temperature of 20 ° C. After raising the temperature to room temperature, the reaction was carried out while further stirring for 1 hour to obtain an epoxide compound. The reaction product containing the obtained epoxide compound was placed in a reduced pressure flask, the solvent was removed under reduced pressure, the reaction product from which the solvent was removed was filtered, and then the filtered solid reaction product was washed three times with methylene chloride, and the washed reaction product was cold distilled water. In 500 ml and rapidly stirred for 1 hour, and then separated to obtain a compound having a hydroxyl group (yield: 90%). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.51 (CH, 2H), 1.98 (CH ₃ , 3H), 2.0 (OH, 2H), 2.06 (CH, 1H), 2.25 (CH, 1H), 2.65 (CH, 1H), 3.24 (CH, 2H), 4.26 (CH ₂ , 2H)}

5) Preparation of Photosensitive Compound (Formula 1a)

As shown in Scheme 1, 0.28 mol (73.99 g) and triethylamine 0.32 mol (44.48 ml) of the compound having a hydroxyl group obtained in Example 1-4) were dissolved in 250 ml of THF, and then the mixed solution. 0.32 mol (38.57 g) of isopropenyl chloride carbonate was added dropwise using a dropping funnel, and the reaction was performed at room temperature for 2 hours. After the reaction was completed, excess tetrahydrofuran (THF) was removed using a rotary evaporator, and the reaction was added to water, the reaction was neutralized with diluted hydrochloric acid and extracted with diethyl ether, followed by anhydrous. Dried over magnesium sulfate. The dried product was purified by column chromatography to prepare a photosensitive compound represented by Chemical Formula 1a (yield: 77%). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.51 (CH, 1H), 2.0 (OH , 2H), 2.02 (CH, 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 2.65 (CH, 1H), 3.75 (CH, 1H), 3.98 (CH, 1H), 4.26 (CH ₂ , 2H), 4.44 (H, 1H), 4.68 (H, 1H)}

Example 2 Preparation of Photosensitive Compound (Formula 1b)

In the final step of preparing the photosensitive compound, in the same manner as in Example 1, except that 0.32 mol (34.08 g) of vinyl chloride carbonate instead of 0.32 mol (38.57 g) of isopropenyl chloride carbonate, The photosensitive compound represented by 1b was prepared (yield: 72%). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.51 (CH, 1H), 2.0 (OH , 2H), 2.02 (CH, 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 2.65 (CH, 1H), 3.75 (CH, 1H), 3.98 (CH, 1H), 4.26 (CH ₂ , 2H), 4.66 (H, 1H), 4.96 (H, 1H), 7.23 (H, 1H)}

Example 3 Preparation of Photosensitive Compound (Formula 1c)

Gluconic acid (Aldrich 369535) was reacted with phosphorus pentoxide (P ₂ O ₅ / silica), a powerful dehydrogenating agent, to prepare a hexagonal lactone compound, followed by dinovo in the same manner as in Example 1. The photosensitive compound represented by Chemical Formula 1c was prepared after preparing a compound having a nene compound, an epoxide compound, and a hydroxyl group (yield 73%): {H-NMR (CDCl ₃ , internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.51 (CH, 1H), 1.86 (CH ₂ , 2H), 1.98 (CH ₃ , 3H), 2.0 (OH, 2H), 2.02 (CH, 1H), 2.05 (CH, 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 3.75 (CH, 1H), 3.98 (CH, 1H), 4.44 ( H, 1H), 4.68 (H, 1H)}

Example 4 Preparation of Photosensitive Compound (Formula 1d)

In the final step of preparing the photosensitive compound, in the same manner as in Example 3 except that 0.32 mol (34.08 g) of vinyl chloride carbonate instead of 0.32 mol (38.57 g) of isopropenyl chloride carbonate, Formula 1d The photosensitive compound represented by was prepared (yield: 69%). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.51 (CH, 1H), 1.86 (CH ₂ , 2H), 2.0 (OH, 2H), 2.02 (CH, 1H), 2.05 (CH, 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 3.75 (CH, 1H), 3.98 (CH , 1H), 4.66 (H, 1H), 4.96 (H, 1H), 7.33 (H, 1H)}

