KR101413079B1 - (meth)acrylate based polymer and photosensitive resist composition including the same - Google Patents

Abstract

[화학식 2]

[화학식 3]

(상기 화학식에서 각 치환기의 정의는 명세서에 기재된 바와 같다.) There is provided a (meth) acrylate-based polymer comprising a repeating unit represented by the following general formulas (1) to (3) and a photosensitive resin composition containing the same.
[Chemical Formula 1]

(2)

(3)

(The definition of each substituent in the above formula is the same as described in the specification.)

Description

(METH) ACRYLATE BASED POLYMER AND PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME (METH) ACRYLATE BASED POLYMER AND PHOTOSENSITIVE RESIST COMPOSITION INCLUDING THE SAME [0002]

The present invention relates to a (meth) acrylate-based polymer and a photosensitive resin composition containing the same.

As the degree of integration of semiconductor chips increases, it is required to form fine patterns for sub-micron chips in a lithography process. In particular, in lithography processes for the fabrication of ultra-high integration circuits, a higher resolution is realized using a short wavelength (DUV region). As a result, a lithography technique using deep ultraviolet rays of shorter wavelength than the existing g-line (436 nm) and i-line (365 nm) was introduced. For this purpose, a chemically amplified type high- .

Resin of chemically amplified resist using deep ultraviolet rays is transparent to a light source to be used and resin having good protection can be used. Therefore, polyhydroxy styrene is used for KrF (248 nm) resist and ArF (193 nm) acrylate polymer is used for resists. Polymers containing hydrocarbon ring compounds such as adamantyl are used in the side chain portion of the ester group to compensate for the relatively low etch resistance as compared to KrF resists.

However, when a conventional hydrocarbon cyclic compound such as adamantyl is used as in the prior art, the solubility of the resin is not sufficient and scum is generated after the pattern is formed, or the pattern adhesion is poor due to poor adhesion with the substrate .

One aspect of the present invention is to provide a (meth) acrylate-based polymer capable of producing a resin film which does not cause scum even at a high film thickness, is excellent in adhesion to a substrate, and is excellent in implant resistance .

Another aspect of the present invention is to provide a photosensitive resin composition comprising the (meth) acrylate-based polymer.

One aspect of the present invention provides a (meth) acrylate-based polymer comprising a repeating unit represented by the following general formulas (1) to (3).

[Chemical Formula 1]

(In the formula 1,

R ¹ includes hydrogen or a methyl group, R ¹⁰ includes a substituted or unsubstituted C 3 to C 20 cycloalkyl group, or a substituted or unsubstituted C 2 to C 20 heterocycloalkyl group, and n is an integer of 0 to 3.)

(2)

(In the formula (2)

R ² comprises hydrogen or a methyl group, R ²⁰ comprises an ester group and includes a substituted or unsubstituted C3 to C20 cycloalkyl group.

(3)

(3)

R ³ includes hydrogen or a methyl group, and R ³⁰ includes a t-butyl group, a triethylcarbyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, a t-amyl group or an acetal group.

The repeating unit represented by the formula (1) may include any one of repeating units represented by the following formulas (4) to (23).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

In the definition of R ¹⁰ in the formula (1), the heterocycloalkyl group may contain a hetero atom of oxygen (O) or nitrogen (N).

R ²⁰ in the general formula (2) may be a γ-butyrolactonyl group, a valerolactonyl group, a 1,3-cyclohexanecarbolactonyl group, a 2,6 (2,6-norbornanecarbolacton-5-yl) group or 7-oxa-2,6-norbornanecarbolacton- -5-yl) group.

The (meth) acrylate-based polymer may have a weight average molecular weight of 3,000 to 20,000 g / mol and a dispersity of 1.3 to 2.5.

The (meth) acrylate-based polymer preferably comprises 10 to 40 mol% of the repeating unit represented by the formula (1); 20 to 60 mol% of the repeating unit represented by the formula (2); And 20 to 50% by mole of the repeating unit represented by the formula (3).

Another aspect of the present invention relates to the above (meth) acrylate-based polymer; Photo acid generator (PAG); And a solvent.

The (meth) acrylate-based polymer may be included in an amount of 5 to 15% by weight based on the total amount of the photosensitive resin composition.

The photoacid generator may include triarylsulfonium perfluoroalkylsulfonate, triarylsulfonium triflate, diaryliodonium triflate, triarylsulfonium nonaplate, diaryliodonium nonaplate, succinimidyl tri Plate, 2,6-dinitrobenzylsulfonate, or a combination thereof. The photoacid generator may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the (meth) acrylate-based polymer.

The photosensitive resin composition may further comprise 0.1 to 5 parts by weight of an organic amine based on 100 parts by weight of the (meth) acrylate-based polymer. The organic amine may be triethylamine, triisobutylamine, trioctylamine, tri Isodecylamine, triethanolamine, hydroxypiperidine, or a combination thereof.

