KR102587517B1 - A composition of photoresist and photosensitive polymers - Google Patents

Abstract

The present invention relates to a photosensitive polymer and resist composition containing a (meth)acrylate compound having the structure of Formula 1 below.
[Formula 1]

The definition of each substituent in Formula 1 is as described in the specification.

Description

Photosensitive polymer and photoresist composition {A COMPOSITION OF PHOTORESIST AND PHOTOSENSITIVE POLYMERS}

The present invention relates to a (meth)acrylate compound having an aromatic fluorene group, a photosensitive polymer, and a resist composition, and more specifically, to a (meth)acrylate compound having an aromatic acid-decomposable fluorene group (which has excellent adhesion properties to the underlying film material and excellent dry etching resistance) It relates to a photosensitive polymer made of a meth)acrylate compound and a resist composition containing the photosensitive polymer.

As semiconductor manufacturing processes become more complex and the degree of integration of semiconductor devices increases, fine pattern formation is required. In terms of photoist materials, resist materials using an ArF excimer laser (193 nm), which uses a shorter wavelength, have come to be used rather than resist materials using the existing KrF excimer laser (248 nm).

However, in semiconductor devices with a capacity of 16 gigabit or more, as the design rule requires a pattern size of 70 nm or less, the thickness of the resist film becomes increasingly smaller and the process margin in the process of etching the lower film material increases. As this decreases, limitations are increasingly emerging in the use of resist materials using ArF excimer lasers.

Resist materials used in lithography using ArF excimer lasers have many problems compared to existing resist materials for commercialization. The most representative problem is the resistance of photosensitive resin to dry etching.

As conventional ArF resists known so far, acrylic or methacrylic polymers have been mainly used. Among them, poly(methacrylate)-based polymer materials were most commonly used. A serious problem with these polymers is that their resistance to dry etching is very poor. In other words, the selectivity of these materials is too low in the dry etching process using plasma gas during the semiconductor device manufacturing process, making it difficult to proceed with the etching process.

Accordingly, in order to increase the resistance to dry etching, alicyclic compounds, which are materials with strong resistance to dry etching, such as isobornyl group, adamantyl group, and tricyclo A method of introducing a decanyl group (tricyclodecanyl group) as a substituent to the polymer was used. However, in order to satisfy the photosensitive resin requirements for satisfying the characteristics of photoresist materials, solubility in developer and adhesion to the underlying film, the polymer form mainly has a structure higher than a triple copolymer (terpolymer). Since the alicyclic group occupies a small portion, the resistance to dry etching is still weak. In addition, since alicyclic compounds are hydrophobic, if a large amount of alicyclic compounds are included in the above triple copolymer structure, the adhesion characteristics to the lower layer of the resist film deteriorate.

As another prior art polymer, COMA (cycloolefin-maleic anhydride) alternating polymer has been proposed. In the production of COMA-type copolymers, the manufacturing cost of raw materials is low, but there are still problems in terms of synthesis yield and resolution during polymer production.

In addition, polymers synthesized with the above structure have a very hydrophobic alicyclic group as a backbone, and therefore have poor adhesion properties to membrane materials. In addition, above all, the COMA type photosensitive resin has a disadvantage in that it has a storage stability problem of the resist composition.

The present invention aims to provide a (meth)acrylate compound having an aromatic acid-decomposable fluorene group that is inexpensive to manufacture, has excellent resistance to dry etching and adhesion characteristics to the underlying film, and is stable and easily applicable to the production of photosensitive polymers. do.

The present invention also seeks to provide a photosensitive polymer with excellent resistance to dry etching, including the (meth)acrylate compound having the aromatic acid-decomposable fluorene group as a monomer.

The present invention also seeks to provide a resist composition that can provide excellent lithography performance even in lithography processes using light sources in extreme wavelength regions such as 248 nm, 193 nm, and EUV (13.5 nm) using the photosensitive polymer.

However, the technical problems to be achieved by the present invention are not limited to the problems mentioned above, and other technical problems will be clearly understood by those skilled in the art from the description below.

In order to achieve the above object, according to one embodiment of the present invention, an aromatic (meth)acrylate compound having an aromatic acid-decomposable fluorene group is provided.

According to another embodiment of the present invention, a photosensitive polymer containing a repeating unit derived from the above compound as a monomer is provided.

According to another embodiment of the present invention, a resist composition containing the photosensitive polymer is provided.