Example 5 Preparation of Photosensitive Compound (Formula 1e)

In the step of preparing a compound having a hydroxyl group, a photosensitive compound represented by Chemical Formula 1e was prepared in the same manner as in Example 1, except that 500 ml of methanol was used instead of 500 ml of distilled water (69% yield). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.75 (CH, 1H), 1.98 (CH ₃ , 3H), 2.02 (CH, 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 2.65 (CH, 1H), 3.24 (CH ₃ , 3H), 3.37 (CH, 1H), 4.22 ( H, 1H), 4.26 (CH ₂ , 2H), 4.44 (H, 1H), 4.68 (H, 1H)}

Example 6 Preparation of Photosensitive Compound (Formula 1f)

In the step of preparing a compound having a hydroxyl group, a photosensitive compound represented by Chemical Formula 1f was prepared in the same manner as in Example 2, except that 500 ml of methanol was used instead of 500 ml of distilled water (66% yield). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.75 (CH, 1H), 2.02 (CH , 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 2.65 (CH, 1H), 3.24 (CH ₃ , 3H), 3.37 (CH, 1H), 4.22 (H, 1H), 4.26 (CH ₂ , 2H), 4.66 (H, 1H), 4.96 (H, 1H), 7.33 (H, 1H)}

Example 7 Preparation of Photosensitive Compound (Formula 1g)

In the step of preparing a compound having a hydroxyl group, a photosensitive compound represented by Chemical Formula 1g was prepared in the same manner as in Example 3, except that 500 ml of methanol was used instead of 500 ml of distilled water (73% yield). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.75 (CH, 1H), 1.86 (CH ₂ , 2H), 1.98 (CH ₃ , 3H), 2.02 (CH, 1H), 2.05 (CH, 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 2.65 (CH, 1H), 3.24 ( CH ₃ , 3H), 3.37 (CH, 1H), 4.22 (H, 1H), 4.26 (CH ₂ , 2H), 4.44 (H, 1H), 4.68 (H, 1H)}

Example 8 Preparation of Photosensitive Compound (Formula 1h)

In the step of preparing a compound having a hydroxyl group, a photosensitive compound represented by Chemical Formula 1h was prepared in the same manner as in Example 4, except that 500 ml of methanol was used instead of 500 ml of distilled water (yield: 70%). {H-NMR (CDCl ₃ , Internal standard): δ (ppm), 1.40 (CH, 2H), 1.42 (CH, 1H), 1.43 (CH ₂ , 4H), 1.75 (CH, 1H), 1.86 (CH ₂ , 2H), 2.02 (CH, 1H), 2.05 (CH, 1H), 2.06 (CH, 1H), 2.25 (CH, 1H), 3.24 (CH ₃ , 3H), 3.37 (CH, 1H), 4.22 ( H, 1H), 4.26 (CH ₂ , 2H), 4.66 (H, 1H), 4.96 (H, 1H), 7.33 (H, 1H)}

Example 9 Preparation of Photosensitive Polymer Resin (Formula 3a)

56.42 g (0.161 mol) of the photosensitive compound represented by Chemical Formula 1a, 75.45 g (0.322 mol) of 2-methyl-2-adamantyl-methacrylate, 38.05 g (0.161 mol) of hydroxy adamantyl methacrylate and azobis 12 g of isobutyronitrile (AIBN) was dissolved in 120 g of anhydrous THF, and gas was removed using an ampoule by a freezing method, and then the reaction was polymerized at 66 ° C. for 12 hours. The precipitate was slowly dropped in an excess of diethyl ether, dissolved in THF, and reprecipitated in diethyl ether to obtain a photosensitive polymer resin represented by Chemical Formula 3a (yield: 62%). {HPLC conversion analysis (mol ratio%) = 2-methyl-2-adamantyl-methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Chemical Formula 1a = 36.0: 29.6: 34.4, GPC analysis: Mn = 4239, Mw = 8931, PD = 1.87, low molecular weight balance = 0.2%}

