KR101365681B1 - Novel photo-acid generator, photosensitive polymer containing the same and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a novel photoacid generator which can be applied as a monomer to the polymerization of a photosensitive polymer, a photosensitive polymer comprising the same, and a method of manufacturing the same. More specifically, the photosensitive polymer is a chemically amplified resist composition used in a semiconductor process. It relates to a photosensitive polymer comprising a photoacid generator in the main chain of and a method for producing the same. Since the photosensitive polymer of the present invention includes a photoacid generator having a vinyl group introduced into an alicyclic ring, the photosensitive polymer can be manufactured as a polymer polymer, thereby minimizing the nonuniformity of the photoacid generator in the resist and the tipping phenomenon, and improving the line edge roughness. It is effective, so you can get better resolution.

Description

Novel photo-acid generator, photosensitive polymer comprising same and manufacturing method thereof {NOVEL PHOTO-ACID GENERATOR, PHOTOSENSITIVE POLYMER CONTAINING THE SAME AND MANUFACTURING METHOD THEREOF}

The present invention relates to a novel photoacid generator which can be applied as a monomer to the polymerization of a photosensitive polymer, a photosensitive polymer comprising the same, and a method of manufacturing the same. More specifically, the photosensitive polymer is a chemically amplified resist composition used in a semiconductor process. It relates to a photosensitive polymer comprising a photoacid generator in the main chain of and a method for producing the same.

In semiconductor microfabrication using lithography, chemically amplified resist compositions generally include photoacid generators and photosensitive polymers that generate acids upon exposure. The chemically amplified resist undergoes a post-exposure heating process, wherein the heated acid component penetrates into the resist of the non-exposed portion and increases the solubility of the non-exposed portion, thereby changing the line width of the resist pattern, or causing the pattern to collapse or line edges. It causes roughness (LER, line edge roughness).

Conventionally, amines or amide compounds are used as quenchers or additives in order to effectively control the acid generated by photoacid generators at the exposure sites. Excessive use of these compounds increases the light absorption and increases the optimal exposure energy. There is a disadvantage, which leads to a decrease in productivity of the exposure equipment. In addition, the finer the pattern, the more difficult it is to control the diffusion of acid generated from the photoacid generator, so that the line edge roughness tends to increase, which further increases the importance of reducing the line edge roughness and decreasing the line width change due to the heating temperature after exposure. It is becoming.

A lithography process that has been used to date is dry lithography, which uses an exposure system in which air is filled between the exposure lens and the wafer. In order to develop a 60nm device using dry lithography, a new exposure system using an F ₂ laser or an EUV laser as a light source must be used. When using an F ₂ laser, a pellicle is difficult to develop and an EUV laser is used. In case of use, there is a problem in developing a mask and a light source.

In order to solve the above problems, an immersion lithography process has been newly developed. Immersion lithography is a technique that improves resolution by filling any water soluble liquid between the final projection lens and the wafer and increasing the numerical aperture (NA) of the optical system by the refractive index of the liquid.

In particular, by using a 193 nm light source (ArF laser) and inserting a liquid having a refractive index higher than air, such as water and ethylene glycol, between the projection lens and the wafer, the numerical aperture NA of the projection lens can be designed to 1.0 or more. ArF immersion lithography is being used which can achieve high resolution.

However, since ArF immersion lithography is filled between the final projection lens and the wafer with an arbitrary water-soluble immersion lithography liquid such as water, not air, the photoacid generator, which constitutes the resist, is dissolved in the liquid for immersion lithography upon exposure. This occurs to cause contamination of the exposure lens and deformation of the formed resist pattern.

In order to improve this problem, the development by the modification of the anion has been progressed to improve the diffusion rate and transparency of the acid and to reduce the elution to water. In addition, in recent years, in connection with a number of experimental results and papers that negative ions can affect more than positive ions as a physical and chemical property that substantially improves the fluidity of the acid and the physical properties of the composition of the resist, in recent years, The invention has been newly made, and thus the focus is on the invention of a photoacid generator that reduces acid diffusion rate and has good permeability to a 193 nm ArF light source.

