KR101308695B1 - Acid amplifier and photosensitive polymer including the same - Google Patents

Abstract

By improving the sensitivity of the chemically amplified resist, an acid increasing agent capable of causing a difference in solubility of the exposed portion and the non-exposed portion and forming a fine pattern, and the acid increasing agent as a monomer constituting the photosensitive polymer Provided is a photosensitive polymer which can easily control acid diffusion and can improve line edge roughness. The acid increasing agent is a compound represented by the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 0 or 1, R ₁ is hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with fluorine (F), R ₂ is oxygen ( O) or an alkylene or cycloalkylene group having 1 to 30 carbon atoms or unsubstituted or substituted with nitrogen (N), or an arylene or alkylarylene group having 6 to 10 carbon atoms, R ₃ is a substitution comprising a hydroxy group (OH) or It is a C6-C30 aryl group, an arylalkyl group, or an alkylaryl group containing an unsubstituted C1-C30 alkyl group, a cycloalkyl group, or a hydroxyl group (OH).

Chemically amplified photoresist, acid multiplier, photoacid generator, sensitivity

Description

Acid amplifier and photosensitive polymer including same

1 is a schematic diagram showing a reaction mechanism of an acid multiplying agent.

2 is a graph showing the sensitivity of the photoresist composition according to the Examples and Comparative Examples of the present invention.

FIG. 3 is a graph showing a first collapse critical dimension (FCCD) in which an initial pattern of a photoresist composition according to examples and comparative examples of the present invention falls.

4 is a graph showing the line edge roughness (LER) of the photoresist composition according to the Examples and Comparative Examples of the present invention.

The present invention relates to an acid amplifier and a photosensitive polymer including the same, and more particularly, by improving the sensitivity of the chemically amplified resist, causing a difference in solubility of the exposed portion and the non-exposed portion, thereby forming a fine pattern. The present invention relates to a photosensitive polymer capable of easily controlling acid diffusion and improving line edge roughness by including an acid increasing agent and the acid increasing agent as monomers constituting the photosensitive polymer.

Recently, with the high integration of semiconductor devices, the development of dynamic random access memory (DRAM) having a storage capacity of more than a gigabit level has been actively progressed. In order to manufacture DRAM of 1 gigabit or more, an ultrafine pattern having a line width of 100 nm or less must be formed. To this end, photolithography technology using a short wavelength exposure source such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm) has been introduced, and not only has high resolution in short wavelength exposure sources, but also transparency and dry etching. Research into photoresist compositions excellent in resistance, adhesion to lower film quality, developability, sensitivity, and the like is being actively conducted.

In general, the positive chemically amplified photoresist includes a photoacid generator (PAG) that generates an acid component by exposure and a photosensitive polymer having a protecting group decomposed by the acid component. When the chemically amplified photoresist is exposed, an acid component is generated from the photoacid generator, and the generated acid component serially decomposes the protecting group bonded to the skeleton of the polymer to change the solubility of the polymer. Form a pattern with high contrast. In the photolithography process using the chemically amplified photoresist, a post exposure bake (PEB) process is performed to activate and diffuse an acid component present in the exposed photoresist.

The sensitivity of chemically amplified resists is determined by the amount of acid generated from the photoacid generator and the acid degree. Therefore, a large amount of photoacid generator can be used to improve the sensitivity of the resist, but when the content of the photoacid generator exceeds 10% by weight based on the total resist composition, the association between the photoacid generators or the large spectral absorption degree Problems requiring this occur. In order to solve this problem, a method of enhancing the sensitivity by adding an acid amplifier to the chemically amplified photoresist has been attempted. 1 is a schematic diagram showing a reaction mechanism of an acid multiplying agent. As shown in FIG. 1, when an acid increasing agent is used, additional acid (H ⁺ ) is generated during the post-exposure heating (PEB) process, so that an effect of sensitivity enhancement may be obtained. That is, during the post-exposure heating (PEB) process, the acid generated from the photoacid generator in the exposed part serves as an acid catalyst to decompose the acid multiplier, and the acid multiplier is much higher than the amount of acid generated from the photoacid generator. By generating (H ⁺ ), the sensitivity of the photoresist can be enhanced, and when the sensitivity of the photoresist is enhanced, a chain deprotection reaction of an acid-sensitive polymer (COOR) occurs, so that the solubility difference between the exposed portion and the non-exposed portion is different. By increasing, fine patterns can be formed. The acid multiplier must be decomposed by (iv) acid catalysis, (ii) thermally stable in the absence of acid, and (iii) the acid produced must be strong enough to catalyze the reaction. Therefore, the development of an acid multiplying agent that satisfies the above conditions is required.