Specific details of other embodiments of the present invention are included in the detailed description below.

By using the (meth)acrylate compound containing an aromatic fluorene group according to the present invention, photosensitive polymer and chemically amplified resist compositions with excellent adhesion properties to film materials and dry etching resistance can be easily manufactured.

In addition, the photosensitive polymer material manufactured using a (meth)acrylate compound containing an aromatic acid-decomposable fluorene group as a monomer has etching resistance to dry etching and has a form in which the aromatic fluorene substituent undergoes a decomposition reaction under an acid catalyst. In other words, it has a compound form that also has a resist contrast control function as its basic structure.

Therefore, the resist composition obtained from the photosensitive polymer according to the present invention has very excellent dry etching properties compared to existing ArF resist materials and can be very useful in manufacturing next-generation semiconductor devices in the future.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, “alkyl” refers to a C1 to C20 alkyl group, more preferably a C1 to C12 alkyl group.

means, “lower alkyl” means a C1 to C4 alkyl group, “alkoxy” means a C1 to C20 alkoxy group, more preferably a C1 to C12 alkoxy group, and “alkylene” means a C1 to C20 alkoxy group. means an alkylene group, more preferably a C1 to C12 alkylene group, “aryl” means a C6 to C20 aryl group, more preferably a C6 to C12 aryl group, and “cycloalkyl” means a C3 to C12 aryl group. It refers to a cycloalkyl group of C14.

The (meth)acrylate compound having an aromatic acid-decomposable fluorene group according to an embodiment of the present invention has the structure of Formula 1 below.

[Formula 1]

In the above formula, R1 is hydrogen or a methyl group, R2 is an alkyl group of C1 to C20; Alkenyl group of C2~C20; An aryl group containing C6 to C20 or a hetero atom; or an aryl group from C6 to C20 that may be substituted with a hydroxyl group, fluorine, nitro, or nitrile group;

Here, the (meth)acrylate having the structure of Formula 1 may preferably be in any of the following forms.

The (meth)acrylate compound having the aromatic acid-decomposable fluorene group can be synthesized through the reaction of various aromatic ketone compounds and Grignard compounds. In particular, in the present invention, desired monomers can be synthesized through Grignard substitution reaction using a fluorenone compound as an aromatic ketone compound.

(Meth)acrylate compounds prepared by the above method have etching resistance to dry etching and also exhibit a resist contrast control function by easily decomposing aromatic aryl groups under acid catalyst conditions. As a result, it overcomes the shortcomings of existing ArF resist materials in terms of dry etching resistance and can serve as a sufficient etch mask even in semiconductor devices that require higher resolution.

Accordingly, according to another embodiment of the present invention, a photosensitive polymer composed of the aromatic acid-decomposable (meth)acrylate of Formula 1 as a monomer is included.

The photosensitive polymer may further include a repeating unit derived from the compounds of formulas 2 and 3 below, along with a repeating unit derived from aromatic (meth)acrylate having an acid-decomposable fluorene group.

[Formula 2]

[Formula 3]

In the above formula, R3 and R5 are each independently hydrogen or a methyl group,

R4 is a C4 to C20 acid-labile group or a lactone derivative that decomposes in the presence of an acid catalyst.

The acid-decomposable group is preferably norbornyl, isobornyl, cyclodecanyl, adamantyl, norbornyl substituted with a lower alkyl group, isobornyl substituted with a lower alkyl group, cyclodecanyl substituted with a lower alkyl group, Substituted adamantyl, alkoxycarbonyl, alkoxycarbonylalkyl, amyloxycarbonyl, amyloxycarbonylalkyl, 2-tetrahydropyranyloxycarbonylalkyl, 2-tetrahydrofuranyloxycarbonylalkyl, tertiary It is selected from the group consisting of an alkyl group and an acetal group, more preferably 2-methyl-2-norbornyl, 2-ethyl-2-norbornyl, 2-methyl-2-isobornyl, and 2-ethyl-2-isobornyl. , 8-methyl-8-tricyclodecanyl, 8-ethyl-8-tricyclodecanyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 2-propyl-2-ah Damantyl, t-butoxycarbonyl, t-butoxycarbonylmethyl, t-amyloxycarbonyl, t-amyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxy Selected from the group consisting of carbonylalkyl, 2-tetrahydrofuranyloxycarbonylalkyl, t-butyl group, triethylcarbyl group, 1-methyl cyclohexyl group, 1-ethylcyclopentyl group, t-amyl group, and acetal group. You can hear what happens.