Therefore, attempts have been made to introduce bulky cycloaliphatic rings, high carbon number alkyl types, alkoxy types or ether types to suitable anion salts as photoacid generators (Korean Patent Application No. 10-2006-0114104, 10-2007-0069049, 10-2005-0107599, 10-2007-0053619).

However, some of the materials in the patent document cause the phenomenon of the photoacid generator in the resist caused by the repulsion of the immersion solution of the excessive hydrophobic photoacid generator by the bulky alicyclic ring introduced to suppress the elution to water and have.

In recent research on resist composition, the photoacid generator has been focused on the invention of photoacid generator which reduces acid diffusion rate, good permeability to 193nm ArF light source, and reduces the phenomenon of photoacid generator in resist caused by repulsion against immersion solution. It is set.

However, chemically amplified resists are generally non-uniform in acid diffusion, and have a limitation in basic resolution because they cannot implement patterns of a size smaller than the distance that mines diffuse and travel.

To solve this problem more fundamentally, photoacid generators can be bonded to photosensitive polymer chains to eliminate non-uniformities and to minimize chemical amplification by acid diffusion, resulting in high resolution, good line edge roughness, process margin and dry etching resistance. Can have

Under such technical background, the present inventors have completed the present invention as a result of diligent efforts.

The technical problem to be achieved by the present invention is to provide a photosensitive polymer that can control the diffusion rate of the acid, exhibits high permeability when transmitting the ArF light source, and can improve the non-uniformity of the photoacid generator and minimize the chemical amplification by acid diffusion in the resist There is.

Another technical problem to be achieved by the present invention is to provide a novel photoacid generator and a photosensitive polymer comprising the same.

Another object of the present invention is to provide a method for producing the photosensitive polymer.

[화학식 1]
(상기 화학식 1 에서, 상기 A는 탄소수 3 내지 40의 단환형 또는 다환형의 탄화수소기이고, 상기 B는 메타아크릴기 또는 아크릴기이며, 상기 T는 유기 짝이온이다)

[화학식 2]
상기 화학식 2에서, 상기 R₁, R₂, R₃ 및 R₄는 서로 독립적인 것으로 수소원자; 또는 에테르기, 에스테르기, 카르보닐기, 아세탈기, 에폭시기, 니트릴기 또는 알데하이드기를 포함하거나 포함하지 않는 탄소수 1 내지 40의 알킬기이고, 상기 R₅는 각각 독립적으로 수소원자 또는 메틸기이고;
상기 l, m, n, o 및 p는 각각 주쇄 내의 반복단위의 몰분율을 나타내는 것으로 l + m + n + o + p = 1 이고, l, m, n 및 o는 0 ~ 0.99 이며, p는 0.01 ~ 1 이다.
일 실시예에 있어서, 상기 T는 설포늄 양이온일 수 있다.
본 발명의 다른 측면에 따르면, 무기염, Na₂S₂O₄ 및 하기 화학식 3으로 표시되는 화합물을 용매에서 반응시켜 하기 화학식 4로 표시되는 화합물을 제조하는 제 1단계;
[화학식 3]

상기 화학식 3 에서 X는 F, Cl, Br 및 I로 이루어진 그룹에서 선택된 1종이다.
[화학식 4]

상기 화학식 4에서 M은 Li, Na 및 K로 이루어진 그룹에서 선택된 1종이다.
산화제와 상기 화학식 4로 표시되는 화합물을 용매에서 반응시켜 하기 화학식 5로 표시되는 화합물을 제조하는 제 2단계;
[화학식 5]

상기 화학식 5로 표시되는 화합물을 하기 화학식 6으로 표시되는 화합물과 용매에서 반응시켜 하기 화학식 7로 표시되는 화합물을 제조하는 제 3단계;
[화학식 6]

상기 화학식 6에서, T는 유기 짝이온이며, Z는 OSO₂CH₃, OSO₂C₄F₉, PF₆, F, Cl, Br 및 I로 이루어진 그룹에서 선택된 1종이다.
[화학식 7]