Accordingly, an object of the present invention is to provide an acid multiplier for improving the energy sensitivity and contrast of alkali dissolution of chemically amplified resists and enhancing plasma etching resistance, and a photosensitive polymer comprising the same. will be.

It is another object of the present invention to provide an acid multiplier which acts as a plasticizer to improve adhesion to a substrate and a photosensitive polymer comprising the same.

Still another object of the present invention is to provide an acid multiplier for easily controlling acid diffusion generated and improving line edge roughness and a photosensitive polymer including the same.

In order to achieve the above object, the present invention provides an acid increasing agent represented by the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 0 or 1, R ₁ is hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with fluorine (F), R ₂ is oxygen ( O) or an alkylene or cycloalkylene group having 1 to 30 carbon atoms or unsubstituted or substituted with nitrogen (N), or an arylene or alkylarylene group having 6 to 10 carbon atoms, R ₃ is a substitution comprising a hydroxy group (OH) or It is a C6-C30 aryl group, an arylalkyl group, or an alkylaryl group containing an unsubstituted C1-C30 alkyl group, a cycloalkyl group, or a hydroxyl group (OH).

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

[Formula 2]

In Formula 2, n is an integer of 0 or 1, R and R ₁ are each independently hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with a fluorine group (F), R ₂ is an alkylene or cycloalkylene group having 1 to 30 carbon atoms or unsubstituted or substituted with oxygen (O) or nitrogen (N) or an arylene or alkylarylene group having 6 to 10 carbon atoms, and R ₃ is a hydroxy group (OH) A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group or an aryl group having 6 to 30 carbon atoms, an arylalkyl group or an alkylaryl group, and R ^* includes or does not include an ether group or an ester group. An unsubstituted alkyl group having 1 to 20 carbon atoms or a cycloalkyl group, a and b are mol% of the repeating units with respect to the total repeating units constituting the photosensitive polymer, each independently 80 to 99 mol% and 1 to 20 % A.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

Acid increasing agent according to the present invention is a compound represented by the following formula (1).

In Formula 1, n is an integer of 0 or 1, R ₁ is hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with fluorine (F), R ₂ is oxygen ( O) or a hydrocarbon containing an alkylene or cycloalkylene group or a benzene group having 1 to 30 carbon atoms substituted or unsubstituted with nitrogen (N), preferably an arylene or alkylarylene group having 6 to 10 carbon atoms, and R ₃ is A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group or a hydrocarbon group containing a hydroxy group (OH) and a benzene group containing a hydroxy group (OH), preferably an aryl group having 6 to 30 carbon atoms including a hydroxy group (OH) , An arylalkyl group or an alkylaryl group.

,

, CH₂,

등을 예시할 수 있고, R₃의 바람직한 예로는

,

,

,

,

,

,

,

등을 예시할 수 있다.(여기서,

표시는 결합부위를 나타낸다.)Preferred examples of R ₁ may include H, CH ₃ , CF ₃ and the like, and preferred examples of R ₂

,

, CH ₂ ,

And the like, and preferred examples of R ₃ include

,

,

,

,

,

,

,

And the like can be exemplified.

The mark indicates the joint.)

R ₃ of the acid multiplying agent can increase the acid generation efficiency in the molecule, including a hydroxy group, and also has a cyclic structure to reduce the entanglement or density between the polymer, thereby increasing the momentum of the molecule It is thermally stable and can generate strong acids as well as act as a plasticizer, improving adhesion to the substrate.

Preferred examples of the acid multiplicant represented by 1 according to the present invention can illustrate a compound represented by the following formula 1a to 1h.

The acid increasing agent represented by Chemical Formula 1 according to the present invention may be prepared by a condensation reaction of a compound containing a hydroxy group and a compound containing a sulfonyl chloride group. For example, as shown in Scheme 1 below, a compound containing a hydroxy group and a compound containing a sulfonyl chloride group are dissolved in pyridine, a reaction solvent, and then condensation reaction (exothermic) is performed at 0 ° C. or lower for 1 to 3 hours. Reaction), hydrochloric acid (HCl) is added to remove pyridine, and then recrystallized with methanol to prepare an acid multiply represented by Chemical Formula 1.