In addition, the lactone derivative includes a lactone derivative group, preferably a substituent group having the structures of the following formulas 4 and 5.

[Formula 4]

[Formula 5]

In the above formula (4), two of X1 to .

In the above formula (5), two of X5 to ; All of X5 to

More preferably, R4 is butyrolactonyl, valerolactonyl, 1,3-cyclohexanecarbolactonyl, 2,6-norbonanecarbolacton-5-yl, and 7-oxa-2,6-nor. is selected from the group consisting of bonancarbolactone-5-yl.

R6 is hydrogen; Or, it is an alkyl group or cycloalkyl group containing a polar group selected from the group consisting of a hydroxy group, a carboxyl group, and a combination thereof. The alkyl group is a C2 to C14 alkyl group, and the cycloalkyl group is a C3 to C14 cycloalkyl group. Preferred examples include 2-hydroxyethyl and 3-hydroxy-1-adamantyl.

That is, the photosensitive polymer is a (meth)acrylate having an aromatic acid-decomposable fluorene group of Formula 1 and a random copolymer of compounds of Formulas 2 and 3. Preferably, the photosensitive polymer has a weight average molecular weight (Mw) of 3,000 to 20,000.

In addition, the photosensitive polymer preferably has a dispersion degree (Mw/Mn) of 1.5 to 2.5. Within the above range, excellent etching resistance and resolution can be achieved.

The photosensitive polymers according to the present invention are in the form of copolymers obtained from acid-decomposable aromatic compounds with new functionality, and have the advantage of producing a resist composition that has excellent resistance to dry etching compared to existing resist materials.

In addition, (meth)acrylate compounds having an aromatic acid-decomposable fluorene group included as monomers are compounds whose aromatic fluorene substituent can be easily decomposed under acid catalyst conditions. Therefore, photosensitive polymers using these compounds can have an improvement effect on etching resistance compared to existing adamantyl acid decomposable groups, and require higher resolution by overcoming the disadvantages of dry etching resistance of existing ArF resist materials. It can also serve as a sufficient etch mask in semiconductor devices.

When the resist composition obtained from this is applied to a photo lithography process, very excellent lithography performance can be obtained.

According to another embodiment of the present invention, a resist composition containing the photosensitive polymer is provided.

Specifically, the resist composition includes (a) the photosensitive polymer, (b) a photoacid generator (PAG), and (c) a solvent.

Hereinafter, each component included in the resist composition according to one embodiment of the present invention will be examined in detail.

(a) Photosensitive polymer

The photosensitive polymer is the same as previously described. Here, the photosensitive polymer is preferably included in an amount of 5 to 50 parts by weight based on 100 parts by weight of the resist composition.

When included in the resist composition in the above content range, excellent etching resistance and adhesion characteristics can be obtained.

(b) Photoacid generator (PAG)

The photoacid generator may be selected from the group consisting of inorganic onium salts, organic sulfonates, and mixtures thereof. Specifically, a sulfonium salt or iodonium salt selected from triarylsulfonium salts, diaryliodonium salts, sulfonates, or mixtures thereof may be used. More preferably, triarylsulfonium triflate, diaryliodonium triflate, triarylsulfonium nonaplate, diaryliodonium nonaplate, succinimidyl triflate, 2,6-dinitrobenzyl sulfonate. and mixtures thereof.

The photoacid generator is preferably included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the photosensitive polymer. If the content of the photoacid generator is less than 1 part by weight, there is a risk that the exposure amount to the resist composition may be excessively increased, and if it exceeds 10 parts by weight, there may be a problem of insufficient transmittance of the resist composition.

(c) solvent

The solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), cyclohexanone, 2-heptanone, and gamma-butyro. One or more types may be selected and used from the group consisting of lactones (GBL) and the like.

The solvent is included as a remaining component in the resist composition and its content is not particularly limited, but is preferably included in an amount of 50 to 95 parts by weight based on 100 parts by weight of the resist composition.

(d) acid quencher

In addition to the components (a) to (c), the resist composition may further include an organic base for the purpose of controlling exposure dose and forming a resist profile.

The organic base is mainly in the form of a trivalent amine, for example, an amine-based compound selected from triethylamine, triisobutylamine, trioctylamine, triisodecylamine, triethanolamine, or mixtures thereof may be used. You can.