상기 화학식 7에서 T는 유기 짝이온이다.
촉매 및 염기 존재하에서, 상기 화학식 7로 표시되는 화합물과 하기 화학식 8로 표시되는 화합물을 용매에서 반응시켜 하기 화학식 9로 표시되는 화합물을 제조하는 제4단계;
[화학식 8]

상기 화학식 8에서, 상기 A는 탄소수 3 내지 40의 단환형 또는 다환형의 탄화수소기이고, 상기 C는 하이드록시기 또는 수소이다.
[화학식 9]

염기 존재하에서, 상기 화학식 9로 표시되는 화합물과 하기 화학식 10으로 표시되는 화합물을 용매에서 반응시켜 하기 화학식 1로 표시되는 화합물을 제조하는 제5단계;
[화학식 10]

또는

[화학식 1]

(상기 화학식 1 에서, 상기 B는 메타아크릴기 또는 아크릴기이다.)
를 포함하는 광산발생제의 제조방법이 제공될 수 있다.
According to one aspect of the present invention, there may be provided a novel photoacid generator of Formula 1 and a photosensitive polymer of Formula 2 comprising the same.

[Chemical Formula 1]
(In Formula 1, A is a monocyclic or polycyclic hydrocarbon group having 3 to 40 carbon atoms, B is a methacryl group or an acryl group, and T is an organic counterion.)

(2)
In Formula 2, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other hydrogen atom; Or an alkyl group having 1 to 40 carbon atoms, including or without an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group or an aldehyde group, and each of R ₅ is independently a hydrogen atom or a methyl group;
Where l, m, n, o and p represent the mole fraction of repeating units in the main chain, respectively, l + m + n + o + p = 1, l, m, n and o are 0 to 0.99, p is 0.01 Is one.
In one embodiment, T may be a sulfonium cation.
According to another aspect of the invention, the first step of preparing a compound represented by the following formula (4) by reacting an inorganic salt, Na ₂ S ₂ O ₄ and a compound represented by the formula (3) in a solvent;
(3)

In Formula 3, X is one selected from the group consisting of F, Cl, Br, and I.
[Chemical Formula 4]

In Formula 4, M is one selected from the group consisting of Li, Na, and K.
A second step of preparing a compound represented by Chemical Formula 5 by reacting an oxidizing agent with a compound represented by Chemical Formula 4 in a solvent;
[Chemical Formula 5]

A third step of preparing a compound represented by Chemical Formula 7 by reacting the compound represented by Chemical Formula 5 with a compound represented by Chemical Formula 6 in a solvent;
[Chemical Formula 6]

In Formula 6, T is an organic counterion, and Z is one selected from the group consisting of OSO ₂ CH ₃ , OSO ₂ C ₄ F ₉ , PF ₆ , F, Cl, Br, and I.
(7)

In Formula 7, T is an organic counterion.
A fourth step of preparing a compound represented by Chemical Formula 9 by reacting the compound represented by Chemical Formula 7 with the compound represented by Chemical Formula 8 in a solvent in the presence of a catalyst and a base;
[Chemical Formula 8]

In Formula 8, A is a monocyclic or polycyclic hydrocarbon group having 3 to 40 carbon atoms, and C is a hydroxy group or hydrogen.
[Chemical Formula 9]

A fifth step of preparing a compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula 9 with the compound represented by Chemical Formula 10 in a solvent in the presence of a base;
[Formula 10]

or

[Chemical Formula 1]

(In Formula 1, B is a methacryl group or an acryl group.)
It can be provided a method for producing a photoacid generator comprising a.

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The photosensitive polymer of the present invention can be manufactured into a polymer polymer by including a photoacid generator having a vinyl group introduced into an alicyclic ring, thereby minimizing the nonuniformity and the tipping phenomenon of the photoacid generator in a resist, and improving line edge roughness. It is effective, so you can get better resolution.

1 is a pattern photograph formed using a photoresist solution prepared using Example 3 (left) and Example 4 (right) according to the present invention.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms “comprise” or “have” are intended to indicate that there is a feature, number, step, or combination thereof described in the specification, but one or more other features or numbers, steps, or combinations thereof. It is to be understood that the existence or addition of ones is not excluded in advance.