In Scheme 1, n, R ₁ , R ₂ and R ₃ are the same as defined in Chemical Formula 1.

The present invention also provides a photosensitive polymer comprising an acid increasing agent represented by the following formula (2).

In Formula 2, n is an integer of 0 or 1, R and R ₁ are each independently hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with a fluorine group (F), R ₂ is an alkylene or cycloalkylene group having 1 to 30 carbon atoms or unsubstituted or substituted with oxygen (O) or nitrogen (N) or an arylene or alkylarylene group having 6 to 10 carbon atoms, and R ₃ is a hydroxy group (OH) A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group or an aryl group having 6 to 30 carbon atoms, an arylalkyl group or an alkylaryl group, and R ^* includes or does not include an ether group or an ester group. An unsubstituted alkyl group having 1 to 20 carbon atoms or a cycloalkyl group, a and b are mol% of the repeating units with respect to the total repeating units constituting the photosensitive polymer, each independently 80 to 99 mol% and 1 to 20 % A.

The photosensitive polymer may be prepared by polymerizing an acid increasing agent according to the present invention and a monomer commonly used in the preparation of the photosensitive polymer, and the commonly used monomer may be represented by the following Chemical Formula 3.

In Formula 3, R and R ^* are as defined in Formula 2.

The monomer of Formula 3 is a monomer having an acid-sensitive protecting group (R ^* ), and as the protecting group (R ^* ), but not limited to t -butyl, tetrahydropyran-2-yl, 2-methyl tetrahydropyran-2 -Yl, tetrahydrofuran-2-yl, 2-methyl tetrahydrofuran-2-yl, 1-methoxy propyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1 -Methylethyl, 1-methoxyethyl, 1-ethoxyethyl, t -butoxyethyl, 1-isobutoxyethyl or 2-acetylment-1-yl, adamantyl and the like can be exemplified. R ^* ) may be substituted with a substituent such as a hydroxy group, a halogen group. Here, the acid-sensitive protecting group is a group that can be released by the acid, and determines whether or not the photoresist material is dissolved in the alkaline developer. That is, when an acid-sensitive protecting group is attached, the photoresist material is suppressed from being dissolved by the alkaline developer, but when the acid-sensitive protecting group is desorbed by the acid generated from the photoacid generator under stimulation of light, the photoresist is released. The substance can be dissolved in the developer. Specific examples of the monomer represented by Chemical Formula 3 may be represented by the following Chemical Formulas 3a to 3c.

In addition, the photosensitive polymer is a monomer commonly used in the production of photosensitive polymers, such as cycloolefin (eg maleic hydride) monomers, in addition to the monomer having an acid-sensitive protecting group represented by the formula (3), crosslinkability Monomers, etc. may be further included, and the content of these auxiliary monomers is 0-5 mol% with respect to a total repeating unit normally. The photosensitive polymer according to the present invention may be a block copolymer or a random copolymer, and a weight average molecular weight (Mw) is 3,000 to 100,000, and polydispersity is preferably 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. Since the acid increasing agent attached to the side chain of the photosensitive polymer according to the present invention is directly connected to the photosensitive polymer, it is possible to efficiently adjust the diffusion of acid generated therefrom to improve line edge roughness. Specific examples of the photosensitive polymer may be represented by the following formula (4).

In Formula 4, n, R, R ₁ , R ₂ and R ₃ are as defined in Formula 2, R ₄ is hydrogen, methyl or ethyl group, a, b, c and d are constituting the photosensitive polymer As mol% of the said repeating unit with respect to all the repeating units, they are each independently 1-60 mol%, 1-60 mol%, 1-60 mol%, 1-20 mol%.

According to the present invention, the photosensitive polymer is a) dissolving the acid increasing agent represented by the formula (1), the monomer having a protecting group sensitive to the acid and the polymerization initiator in a polymerization solvent, b) nitrogen, argon and the like In an inert atmosphere of, it can be prepared by reacting at a temperature of 30 to 70 ℃ for 4 to 24 hours. In addition, the polymerization may be performed by a radical polymerization reaction, a solution polymerization reaction, a bulk polymerization reaction or a polymerization reaction using a metal catalyst. In addition, the preparation method may further comprise the step of (b) purifying the reaction product using a lower alcohol, water, a mixture thereof, and the like, including diethyl ether, petroleum ether, methanol, ethanol or isopropanol. It may be. As the polymerization solvent, a polymerization solvent commonly known in the art may be widely used, but is not limited to cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane and methylethyl. Ketones, benzene, toluene, xylene, or mixtures thereof, and the polymerization initiator may also be widely used as polymerization initiators commonly known in the art, but is not limited to benzoyl peroxide, 2,2 '. Azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butylperacetate, t-butylhydroperoxide, di-t-butylperoxide or mixtures thereof.