The content of the organic base is preferably 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive polymer. If the content of the organic base is less than 0.01 parts by weight, the desired effect cannot be expected, and if it exceeds 1 part by weight, the exposure amount is excessively increased and in severe cases, there may be a problem of pattern formation not being possible.

The following process is used to form a desired pattern using a resist composition having the above composition.

Prepare a bare silicon wafer or a silicon wafer on which a lower layer such as a silicon oxide film, silicon nitride film, or silicon oxynitride film is formed on the upper surface, and the silicon wafer is treated with HMDS treatment or an organic anti-reflection film. Thereafter, the resist composition is coated on the silicon wafer to a thickness of approximately 100 to 500 nm to form a resist film.

The silicon wafer on which the resist film is formed is prebaked (SB) for about 60 to 120 seconds at a temperature range of about 90 to 150° C. to remove the solvent, and then exposed to various exposure light sources, such as KrF, ArF, or extreme UV (EUV). After exposure using an E-beam, etc., post-exposure baking (PEB) is performed for about 60 to 120 seconds at a temperature range of about 90 to 120°C to cause a chemical reaction in the exposed area of the resist film.

Then, the resist film is developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) solution. At this time, the exposed area shows very high solubility in a basic aqueous developer solution, so it is easily dissolved and removed during development. When the exposure source used is an ArF excimer laser, a line and space pattern of 80 to 100 nm can be formed at a dose of about 5 to 30 mJ/cm2.

The resist pattern obtained from the process described above is used as a mask, and the lower film material, such as a silicon oxide film, is etched using a specific etching gas, such as plasma such as halogen gas or CxFy gas. Subsequently, the resist pattern remaining on the wafer can be removed using a stripper to form a desired silicon oxide film pattern.

The present invention will be described in more detail with reference to examples below. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

Example-1) Synthesis of Monomer-I

17 g of fluorenone was dissolved in THF (100 mL) in a round bottom flask, and then 200 mL of methylmagnesium bromide solution (0.5 M in THF) was slowly added dropwise, followed by reaction at a temperature of about 60 degrees for about 2 hours.

After the reaction was completed, an appropriate amount of THF solvent was blown off using a rotary evaporator, the reactant was dropped into excess water, neutralized with diluted hydrochloric acid, extracted using diethyl ether, and column chromatography (hexane:ethyl The product was obtained by purification using acetate=2:1).

13.2 g (50 mmol) of the obtained product and 5 g of triethylamine (TEA) were dissolved in 200 mL of THF, and then 6 g of methacryloyl chloride was slowly added thereto and reacted at a temperature of about 50 degrees for about 4 hours. After the reaction was over, the excess THF was blown away, the obtained product was dropped into excess water, neutralized with diluted hydrochloric acid, and the product was extracted using diethyl ether and subjected to column chromatography (hexane:ethyl acetate=3:1). ) was purified to obtain monomer-I (yield: 50%)

Example-2) Synthesis of Monomer-II

Specifically, monomer-II was prepared in the same manner as in Example 1, except that cyclopentylmagnesium chloride was used instead of methylmagnesium bromide (yield: 50%).

Example-3) Synthesis of Monomer-III

Specifically, monomer-III was prepared in the same manner as in Example 1, except that benzylmagnesium chloride was used instead of methylmagnesium bromide (yield: 40%).

Example-4) Synthesis of photosensitive polymer

Monomer synthesized in Example-1) (20 mmol), t-butyl methacrylate (20 mmol), γ-butyrolactonyl methacrylate (GBLMA) (40 mmol), and 3-hydroxy-1-adamantyl Put methacrylate (HAMA) (20 mmol) in a round flask and dissolve it in dioxane solvent (3 times the total weight of monomers), then add BPO (2% of monomer concentration) as a polymerization initiator and incubate under nitrogen for about 20 minutes. After purging for some time, polymerization was performed at a temperature of 80°C for about 20 hours.

After polymerization was completed, the reactant was slowly precipitated in an excess of methanol/water co-solvent, the resulting precipitate was filtered, and then the precipitate was dissolved in an appropriate amount of THF and reprecipitated in the methanol/water co-solvent. Afterwards, the obtained precipitate was dried in a vacuum oven at 80°C for about 24 hours to synthesize a polymer (yield: 80%).