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

Sulfonium salt which is a photoacid generator according to the present invention is represented by the following formula (1).

[Formula 1]

상기 화학식 1에서, 상기 A는 탄소수 3 내지 40의 단환형 또는 다환형의 탄화수소기이고, 상기 B는 메타아크릴기 또는 아크릴기이며, 상기 T는 유기 짝이온이다.

In Formula 1, A is a monocyclic or polycyclic hydrocarbon group having 3 to 40 carbon atoms, B is a methacryl group or an acryl group, and T is an organic counterion.

T may be a sulfonium cation as an organic counterion, preferably triphenylsulfonium cation.

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The method for preparing the sulfonium salt according to the present invention includes the reaction of the first to fifth steps described in detail below.

The photosensitive polymer according to the present invention is represented by the following formula (2).

(2)

In Formula 2, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other hydrogen atom; Or an alkyl group having 1 to 40 carbon atoms, including or without an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group or an aldehyde group, and each of R ₅ is independently a hydrogen atom or a methyl group;

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Wherein l, m, n, o and p each represent a mole fraction of repeating units in the main chain and l + m + n + o + p = 1, and l, m, n and o are 0 to 0.99, wherein p is 0.01-1.

Method for producing a photosensitive polymer according to the present invention will be described in more detail in each step below.

Step 1

The reaction of the first step for preparing the photosensitive polymer according to the present invention is carried out at 0 ° C to 100 ° C, using an aqueous salt solvent selected from the group consisting of water, acetonitrile, methanol and ethanol, as an inorganic salt. A compound represented by the following Chemical Formula 4 is prepared by adding one selected from the group consisting of Na ₂ CO ₃ , NaHCO ₃ , NaOH, and KOH and reacting Na ₂ S ₂ O ₄ with the compound represented by the following Chemical Formula 3.

(3)

In Formula 3, X is one selected from the group consisting of F, Cl, Br, and I.

[Chemical Formula 4]

In Formula 4, M is one selected from the group consisting of Li, Na, and K.

Step 2

The reaction of the second step for preparing the photosensitive polymer according to the present invention is carried out at 0 ° C to 100 ° C, using one water-soluble solvent selected from the group consisting of water, methanol and ethanol, H ₂ O ₂ as an oxidant Alternatively, when HClO ₄ is added to react with the compound represented by Chemical Formula 4, a compound represented by Chemical Formula 5 is prepared.

[Chemical Formula 5]

Step 3

The reaction of the third step for preparing the photosensitive polymer according to the present invention is carried out at 0 ℃ to 100 ℃, using one selected from the group consisting of dichloromethane, chloroform, dichloroethane, methanol and ethanol alone or water When the mixture is used together with the compound represented by Formula 5 to react with the compound represented by Formula 6, a sulfonium salt represented by Formula 7 is prepared.

[Chemical Formula 6]

In Formula 6, T may be an sulfonium cation as an organic counterion, and preferably triphenylsulfonium. Z may be one selected from the group consisting of OSO ₂ CH ₃ , OSO ₂ C ₄ F ₉ , PF ₆ , F, Cl, Br and I.

[Formula 7]

Step 4

The reaction of the fourth step for producing the photosensitive polymer according to the present invention is carried out at 0 ℃ to 100 ℃, using an organic solvent selected from the group consisting of dichloromethane, dichloroethane, add EDCI as a reaction catalyst When the base compound is reacted with the compound represented by Chemical Formula 7 and the following Chemical Formula 8 using DMAP, the compound represented by the following Compound 9 is prepared.

[Formula 8]

In Formula 8, A is a monocyclic or polycyclic hydrocarbon group having 3 to 40 carbon atoms, and C is a hydroxyl group or hydrogen.

[Chemical Formula 9]

5th step

The reaction of the fifth step for preparing the photosensitive polymer according to the present invention is carried out at 0 ℃ to 100 ℃, using one species selected from the group consisting of dichloromethane, dichloroethane, using a TEA as a base to the formula When reacted with the compound represented, a sulfonium salt represented by Formula 1, which is one of the desired products of the present invention, is prepared.