Photoresist composition according to the invention is a photosensitive polymer represented by the formula (2) comprising an acid increasing agent; Photoacid generators generating acid; And an organic solvent, and may further include various additives as necessary. The content of the photosensitive polymer represented by Formula 2 is preferably 1 to 30% by weight, more preferably 3 to 15% by weight based on the total photoresist composition. If the content of the photosensitive polymer is less than 1% by weight, the resist layer remaining after coating may be too thin to form a pattern having a desired thickness, and may not obtain the expected effect of acid growth, and may exceed 30% by weight. There is a problem that the uniformity is lowered and the contrast is reduced by the excessive amount of acid generation.

The photoacid generator generates an acid component such as H ⁺ by exposure, and serves to deprotect the protecting group of the photosensitive polymer, and any compound capable of generating an acid by light may be used. Can be used sulfide salt compounds such as eutectic acid, onium salt compounds such as onium salts, and mixtures thereof. Non-limiting examples of photoacid generators include phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone, nap having low absorbance at 157 nm and 193 nm. Naphthylimido trifluoromethane sulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroarsenate (diphenyliodonium hexafluoroarsenate) diphenyliodonium hexafluoroantimonate), diphenylparamethoxyphenylsulfonium triflate, diphenylparatoluenylsulfonium triflate, diphenylparaisobutylphenylsulfonium triflate , Triphenylsulfo Triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate and Mixtures of these can be exemplified. The content of the photoacid generator is preferably 0.05 to 20 parts by weight based on 100 parts by weight of the photosensitive polymer. If the amount is less than 0.05 parts by weight, the sensitivity of the photoresist composition to light may be deteriorated, which may make it difficult to deprotect the protecting group. If the amount is more than 20 parts 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.

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 Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol, propylene glycol monoacetate, toluene, xylene, methyl ethyl ketone, Methyl isoamyl ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxy propionate, ethyl ethoxy propionate, N, N-dimethylformamide , N, N-dimethylacetamide, N-methyl 2-pyrrolidone, 3-ethoxyethyl Propionate, 2-heptanone, gamma-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy 2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2-hydroxy 3-methyl moiety Methyl carbonate, methyl 3-methoxy 2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methylpropionate, ethyl acetate, butyl acetate and mixtures thereof.

In addition, the photoresist composition according to the present invention may further include an organic base, if necessary, 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% by weight based on the total photoresist composition. If the content of the organic base is less than 0.01% by weight, a t-top phenomenon may occur in the resist pattern, and if the content is more than 10% by weight, the sensitivity of the photoresist composition may be reduced and the pattern formation rate may be lowered. .

The photoresist composition according to the present invention may be prepared by mixing the photosensitive polymer represented by Formula 2 including the acid increasing agent, a photoacid generator for generating an acid, an organic solvent, and various additives, and filtering with a filter as necessary. Can be.

In order to form a photoresist pattern using the photoresist composition according to the present invention, first, the photoresist composition is applied to a substrate such as a silicon wafer or an aluminum substrate using a spin coater to form a photoresist film. After exposing the photoresist film with a predetermined pattern, and then forming the photoresist pattern by a conventional photolithography process in which the exposed photoresist pattern is exposed and heated after exposure and developed, a semiconductor device having a desired pattern can be provided. The exposure process may use not only ArF but also KrF, F ₂ , Extreme Ultra Violet (EUV), Vacuum Ultra Violet (VUV), E-beam, X-ray, Immersion lithography or ion beam, and 1 to 100 mJ. It is preferable to carry out with an exposure energy of / cm ² . The developing solution used in the developing step may be an aqueous alkaline solution prepared by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide (TMAH) in a concentration of 0.1 to 10 wt% , An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, etc. and a surfactant may be added to the developer. In addition, after the development process, the cleaning process may be further performed to clean the substrate with ultrapure water.