Example 10 Preparation of Photosensitive Polymer Resin (Formula 3b)

 Example 9, except that 79.97 g (0.322 mol) of 2-ethyl-2-adamantyl-methacrylate was used instead of 75.45 g (0.322 mol) of the 2-methyl-2-adamantyl-methacrylate In the same manner as in the photosensitive polymer resin represented by the formula (3b) was obtained (yield 54%). {HPLC conversion analysis (mol ratio%) = 2-ethyl-2-adamantyl-methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Chemical Formula 1a = 35.7: 30.0: 34.3, GPC analysis: Mn = 4401, Mw = 8912, PD = 1.80, low molecular weight balance = 0.2%}

Example 11 Preparation of Photosensitive Polymer Resin (Formula 3c)

 Example except that 84.49 g (0.322 mol) of 2-isopropyl-2-adamantyl-methacrylate was used instead of 75.45 g (0.322 mol) of the 2-methyl-2-adamantyl-methacrylate. In the same manner as in 9, a photosensitive polymer resin represented by Chemical Formula 3c was obtained (yield 55%). {HPLC conversion analysis (mol ratio%) = 2-isopropyl-2-adamantyl-methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Chemical Formula 1a = 38.2: 29.2: 32.6, GPC analysis: Mn = 4596, Mw = 8703, PD = 1.68, low molecular weight balance = 0.6%}

Example 12 Preparation of Photosensitive Polymer Resin (Formula 3d)

In the same manner as in Example 9, except that 45.79 g (0.322 mol) of t-butyl methacrylate was used instead of 75.45 g (0.322 mol) of 2-methyl-2-adamantyl-methacrylate The photosensitive polymer resin represented by 3d was obtained (yield 59%). {HPLC conversion analysis (mol ratio%) = t-butyl methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Chemical Formula 1a = 40.4: 27.8: 31.8 GPC analysis: Mn = 4958, Mw = 9669, PD = 1.75, low molecular weight balance = 0.4%}

Example 13 Preparation of Photosensitive Polymer Resin (Formula 3e)

Photosensitive compound represented by Chemical Formula 3e in the same manner as in Example 9, except that 58.35 g (0.161 mol) of the photosensitive compound represented by Chemical Formula 1c were used instead of 56.42 g (0.161 mol) of the compound represented by Chemical Formula 1a. A polymer resin was obtained (yield 52%). {HPLC conversion analysis (mol ratio%) = 2-methyl-2-adamantyl-methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Chemical Formula 1c = 37.4: 29.4: 33.2, GPC analysis: Mn = 5645, Mw = 10151, PD = 1.80, low molecular weight balance = 0.8%}

Example 14 Preparation of Photosensitive Polymer Resin (Formula 3f)

Photosensitive compound represented by Chemical Formula 3f in the same manner as in Example 9, except that 58.67g (0.161mol) of the photosensitive compound represented by Chemical Formula 1e were used instead of 56.42g (0.161mol) of the compound represented by Chemical Formula 1a. A polymer resin was obtained (yield 52%). {HPLC conversion analysis (mol ratio%) = 2-methyl-2-adamantyl-methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Chemical Formula 1e = 38.3: 29.1: 32.6, GPC analysis: Mn = 4775, Mw = 8847, PD = 1.85, low molecular weight balance = 0.3%}

Example 15 Preparation of Photosensitive Polymer Resin (Formula 3g)

Photosensitive compound represented by Chemical Formula 3g in the same manner as in Example 9, except that 54.16g (0.161mol) of the photosensitive compound represented by Chemical Formula 1b was used instead of 56.42g (0.161mol) of the compound represented by Chemical Formula 1a. A polymer resin was obtained. (Yield 50%) {HPLC conversion analysis (mol ratio%) = 2-methyl-2-adamantyl-methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Formula 1b = 36.6: 29.9: 33.4, GPC analysis: Mn = 5323, Mw = 9459, PD = 1.78, Low molecular weight balance = 0.5%}

Example 16 Preparation of Photosensitive Polymer Resin (Formula 3h)