[Formula 10]

또는

or

In Formula 1, T may be a sulfonium cation as an organic counterion, and preferably triphenylsulfonium. A is a monocyclic or polycyclic hydrocarbon group of 3 to 40. B is a C3-C10 alkyl group containing a double bond, Preferably it is a C3-C5 alkyl group.

6th step

The reaction of the sixth step for preparing the photosensitive polymer according to the present invention is carried out at 40 ℃ to 100 ℃, at least one selected from the group consisting of benzene, toluene, xylene, halogenated benzene, diethyl ether, tetrahydrofuran In this case, the radical polymerization initiator is selected from the group consisting of general radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, azobisisocapronitrile and azobisisovaleronitrile. To prepare a photosensitive polymer represented by the formula (2) which is one of the desired products of the invention.

(2)

In Formula 2, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other hydrogen atom; Or an alkyl group having 1 to 40 carbon atoms, including or without an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group or an aldehyde group, and each R ₅ is independently a hydrogen atom or a methyl group, and l, m, n , o and p represent the mole fraction of repeating units in the main chain, respectively, l + m + n + o + p = 1, and l, m, n, o are 0 to 0.99, where p is 0.01 to 1.

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Hereinafter, the present invention will be described in more detail with reference to Examples. It should be understood, however, that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the present invention.

Analysis method

In order to confirm the structure of the product obtained in this experiment, nuclear magnetic resonance spectrum ( ¹ H NMR) 300 MHz (JEOL, NMR spectrometer) and mass spectrometer (Agilent , Mass spectrometer), and Kelper mission chromatography (WATERS, GPC) and Scanning Electronic Microscopy were used for circuit pattern confirmation.

Example  One:

1.Sodium 1,1,2,2- Tetrafluoro -4- Hydroxybutane -One- Sulfinate  Synthesis of

1-bromo-1,1,2,2-tetrafluoro-4-butanol (0.05mol, 11.3g) was added to a 200ml reaction flask, and H ₂ O (70ml) and acetonitrile (40ml) were added thereto. Was prepared. NaHCO ₃ (0.1mol, 8.4g) and Na ₂ S ₂ O ₄ (0.1mol, 20.5g) were added to the mixture, followed by stirring at 65 ° C for 24 hours. After the reaction, the mixture was confirmed by thin layer chromatography (TLC, Thin-Layer Chromatography) (R _f : 0.2, CH ₂ Cl ₂ : CH ₃ OH = 10: 1), and the reaction was terminated. After the reaction, the mixture was concentrated, dissolved in ethyl acetate (CH ₃ CH ₂ COOCH ₃ ), filtered, and the filtrate was concentrated again to yield 85% sodium 1,1,2,2-tetrafluoro-4-hydroxybutane. -1-sulfinate [Compound represented by Formula 3a] was obtained.

[Chemical Formula 3]

¹ H-NMR (300 MHz, CDCl ₃ , δ): 2.28-2.45 (t, 2H), 3.77-3.81 (m, 2H).

2. Sodium 1,1,2,2- Tetrafluoro -4- Hydroxybutane -One- Sulfonate  Synthesis of

To a 200 ml reaction flask was added H ₂ O (75 ml) to sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfinate (0.04 mol, 9.3 g) to prepare a mixture. 30% hydrogen peroxide (0.08mol, 9.1g) was added to the mixture, followed by stirring at 25 ° C for 4 hours. After the reaction, the mixture was confirmed by thin layer chromatography (TLC, Thin-Layer Chromatography) (R _f : 0.4, CH ₂ Cl ₂ : CH ₃ OH = 10: 1) and the reaction was terminated. After the reaction, the mixture was concentrated, ethyl acetate (CH ₃ CH ₂ COOCH ₃ ) was added to the concentrate, the mixture was stirred for 1 hour, filtered, and the filtrate was concentrated to yield 70% sodium 1,1,2,2-tetrafluoro. 4-hydroxybutane-1-sulfonate [compound represented by formula 4a] was obtained.