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 1-1 Preparation of Acid Multiplier Represented by Chemical Formula 1a

1 g (8.61 mmol) of the compound represented by the following formula (5a) and 100 mL of pyridine were added to a 500 mL flask, and then 2.34 g (10.33 mmol) of the compound represented by the following formula (6a) was added to 30 mL of pyridine in a stirred solution at 0 ° C. The melted solution was added dropwise while maintaining 0 ° C., stirred for 2 hours, and neutralized by adding 200 mL of cold 10% hydrochloric acid (HCl) while maintaining the temperature below 20 ° C. After neutralization, the resulting compound was filtered, washed 3 to 5 times with 10% HCl and water, and then recrystallized with 200 mL of methanol to obtain a compound represented by Chemical Formula 1a in a yield of 74.1%. {1H-NMR, CDCl ₃ : H (d, 6.15), H (d, 5.58), CH (m, 4.86), CH ₂ (t, 4.15), CH ₂ (t, 3.41), CH (m, 3.35), CH ₂ (m, 2.13 ), CH ₃ (m, 1.93), 4CH ₂ (m, 1.40)}.

Example 1-2 Preparation of Acid Extender Represented by Formula (1b)

A compound represented by Chemical Formula 1b in the same manner as in Example 1-1, except that 1 g (7.80 mmol) of Compound 5b and 2.12 g (9.36 mmol) of Compound 6a were used. Was prepared in a yield of 75.5% {1H-NMR, CDCl ₃ : H (d, 6.15), H (d, 5.58), CH (t, 4.88), CH ₂ (t, 4.15), CH ₂ (t, 3.41), CH (t, 3.37), CH ₂ (m, 2.13), CH ₃ (m, 1.93), 2CH, (m, 1.60), 3CH ₂ (m, 1.47)}.

Example 1-3 Preparation of Acid Extender Represented by Chemical Formula 1c

A compound represented by Chemical Formula 1c in the same manner as in Example 1-1, except that 1 g (4.42 mmol) of Compound 5c and 1.25 g (5.30 mmol) of Chemical Formula 6b were used. Was prepared in a yield of 70.9% {H-NMR, CDCl ₃ : H (d, 5.89), H (d, 5.49), CH (t, 4.85), CH ₂ (s, 3.59), CH (t, 3.34 ), CH ₃ (m, 1.93), 2CH (m, 1.61), 2CH ₃ (s, 1.35), 10CH ₂ (m, 1.29)}.

[Example 1-4] The acid-amplifier producing represented by the following general formula 1d

A compound represented by Chemical Formula 1d in the same manner as in Example 1-1, except that 1g (5.87 mmol) of Compound 5d and 1.69 g (7.05 mmol) of Compound 6b were used. Was prepared in a yield of 70.4% {H-NMR, CDCl ₃ : H (d, 5.89), H (d, 5.49), CH ₂ (s, 3.59), CH ₃ (m, 1.93), 4CH ₂ (t , 1.62), 4CH ₂ (m, 1.51), 2CH ₃ (s, 1.35)}.

Example 1-5 Acid Producing Agents Represented by Chemical Formula 1e

A compound represented by Chemical Formula 1e in the same manner as in Example 1-1, except that 1 g (5.87 mmol) of Compound 5e and 1.09 g (7.05 mmol) of Compound 6c were used. Was prepared in a yield of 81.7% {H-NMR, CDCl ₃ : CH (m, 4.77), 2H (d, 4.75), CH ₂ (s, 4.08), CH (m, 3.20), CH ₃ (s, 1.71), 2CH (m, 1.60), 2CH ₂ (m, 1.44), 4CH ₂ (m, 1.29)}.

Example 1-6 Preparation of Acid Proliferator Represented by Formula (1f)

A compound represented by Chemical Formula 1f was prepared by the same method as Example 1-1, except that 1 g (5.37 mmol) of Compound 5f and Compound 1g (6.44 mmol) represented by Chemical Formula 6c were used. It was prepared in a yield of 78.8% {H-NMR, CDCl ₃ : 2CH (d, 7.55), 2CH (d, 7.31), 2CH (d, 7.27), 2CH (d, 6.79), 2H (d, 4.75), CH ₂ (s, 4.08), CH ₃ (s, 1.71)}.

Example 1-7 Acid Producing Agent Represented by Chemical Formula 1g

A compound represented by Chemical Formula 1g in the same manner as in Example 1-1, except that 1 g (6.93 mmol) of Compound represented by Chemical Formula 5g and 1.80 g (8.32 mmol) of Compound represented by Chemical Formula 6d were used. Was prepared in a yield of 80.5% {H-NMR, CDCl ₃ : 2CH (d, 7.89), 2CH (d, 7.64), H (d, 5.33), H (d, 4.96), 2CH ₂ (t, 3.49 ), CH ₃ (s, 1.71), 2CH (m, 1.62), 4CH ₂ (m, 1.25)}.