Photosensitive compound represented by Chemical Formula 3h in the same manner as in Example 9, except that 56.09g (0.161 mol) of the photosensitive compound represented by Chemical Formula 1d were used instead of 56.42 g (0.161 mol) of the compound represented by Chemical Formula 1a. A polymer resin was obtained (yield 49%). {HPLC conversion analysis (mol ratio%) = 2-methyl-2-adamantyl-methacrylate: hydroxy adamantyl methacrylate: photosensitive compound represented by Chemical Formula 1d = 37.8: 29.4: 32.7, GPC analysis: Mn = 4686, Mw = 8493, PD = 1.81, low molecular weight balance = 0.3%}

Examples 17 to 24 and Comparative Example 1 Preparation of Chemically Amplified Photoresist Compositions

2.0 g of each photosensitive polymer resin and 0.02 g of triphenyl sulfonium triflate (TPS-105) obtained in Examples 9 to 16 were completely dissolved in 20 g of propylene glycol monomethyl ether acetate (PGMEA), followed by 0.2 μm of Filtration with a disk filter yielded a chemically amplified photoresist tm composition. The obtained photoresist composition was coated on a silicon wafer treated with hexamethyldisilazane (HMDS) to a thickness of about 0.2 μm. The wafer coated with the photoresist composition was prebaked at 100 ° C. (or 120 ° C.) for 90 seconds and exposed in a predetermined pattern using an ArF excimer laser having a numerical aperture of 0.60, and then exposed as shown in Table 1 below. The wafer was heated after exposure (PEB) at 100 ° C. (or 120 ° C.) for 90 seconds. The post-exposure heated wafer was developed for 30 seconds using a 2.38 wt% tetramethylammonium hydroxide (TMAH) solution to obtain a photoresist pattern of equal lines and spaces of 0.1 μm. Electron scanning micrographs of the obtained photoresist pattern are shown in Figs.

In addition, instead of 2.0 g of the photosensitive polymer resin obtained in Example 9, the photosensitive polymer resin represented by the following Chemical Formula 6 (HPLC conversion analysis (mol ratio%) = 2-methyl-2-adamantyl-methacrylate: gamma butyl) Lactone methacrylate = 42.8: 57.2, GPC analysis: Mn = 4985, Mw = 9578, PD = 1.92, low molecular weight residual = 0.1%), except that the chemically amplified photoresist composition in the same manner as in Example 17 Was prepared.

[Table 1]

division
The Number average
Molecular Weight (Mn) Weight average
Molecular Weight (Mw) Dispersion
(Pd) Low molecular weight
Remaining amount (%) Heating process
Process conditions
(℃ / 90sec) LER
(nm) Example 17 3a 4239 8931 1.87 0.2 120 6.7 Example 18 3b 4401 8912 1.80 0.2 100 5.3 Example 19 3c 4596 8703 1.68 0.6 100 6.4 Example 20 3d 4958 9669 1.75 0.4 120 5.1 Example 21 3e 5645 10151 1.80 0.8 120 4.5 Example 22 3f 4775 8847 1.85 0.3 120 4.2 Example 23 3g 5323 9459 1.78 0.5 120 5.1 Example 24 3h 4686 8493 1.81 0.3 120 4.9 Comparative Example 1 6 4985 9578 1.92 0.1 120 9.8

[Examples 25-1 to 25-8, Comparative Example 2] Comparison of etching resistance to oxide and polysilicon according to chemically amplified photoresist composition

Using the photoresist composition prepared in Examples 17 to 24 and Comparative Example 1, and the photoresist composition prepared in Comparative Example 1, etching resistance to oxides and polysilicon was measured and shown in FIG. 7.

As shown in Table 1 and FIGS. 1 to 8, the photosensitive polymer resin according to the present invention includes a bulky dinorbornene group and a lactone group, and has excellent etching resistance and adhesion to a semiconductor circuit board, Since it contains a functional group that is easily deprotected, the solubility of the developer is increased and the line edge roughness is excellent. Thus, the chemically amplified photoresist composition including the photosensitive polymer resin is used to form a thin photolithography process. It can be seen that one photoresist pattern is excellent. In addition, as shown in Figure 9, it can be seen that the etching resistance to the oxide and polysilicon of the chemically amplified photoresist composition according to the present invention is superior to the etching resistance of the conventional resist composition.