[Chemical Formula 4a]

3. Triphenylsulfonium  1,1,2,2- Tetrafluoro -4- Hydroxybutane -One- Sulfonate  Synthesis of

Sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate (0.03 mol, 7.4 g), methanol (70 ml) and triphenyl sulfonium chloride (0.03 mol, 9.0) in a 200 ml reaction flask g) was added and stirred at 25 ° C. for 3 hours and then concentrated. The concentrate was purified by column chromatography on silica gel to yield 75% of triphenylsulfonium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate [compound represented by Formula 7a] ] Was obtained.

[Formula 7a]

4. Triphenylsulfonium  1,1,2,2- Tetrafluoro -4- (3- Hydroxy -One- Adamantalcarboxyl Butane-1- Sulfonate  Synthesis of

A mixture was prepared by adding dichloromethane (100 ml) to triphenylsulfonium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate (0.02 mol, 9.8 g) in a 200 ml reaction flask. 3-hydroxy-1-adamantanecarboxylic acid is slowly added to this mixture. EDCI (0.03 mol, 5.8 g) and DMAP (0.01, 1.2 g) were added thereto, followed by stirring at 25 ° C. for 12 hours. The reaction mixture is washed with water and saturated aqueous sodium chloride solution and then concentrated. The concentrate was purified by column chromatography on silica gel to give a 70% yield of reactant [Formula 9a].

[Formula 9a]

MS (m / z): Positive mode 263.2 (equivalent to (C ₆ H ₅ ) ₃ S), negative mode 403.2 (equivalent to C ₁₅ H ₁₉ F ₄ O ₆ S).

¹ H-NMR (300 MHz, CDCl ₃ , δ): 1.52-1.78 (m, 12H), 2.15-2.20 (m, 2H), 2.65-2.77 (m, 2H), 4.28-4.33 (t, 2H), 7.70 ˜7.74 (m, 15 H).

5. Triphenylsulfonium  1,1,2,2- Tetrafluoro -4- (3-acryloyl-1- Adamantalcarboxyl Butane-1- Sulfonate  synthesis

To a 200 ml reaction flask was added dichloromethane (70 ml) to 9a (0.01 mol, 6.7 g) to prepare a mixture. After trimethylamine (0.016mol, 1.6g) was added to the mixture and the internal temperature was maintained at 10 ° C or lower, acryloyl chloride (0.015mol, 1.4g) was added slowly and stirred at 25 ° C for 7 hours. do. After the reaction, the mixture is washed with water and saturated aqueous sodium chloride solution and then concentrated. The concentrate was purified by column chromatography on silica gel to give 60% yield of reactant [Formula 1a].

[Formula 1a]

MS (m / z): Positive mode 263.2 (equivalent to (C ₆ H ₅ ) ₃ S), negative mode 457.2 (equivalent to C ₁₈ H ₂₁ F ₄ O ₇ S)

¹ H-NMR (300 MHz, CDCl ₃ , δ): 1.54-2.24 (m, 14H), 2.63-2.80 (m, 2H), 4.29-4.33 (t, 2H), 5.69-5.73 (d, 1H), 5.95 ~ 6.04 (q, 1H), 6.24-6.30 (d, 1H), 7.65-7.80 (m, 15H)

Example  2: Triphenylsulfonium  1,1,2,2- Tetrafluoro -4- (3-acryloyl-1- Ada Mantalcarboxyl) butane-1- Sulfonates  Polymerization of Photosensitive Polymer Containing

Triphenylsulfonium 1,1,2,2-tetrafluoro-4- (3-acryloyl-1-adamantalcarboxyl) butane-1-sulfonate (0.01mol, 7.2g) in 200ml reaction flask , gamma-Butyrolactyl methacrylate (0.07mol, 11.92g), ethyl cyclopentyl methacrylate (0.04mol, 7.3g), ethyl adamantyl methacrylate (0.08mol, 19.86g) in 50 ml of tetrahydrofuran After dissolving, azobisisobutyronitrile (0.02 mol, 3.28 g) is added as a radical polymerization initiator, followed by stirring at 60 ° C for 3 hours. After 3 hours, the temperature was lowered to room temperature, and the reactant was added to 1 L of hexane to precipitate the polymer. The precipitated polymer is filtered, dried under reduced pressure at room temperature, and dried for 24 hours to obtain a polymer represented by the following [Formula 2a]. (Yield 80%)