Example 1-8 Acid Producing Agents Represented by Chemical Formula 1h

A compound represented by Chemical Formula 1h in the same manner as in Example 1-1, except that 1 g (5.09 mmol) of Compound 5h and 1.32 g (6.11 mmol) of Compound 6d were used. Was prepared in a yield of 80.3% {H-NMR, CDCl ₃ : 2CH (d, 7.89), 2CH (d, 7.64), H (d, 5.33), H (d, 4.96), 2CH ₂ (t, 3.49 ), CH ₃ (s, 1.71), 2CH (m, 1.65), 4CH (M, 1.48), 4CH ₂ (M, 1.43)}.

Example 2-1 Preparation of Photosensitive Polymer Including Acid Producing Agent Prepared in Example 1-1

8 g of the acid increasing agent represented by Chemical Formula 1a, 25.8 g of Compound represented by Chemical Formula 3a, 13.3 g of Compound represented by Chemical Formula 3b, 12.3 g of Compound represented by Chemical Formula 3c, and azobis (isobutyronitrile) ) (AIBN) 3g was added, the reaction was dissolved in anhydrous THF 200ml, the gas was removed using an ampoule (freeze method), and the gas-free reaction was polymerized at 66 ° C. for 12 hours. After the polymerization was completed, the precipitate was slowly added dropwise to an excess of diethyl ether, followed by precipitation. The precipitate was dissolved again with THF, and the dissolved reactant was reprecipitated in diethyl ether to give a polymer represented by the following Chemical Formula 4a. Was prepared in a yield of 73.1% (Molecular weight (Mw): 7,888, polydispersity: 1.81).

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

[Example 2-2] The photosensitive polymer containing the acid proliferator prepared in Example 1-2 Preparation

Example 2-1 except that 8.3g of the acid increasing agent represented by 1b prepared in Example 1-2 was used instead of 8g of the acid increasing agent represented by Formula 1a prepared in Example 1-1. In the same manner as in the polymer represented by the following formula 4b was prepared in a yield of 72.4% (molecular weight (Mw): 7,254, polydispersity: 1.69).

[Example 2-3] The photosensitive polymer containing the above-described one acid-amplifier manufactured by the manufacturing example 1-3

Example 2-1, except that 11.2 g of the acid increasing agent represented by 1c prepared in Example 1-3 was used instead of 8 g of the acid increasing agent represented by Chemical Formula 1a prepared in Example 1-1. The polymer represented by the following Chemical Formula 4c was prepared in the same manner as in the yield of 75.5% (molecular weight (Mw): 7,629, polydispersity: 1.72).

[Example 2-4] Preparation of a photosensitive polymer containing the acid proliferator prepared in Examples 1 to 4

Example 2-1 except that 9.7 g of the acid increasing agent represented by 1d prepared in Example 1-4 was used instead of 8 g of the acid increasing agent represented by Chemical Formula 1a prepared in Example 1-1. In the same manner as in the polymer represented by the following formula 4d was prepared in a yield of 70.9% (molecular weight (Mw): 7,677, polydispersity: 1.69).

[Example 2-5] The photosensitive polymer containing the acid proliferator prepared in Example 1-5 Preparation

Example 2-1, except that 7.5g of the acid multiplier represented by 1e prepared in Example 1-5 was used instead of 8g of the acid multiplier represented by Formula 1a prepared in Example 1-1 A polymer represented by the following Chemical Formula 4e was prepared in the same manner as in the yield of 70.1% (molecular weight (Mw): 8,190, polydispersity: 1.75).

[Example 2-6] The photosensitive polymer containing the acid proliferator prepared in Example 1-6 Preparation

Example 2-1 except that 7.9 g of the acid increasing agent represented by 1f prepared in Example 1-6 was used instead of 8 g of the acid increasing agent represented by Chemical Formula 1a prepared in Example 1-1. A polymer represented by the following Chemical Formula 4f was prepared in the same manner as in the yield of 75.3% (molecular weight (Mw): 7,336, polydispersity: 1.81).

[Example 2-7] The photosensitive polymer containing the acid proliferator prepared in Example 1-7 Preparation

Example 2-1, except that 8.4g of the acid multiplier represented by 1g prepared in Example 1-7 was used instead of 8g of the acid multiplier represented by Formula 1a prepared in Example 1-1. A polymer represented by the following Chemical Formula 4g was prepared in the same manner as in the yield of 76.1% (molecular weight (Mw): 7,997, polydispersity: 1.74).