As described above, the photosensitive compound, the photosensitive polymer resin, and the photoresist composition including the same according to the present invention exhibit etching resistance, adhesion to semiconductor substrates, and line edge roughness even under short exposure wavelengths of 248 nm and 193 nm or less. Is excellent.

Claims (10)

The photosensitive compound represented by following formula (1). [Formula 1]

In Formula 1, R ₁ is H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thio alkyl group, and n is an integer of 1 or 2. The photosensitive compound of claim 1, wherein the photosensitive compound is selected from the group consisting of compounds represented by the following Chemical Formulas 1a to 1h. [Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

A photosensitive polymer resin comprising a repeating unit represented by the following formula (2). [Formula 2]

In Formula 2, R ₁ is H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thio alkyl group, n is an integer of 1 or 2, c is the photosensitive polymer It is 1-60 mol% as mol% of the said repeating unit with respect to the total repeating unit which comprises resin. The photosensitive polymer resin of claim 3, wherein the photosensitive polymer resin is represented by Formula 3 below. (3)

In Formula 3, R ₁ is each independently H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thio alkyl group, and R ₄ is an alkyl group having 1 to 20 carbon atoms or carbon atoms A cycloalkyl group having 5 to 40 carbon atoms, R ₅ is a cycloalkyl group having 5 to 10 carbon atoms including a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms having a halogen substituent, an ether group or an ester group, and n Is an integer of 1 or 2, and a, b and c are mole% of each repeating unit with respect to the entire photosensitive compound constituting the photosensitive polymer resin, and each 1 to 60 mole%: 1 to 60 mole%: 1 to 60 mole %to be. The photosensitive polymer resin of claim 3, wherein the photosensitive polymer resin is selected from the group consisting of compounds represented by the following Chemical Formulas 3a to 3h. [Chemical Formula 3]

(3b)

[Formula 3c]

[Formula 3d]

[Formula 3e]

[Formula 3f]

[Formula 3g]

[Formula 3h]

In Formulas 3a to 3h, a, b, and c are mole% of each repeating unit with respect to the entire photosensitive compound constituting the photosensitive polymer resin, and each 1 to 60 mole%: 1 to 60 mole%: 1 to 60 mole %to be. The photosensitive polymer resin according to claim 3, wherein the photosensitive polymer resin has a weight average molecular weight of 3,000 to 100,000.  Chemically amplified photoresist composition comprising a photosensitive polymer resin, a photoacid generator and an organic solvent comprising a repeating unit represented by the formula (2). [Formula 2]

In Formula 2, R ₁ is H or an alkyl group having 1 to 4 carbon atoms, R ₂ is OH, an alkoxyl group having 1 to 8 carbon atoms, or a thio alkyl group, n is an integer of 1 or 2, c is the photosensitive polymer It is 1-60 mol% as mol% of the said repeating unit with respect to the total repeating unit which comprises resin.  The chemically amplified photoresist composition of claim 7, wherein the photosensitive polymer resin is present in an amount of 1 to 30 wt% based on the total photoresist composition. The photoacid generator according to claim 7, wherein the photoacid generator is selected from the group consisting of eutechonic acid, sulfide-based compounds, onium salt-based compounds, and mixtures thereof, and the content of the photoacid generator is 0.1 to about photosensitive polymer resin. 20 wt% of the chemically amplified photoresist composition. The method of claim 7, wherein the organic solvent is ethylene glycol monomethyl ethyl, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, toluene, xylene, methyl ethyl ketone, Cyclohexanone, 2-hydroxypropionethyl, 2-hydroxyethyl 2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy 3-methylbutyrate, 3-methoxy 2-methylpropionic acid A chemically amplified photoresist composition selected from the group consisting of methyl, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methylpropionate, ethyl acetate, butyl acetate, and mixtures thereof.

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