(2a)

LER  (Line edge Roughness ) evaluation

Example 3 below was prepared by dissolving the photoacid generator prepared in Example 1 by adding a polymer and a photoacid generator to a photoresist solvent (PGMEA, Propylene glycol monomethyl ether acetate), which is a method of making a general photoresist solution. In Example 4, a photoresist solution was prepared by dissolving the polymer including the photoacid generator prepared in Example 2 in PGMEA (Propylene glycol monomethyl ether acetate) as a photoresist solvent.

Each prepared photoresist solution was coated with BARC (Bottom Anti-reflective Coating) on a 330Å coated Si wafer at 600Å thickness and exposed using ArF Stepper (ASML 1200, 0.85NA, DJLS 70nm 1: 1). It developed in aqueous alkali solution and formed the pattern. The formed pattern was confirmed through CD-SEM (Hitachi 9220 # 1, Magnification 120K). The confirmed results are shown in Table 1 and FIG.

Example 3 Example 4 Exposure amount (mJ) 7.5 5 Circuit width (nm) 68.6 71.1 LER (Line Edge Roughness ) 7.98 6.38

In Fig. 1, the pattern photograph (left) of Example 3 and the pattern photograph (right) of Example 4 are shown. Referring to Table 1 and FIG. 1, when the chemically amplified resist composition according to the present invention is used, a circuit width of 100 nm or less can be obtained even with a small exposure amount, and a very good LER value can be obtained.

As described above, the photoacid generator of the present invention can be produced as a polymer polymer by introducing a vinyl group into the alicyclic ring, thereby minimizing the nonuniformity and tilting of the photoacid generator in the resist, thereby improving the line edge roughness. This results in better resolution.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (5)

New photoacid generator of the formula (1);

[Chemical Formula 1]
(In Formula 1, A is a monocyclic or polycyclic hydrocarbon group having 3 to 40 carbon atoms, B is a methacryl group or an acryl group, and T is an organic counterion.)
The method of claim 1,
T is a photoacid generator, characterized in that the sulfonium cation.
A first step of preparing a compound represented by Chemical Formula 4 by reacting an inorganic salt, Na ₂ S ₂ O _4, and a compound represented by Chemical Formula 3 in a solvent;
(3)

In Formula 3, X is one selected from the group consisting of F, Cl, Br, and I.
[Chemical Formula 4]

In Formula 4, M is one selected from the group consisting of Li, Na, and K.
A second step of preparing a compound represented by Chemical Formula 5 by reacting an oxidizing agent with a compound represented by Chemical Formula 4 in a solvent;
[Chemical Formula 5]

A third step of preparing a compound represented by Chemical Formula 7 by reacting the compound represented by Chemical Formula 5 with a compound represented by Chemical Formula 6 in a solvent;
[Chemical Formula 6]

In Formula 6, T is an organic counterion, and Z is one selected from the group consisting of OSO ₂ CH ₃ , OSO ₂ C ₄ F ₉ , PF ₆ , F, Cl, Br, and I.
(7)

In Formula 7, T is an organic counterion.
A fourth step of preparing a compound represented by Chemical Formula 9 by reacting the compound represented by Chemical Formula 7 with the compound represented by Chemical Formula 8 in a solvent in the presence of a catalyst and a base;
[Chemical Formula 8]

In Formula 8, A is a monocyclic or polycyclic hydrocarbon group having 3 to 40 carbon atoms, and C is a hydroxy group or hydrogen.
[Chemical Formula 9]

A fifth step of preparing a compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula 9 with the compound represented by Chemical Formula 10 in a solvent in the presence of a base;
[Formula 10]

or

[Chemical Formula 1]

(In Formula 1, B is a methacryl group or an acryl group.)
Method of producing a photoacid generator comprising a. delete delete

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