Example 2-8 Preparation of Photosensitive Polymer Containing Acid Producing Agent Prepared in Example 1-8

Example 2-1 except that 9.8 g of the acid increasing agent represented by 1h prepared in Example 1-8 was used instead of 8g of the acid increasing agent represented by Chemical Formula 1a prepared in Example 1-1. A polymer represented by the following Chemical Formula 4h was prepared in the same manner as in the yield of 69.4% (molecular weight (Mw): 7,543, polydispersity: 1.77).

[Comparative Example 1] Preparation of photosensitive polymer containing no acid increasing agent

A polymer represented by the following Chemical Formula 7 was prepared in a yield of 70.2% in the same manner as in Example 2-1, except that no acid increasing agent was used (molecular weight (Mw): 8,001, polydispersity) : 1.84).

[Examples 3-1 to 3-8 and Comparative Example 2] Preparation of a photoresist composition containing the photosensitive polymer prepared in Examples 2-1 to 2-8 and Comparative Example 1

1 g of the photosensitive polymer prepared in Example 2-1 and 0.05 g of phthalimidotrifluoromethanesulfonate were dissolved in 14 g of propylene glycol monomethyl ether acetate (PGMEA), and then filtered through a 0.20 μm filter to prepare a photoresist composition. (Example 3-1), except that 1g of the photosensitive polymer prepared in Examples 2-2 to 2-8 and Comparative Example 1 was used instead of 1g of the photosensitive polymer prepared in Example 2-1. Photoresist compositions were prepared in the same manner (Examples 3-2 to 3-8 and Comparative Example 2).

[Examples 4-1 to 4-8 and Comparative Example 3] Exposure pattern formation and sensitivity measurement using photoresist composition

Photoresist was prepared by spin coating the photoresist composition prepared in Examples 3-1 to 3-8 and Comparative Example 2 on the etched layer of the silicon wafer treated with hexamethyldisilazane (HMDS) to a thickness of 0.1 μm. After manufacturing the thin film, soft heat treatment for 90 seconds in an oven or hot plate at 100 ℃ (or 120 ℃), exposed using an ArF laser exposure equipment having a numerical aperture of 0.6, and then 90 at 100 ℃ (or 120 ℃) Bake again for a second. The heated wafer was immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds and developed to form an equal line and a space (L / S) pattern of 0.1 μm at the same time. The first collapse critical dimension (FCCD) and line edge roughness (LER) were measured and shown in Table 1 below. Sensitivity in the positive resist is defined as the minimum amount of exposure necessary to completely remove the photoresist of the exposed portion by development.

Photoresist composition Sensitivity (mJ / cm ² ) FCCD (nm) LER (nm) Example 3-1 24 69.1 3.1 Example 3-2 24 64.8 2.9 Example 3-3 29 67.4 3.0 Example 3-4 29 67.3 3.3 Example 3-5 26 69.9 3.2 Examples 3-6 31 71.1 3.5 Examples 3-7 27 68.2 3.6 Examples 3-8 26 65.7 3.7 Comparative Example 2 38 75 4.7

From Table 1, when the pattern is formed using a photoresist composition (Examples 3-1 to 3-8) containing an acid increasing agent according to the present invention, a photoresist composition containing no acid increasing agent (comparison Compared to Example 2, it can be seen that the energy sensitivity, the critical dimension FCCD and the line edge roughness LER are improved, thereby forming a fine pattern.

2 is a graph showing the sensitivity of the photoresist composition according to the Examples and Comparative Examples of the present invention, Figure 3 is a critical dimension (FCCD; First fall) the first pattern of the photoresist composition according to the Examples and Comparative Examples of the present invention collapse critical dimension), Figure 4 is a graph showing the line edge roughness (LER) of the photoresist composition according to the Examples and Comparative Examples of the present invention.

As described above, the acid increasing agent and the photosensitive polymer including the same according to the present invention may improve the sensitivity of the chemically amplified resist and contrast against alkali decomposition, and enhance plasma etching resistance. In addition, the acid increasing agent and the photosensitive polymer including the same according to the present invention can act as a plasticizer to improve adhesion to the substrate, and since the acid increasing agent forms a photosensitive polymer, it is easy to control the acid diffusion generated. Edge roughness can be improved.