Other details of the embodiments of the present invention are included in the following detailed description.

The (meth) acrylate-based polymer is excellent in solubility in a developing solution and does not cause scum, has excellent resistance to implant and dry etch, has good hydrophilic property and is excellent in adhesiveness to a substrate, There is little occurrence of lifting. Thus, a resin film suitable for the ion implantation process can be provided.

1A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E _op )) obtained using the photosensitive resin composition according to Example 1. Fig.
1B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm ² less than the optimum energy (E _op )) obtained using the photosensitive resin composition according to Example 1.
1C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm ² less than the optimum energy (E _op )) obtained using the photosensitive resin composition according to Example 1. Fig.
2A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 1. Fig.
2B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm ² less than the optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 1.
2C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm ² less than the optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 1. Fig.
3A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 2. Fig.
3B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm ² less than the optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 2. Fig.
3C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm ² less than the optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 2. Fig.
4 is a graph showing the relationship between the depth of focus (DOF) margin at the 150 nm pattern (optimum energy (E _op ): 36 mJ / cm ² ) obtained using the photosensitive resin composition according to Example 1 and the This is a CD-SEM photo showing
5 is a graph showing the exposure latitude (EL) margin of a 150 nm pattern (optimum energy (E _op ): 36 mJ / cm ² ) obtained using the photosensitive resin composition according to Example 1, It is a CD-SEM photograph.

Hereinafter, embodiments of the present invention will be described in more detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, an imino group C10 alkyl group), an amino group (wherein -NR'R ", R 'and R" are each independently hydrogen or a C1 to C10 alkyl group), amidino group, azido group, hydrazine group, hydrazone group, carbonyl group, A thiol group, an ester group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkoxy group, a C3 to C30 alkoxy group, A C3 to C30 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, a C2 to C30 heterocycloalkenyl group, a C2 to C30 heterocycloalkynyl group, a C6 to C30 aryl group, a C6 to C30 aryl group, a C3 to C30 cycloalkenyl group, It means for interrogating an aryl group or a C6 to C30 substituted aryloxy groups.

Unless otherwise specified in the present specification, the "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heteroaryl group" each have at least one hetero atom of N, O, S or P in the ring compound Means included.

The (meth) acrylate-based polymer according to one embodiment includes the repeating units represented by the following general formulas (1) to (3).

[Chemical Formula 1]

(In the formula 1,

R < ^{1 >} is hydrogen or a methyl group,

R ¹⁰ is a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C2 to C20 heterocycloalkyl group,

and n is an integer of 0 to 3.)

(2)

(In the formula (2)

R ² includes hydrogen or a methyl group,

R ²⁰ comprises an ester group and includes a substituted or unsubstituted C3 to C20 cycloalkyl group.

(3)

(3)

R ³ includes hydrogen or a methyl group,

R ³⁰ includes t-butyl group, triethylcarbyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, t-amyl group or acetal group.

The repeating unit represented by the above formula (1) has a cyclic alkyl group, so that the etch resistance of the (meth) acrylate-based polymer can be enhanced.

The cyclic alkyl group may be a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C2 to C20 heterocycloalkyl group wherein the substitution may specifically mean that it is substituted by a C1 to C4 alkyl group, Specifically, it may mean that a methyl group, an ethyl group, an n-propyl group, an iso-propyl group or the like is substituted.

The heterocycloalkyl group may specifically include a hetero atom of oxygen (O) or nitrogen (N).

Specific examples of the repeating unit represented by the formula (1) include any one of repeating units represented by the following formulas (4) to (23).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

The repeating unit represented by the formula (1) may be contained in an amount of 10 to 40 mol%, specifically 20 to 30 mol% based on the total amount of the (meth) acrylate-based polymer. When the repeating unit represented by the above-mentioned formula (1) is included in the above range, excellent etch resistance and lifting resistance are obtained.

The repeating unit represented by the above-mentioned general formula (2) is a monocyclic or polycyclic (meth) acrylate repeating unit containing an ester group. This increases the hydrophilicity of the photosensitive resin composition and improves adhesion with the substrate.

R ²⁰ in Formula 2 may be a lactone derivative. Examples of the lactone derivative include a gamma-butyrolactonyl group, a valerolactonyl group, a 1,3-cyclohexanecarbolactonyl group, a 2,6- (2,6-norbornanecarbolacton-5-yl) group, 7-oxa-2,6-norbornanecarbolacton- 5-yl) group and the like.

The repeating unit represented by the formula (2) may be contained in an amount of 20 to 60 mol%, specifically 30 to 50 mol% based on the total amount of the (meth) acrylate-based polymer. When the repeating unit represented by the above-mentioned formula (2) is contained within the above range, the adhesion to the substrate is excellent.