The weight average molecular weight (Mw) of the synthesized polymer was 14,800, and the dispersion degree (Mw/Mn) was 1.6.

Example-5) Synthesis of photosensitive polymer

The monomer synthesized in Example-2) (20 mmol), t-butyl methacrylate (20 mmol), γ-butyrolactonyl methacrylate (GBLMA) (40 mmol), and 3-hydroxy-1-adamane A polymer was synthesized by polymerizing hel methacrylate (HAMA) (20 mmol) in the same manner as in Example-4) (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 13,600, and the dispersion degree (Mw/Mn) was 1.7.

Example-6) Synthesis of photosensitive polymer

The monomer synthesized in Example-3) (20 mmol), t-butyl methacrylate (20 mmol), γ-butyrolactonyl methacrylate (GBLMA) (40 mmol), and 3-hydroxy-1-adamane A polymer was synthesized by polymerizing hel methacrylate (HAMA) (20 mmol) in the same manner as in Example-4) (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 14,500, and the dispersion degree (Mw/Mn) was 1.7.

Example-7) Synthesis of photosensitive polymer

The monomer synthesized in Example-1) (20 mmol), t-butyl methacrylate (20 mmol), 2-hydroxyethyl methacrylate (HEMA) (40 mmol), and 1-adamantyl acrylate (HAMA) ) (20 mmol) was polymerized in the same manner as in Example-4) to synthesize a polymer (yield: 70%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 15,500, and the dispersion degree (Mw/Mn) was 1.7.

Example-8) Synthesis of photosensitive polymer

The monomer synthesized in Example-1) (20 mmol), γ-butyrolactonyl methacrylate (GBLMA) (30 mmol), 2-hydroxyethyl methacrylate (HEMA) (20 mmol), and 2-methyl- 2-Adamantyl methacrylate (MAMA) (30 mmol) was polymerized in the same manner as in Example-4) to synthesize a polymer (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 15,500, and the dispersion degree (Mw/Mn) was 1.7.

Example-9) Synthesis of photosensitive polymer

The monomer synthesized in Example-1) (20 mmol), styrene (10 mmol), 2-hydroxyethyl methacrylate (40 mmol), and 2-methyl-2-adamantyl methacrylate (MAMA) (30 mmol) ) was polymerized in the same manner as in Example-4) to synthesize a polymer (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 15,300, and the dispersion degree (Mw/Mn) was 1.7.

Example-10) Synthesis of photosensitive polymer

The monomer (40 mmol), styrene (10 mmol), γ-butyrolactonyl methacrylate (20 mmol) and 3-hydroxy-1-adamantyl methacrylate (30 mmol) synthesized in Example-1) above were A polymer was synthesized by polymerization in the same manner as in Example-4) (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 15,800, and the dispersion degree (Mw/Mn) was 1.7.

Example-11) Synthesis of photosensitive polymer

The monomer (20 mmol), t-butyl methacrylate (20 mmol), γ-butyrolactonyl methacrylate (40 mmol), and styrene (20 mmol) synthesized in Example-1) were mixed with Example-4). A polymer was synthesized by polymerization using the same method (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 15,800, and the dispersion degree (Mw/Mn) was 1.7.

Example-12) Synthesis of photosensitive polymer

The monomer (20 mmol), t-butyl methacrylate (20 mmol), γ-butyrolactonyl methacrylate (40 mmol), and 4-hydroxystyrene (20 mmol) synthesized in Example-1) above were A polymer was synthesized by polymerization in the same manner as in -4) (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 15,300, and the dispersion degree (Mw/Mn) was 1.7.

Example-13) Synthesis of photosensitive polymer

The monomer (20 mmol), t-butyl methacrylate (20 mmol), 2-hydroxyethyl methacrylate (40 mmol), and styrene (20 mmol) synthesized in Example-1) were mixed with Example-4). A polymer was synthesized by polymerization using the same method (yield: 75%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 16,100, and the dispersion degree (Mw/Mn) was 1.7.

Comparative Example) Synthesis of photosensitive polymer

t-butyl methacrylate (40 mmol), γ-butyrolactonyl methacrylate (GBLMA) (40 mmol), and 3-hydroxy-1-adamantyl methacrylate (HAMA) (20 mmol) were prepared in Example- A polymer was synthesized by polymerization in the same manner as in 4) (yield: 80%).