Claims (7)

An acid increasing agent represented by the following formula (1). [Formula 1]

In Formula 1, n is 1, R ₁ is hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with a fluorine group (F), R ₂ is oxygen (O) or nitrogen An alkylene or cycloalkylene group having 1 to 30 carbon atoms substituted or unsubstituted with (N) or an arylene or alkylarylene group having 6 to 10 carbon atoms, and R ₃ is a substituted or unsubstituted carbon atom containing a hydroxy group (OH) It is a C6-C30 aryl group, an arylalkyl group, or an alkylaryl group containing an alkyl group, a cycloalkyl group, or a hydroxyl group (OH) of 1-30. According to claim 1, wherein the acid multiplying agent

,

,

, And

Acid increasing agent which is selected from the group represented by. A photosensitive polymer comprising a repeating unit represented by the following formula (2). [Formula 2]

In Formula 2, n is 1, R and R ₁ are each independently hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with fluorine (F), R ₂ is oxygen (O) or a C 1-30 alkylene or cycloalkylene group substituted or unsubstituted with nitrogen (N) or an arylene or alkylarylene group having 6 to 10 carbon atoms, R ₃ is a substitution comprising a hydroxy group (OH) Or an unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group or an aryl group having 6 to 30 carbon atoms, an arylalkyl group or an alkylaryl group, and R ^* includes or does not include an ether group or an ester group. It is an alkyl group or a cycloalkyl group of 1-20, and a and b are mol% of the said repeating unit with respect to the total repeating unit which comprises the said photosensitive polymer, and are each independently 80-99 mol% and 1-20 mol%. The photosensitive polymer according to claim 3, wherein the photosensitive polymer is represented by the following Chemical Formula 4. [Formula 4]

In Formula 4, n, R, R ₁ , R ₂ and R ₃ are as defined in Formula 2, R ₄ is hydrogen, methyl or ethyl group, a, b, c and d are constituting the photosensitive polymer As mol% of the said repeating unit with respect to all the repeating units, they are each independently 1-60 mol%, 1-60 mol%, 1-60 mol%, 1-20 mol%. A photosensitive polymer represented by Formula 2 below; Photoacid generators generating acid; And Photoresist composition comprising an organic solvent. [Formula 2]

In Formula 2, n is 1, R and R ₁ are each independently hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with fluorine (F), R ₂ is oxygen (O) or a C 1-30 alkylene or cycloalkylene group substituted or unsubstituted with nitrogen (N) or an arylene or alkylarylene group having 6 to 10 carbon atoms, R ₃ is a substitution comprising a hydroxy group (OH) Or an unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group or an aryl group having 6 to 30 carbon atoms, an arylalkyl group or an alkylaryl group, and R ^* includes or does not include an ether group or an ester group. It is an alkyl group or a cycloalkyl group of 1-20, and a and b are mol% of the said repeating unit with respect to the total repeating unit which comprises the said photosensitive polymer, and are each independently 80-99 mol% and 1-20 mol%. The photoresist composition of claim 5, wherein the photoresist composition comprises 1 to 30% by weight of the photosensitive polymer based on the total photoresist composition, 0.05 to 20 parts by weight of the photoacid generator and the remaining organic solvent based on 100 parts by weight of the photosensitive polymer. Photoresist composition. A photosensitive polymer represented by Formula 2 below; Photoacid generators generating acid; And applying a photoresist composition comprising an organic solvent to the substrate to form a photoresist film. And Exposing the photoresist film in a predetermined pattern; and then heating and developing the exposed photoresist pattern after exposure. [Formula 2]

In Formula 2, n is 1, R and R ₁ are each independently hydrogen (H), or an alkyl or cycloalkyl group having 1 to 30 carbon atoms unsubstituted or substituted with fluorine (F), R ₂ is oxygen (O) or a C 1-30 alkylene or cycloalkylene group substituted or unsubstituted with nitrogen (N) or an arylene or alkylarylene group having 6 to 10 carbon atoms, R ₃ is a substitution comprising a hydroxy group (OH) Or an unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group or an aryl group having 6 to 30 carbon atoms, an arylalkyl group or an alkylaryl group, and R ^* includes or does not include an ether group or an ester group. It is an alkyl group or a cycloalkyl group of 1-20, and a and b are mol% of the said repeating unit with respect to the total repeating unit which comprises the said photosensitive polymer, and are each independently 80-99 mol% and 1-20 mol%.

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