At this time, the weight average molecular weight (Mw) of the obtained polymer was 15,500, and the dispersion degree (Mw/Mn) was 1.7.

Example-14) Preparation and lithography performance of resist composition

Each photosensitive polymer (1g) synthesized in Examples-4 to 13) and Comparative Examples was dissolved in PGMEA/EL (6/4) (17g) together with triphenylsulfonium nonaplate (0.02g). , triethanolamine (1 mg), an organic base, was added and completely dissolved to prepare each resist composition.

Example-15) Resolution evaluation

Each resist solution prepared in Example-14) was filtered using a 0.1㎛ membrane filter. The filtered resist solution was coated to a thickness of 140 nm on a 600Å thick organic BARC (AR46, Rhom & Hass Company) silicon wafer, and then pre-baked (soft baking: SB) at a temperature of 130 degrees for 60 seconds.

After exposure at 20~50mj/cm2 using an ArF scanner (0.78NA, dipole), PEB (post-exposure bake) was performed at 110 degrees for 60 seconds, and then developed in a 2.38% by weight TMAH solution for 60 seconds. As a result, a clean 90~100nm L/S pattern result was obtained as shown in Table-1 below, and it was confirmed that the resolution was superior to that of the comparative example polymer.

polymer type Exposure energy (Eop) resolution Example 4 30mJ/cm2 90 nm Example 5 30mJ/cm2 100nm Example 6 30mJ/cm2 100 nm Example 7 30mJ/cm2 90nm Example 8 30mJ/cm2 90 nm Example 9 30mJ/cm2 100nm Example 10 30mJ/cm2 100nm Example 11 30mJ/cm2 100nm Example 12 30mJ/cm2 100 nm Example 13 30mJ/cm2 100nm Comparative Example 30mJ/cm2 120nm

Example-16) Etch resistance evaluation

In order to evaluate the etching characteristics of each resist composition prepared in Example-14), bulk etching (composition; power 100W, pressure 5Pa, flow rate 30ml/min) was performed using RIE (reactive ion etching) under CF4 gas (composition; power 100W, pressure 5Pa, flow rate 30ml/min) bulk etch) evaluation was conducted. At this time, the reference used was normalized and evaluated based on the etching rate of polyhydroxystyrene (PHS) polymer, which is a resist for KrF. The measurement results are shown in Table-2, and the polymer of the present invention shows an etching rate of about 1.1 times (normalized) compared to the polymer for KrF, and the polymer of the comparative example shows an etching rate of about 1.5 times. It was confirmed that the polymers of the present invention have very strong etch resistance.

Above, the present invention has been described in detail with preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. possible.

polymer type PHS (normalized) Etch rate (%) Example 4 100% 110 Example 5 100% 110 Example 6 100% 110 Example 7 100% 108 Example 8 100% 106 Example 9 100% 105 Example 10 100% 105 Example 11 100% 105 Example 12 100% 103 Example 13 100% 105 Comparative Example 100% 150

Claims (7)

A photosensitive polymer comprising a repeating unit derived from a (meth)acrylate compound having an aromatic fluorene group of Formula 1 below and a repeating unit derived from Formula 2 below.
[Formula 1] [Formula 2]

In the above formula, R1 and R3 are hydrogen or methyl groups,
R2 is an alkyl group of C1~C20; Alkenyl group of C2~C20; An aryl group containing C6 to C20 or a hetero atom; Or an aryl group from C6 to C20 that may be substituted with a hydroxyl group, fluorine, nitro, or nitrile group;
R4 is a t-butyl group. According to paragraph 1,
The compound is a photosensitive polymer comprising a repeating unit derived from a (meth)acrylate compound selected from the group consisting of compounds having the following structure.
According to paragraph 1,
A photosensitive polymer further comprising a repeating unit derived from a compound of formula 3 below.
[Formula 3]

In Formula 3, R5 is hydrogen or a methyl group,
R6 is hydrogen; It is an alkyl group or cycloalkyl group containing a polar group selected from the group consisting of a hydroxy group, a carboxyl group, and a combination thereof. delete delete According to paragraph 1,
The photosensitive polymer wherein R2 is a methyl, ethyl, isobutyl, cyclopentyl, cyclohexyl, or benzyl group. (a) the photosensitive polymer according to any one of claims 1 to 3 or 6;
(b) photoacid generator (PAG); and
(c) A resist composition containing an organic solvent.