The repeating unit represented by the above-mentioned general formula (3) is a (meth) acrylate repeating unit containing an acid labile group which is decomposed in the presence of an acid catalyst. The repeating unit is decomposed by an acid catalyst generated upon exposure, The rate-based polymer can help dissolve well in the alkaline developer.

Examples of the acid-decomposable group include a t-butyl group, a triethylcarbyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, a t-amyl group and an acetal group, T-butyl group can be used. 　

The repeating unit represented by the formula (3) may be contained in an amount of 20 to 50 mol%, specifically 30 to 40 mol% based on the total amount of the (meth) acrylate-based polymer. When the repeating unit represented by the above formula (1) is included in the above range, the developing speed is excellent.

The (meth) acrylate-based polymer containing the repeating units represented by the above formulas (1) to (3) may be a terpolymer, or may be a polycaprolactone containing the same type or other types of repeating units , Random copolymers, block copolymers, alternating copolymers, branched copolymers and the like.

The (meth) acrylate-based polymer may have a weight average molecular weight of 3,000 to 20,000 g / mol, and specifically 5,000 to 10,000 g / mol. When the weight average molecular weight is in the above range, the resin film obtained from the photosensitive resin composition has excellent line edge roughness (LER) characteristics.

The (meth) acrylate-based polymer may have a dispersion degree of 1.3 to 2.5, and more specifically 1.5 to 2.0. The degree of dispersion is a value obtained by dividing the weight average molecular weight by the number average molecular weight. When the (meth) acrylate-based polymer has a degree of dispersion in the above range, it is excellent in etch resistance and developability.

The (meth) acrylate-based polymer may be produced by a general radical polymerization method using the repeating unit derived monomers represented by the formula (1), the repeating unit derived monomers represented by the formula (2), and the repeating unit derived monomers represented by the formula (3) Lt; / RTI >

Another embodiment includes a photosensitive resin composition comprising the (meth) acrylate-based polymer described above.

The photosensitive resin composition includes the (meth) acrylate-based polymer, a photo acid generator, and a solvent.

The (meth) acrylate-based polymer may be contained in an amount of 5 to 15% by weight, and more preferably 7 to 12% by weight based on the total amount of the photosensitive resin composition. When the (meth) acrylate-based polymer is contained within the above range, excellent etch resistance and adhesion can be obtained.

The photoacid generator may be an inorganic onium salt, an organic triflate, an organic sulfonate, or a combination thereof.

Examples of the inorganic onium salt include triarylsulfonium salt, diaryliodonium salt, and the like.

Specific examples of the photoacid generator include triarylsulfonium perfluoroalkylsulfonate, triarylsulfonium triflate, diaryliodonium triflate, triarylsulfonium nonaflate, diaryliodonium nonaflate, Succinimidyl triflate, 2,6-dinitrobenzylsulfonate, or a combination thereof.

When the compound is used as a photoacid generator, it is possible to improve the process margin and the pattern shape by controlling the intensity of the acid, the acid diffusion rate, and the degree of absorption.

The photoacid generator may be included in an amount of 1 to 15 parts by weight, and more preferably 3 to 8 parts by weight based on 100 parts by weight of the (meth) acrylate-based polymer. When the photoacid generator is contained within the above range, excellent exposure amount and transmittance of the photosensitive resin composition can be obtained.

Examples of the solvent include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), cyclohexanone, 2-heptanone (2 -heptanone), and the like can be used alone or in combination.

The solvent may be included as a remainder with respect to 100 parts by weight of the (meth) acrylate-based polymer, specifically, 80 to 95 parts by weight. When the solvent is contained within the above range, the uniformity of the film thickness of the photosensitive resin composition is excellent and the coating defects can be reduced upon application to a wafer.

The photosensitive resin composition may further comprise an organic amine as a quencher for the purpose of adjusting an exposure amount and forming an excellent profile together with the above components.

The organic amine may be an amine compound, for example, triethylamine, triisobutylamine, trioctylamine, triisodecylamine, triethanolamine, hydroxypiperidine or a mixture thereof.

The organic amine may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylate-based polymer, and specifically 0.5 to 3 parts by weight. When the organic amine is included in the above range, adjustment of a depth of focus (DOF) margin, an energy latitude (EL) margin, etc. and formation of an excellent profile can be achieved without excessively increasing the exposure amount.

The following process is used to form a desired pattern using the above-mentioned photosensitive resin composition.

A bare silicon wafer or a silicon wafer having a silicon oxide film, a silicon nitride film or a silicon oxide nitride film formed on the top surface thereof is prepared, and the silicon wafer is treated with hexamethyl disilazane (HMDS) Or a bottom anti-reflective coating (BARC). Thereafter, the photosensitive resin composition is coated on the silicon wafer to a thickness of about 3800 Å to about 4000 Å to form a photosensitive resin film.

The silicon wafer on which the photosensitive resin film is formed is soft-baked (SB) (pre-baking) for about 60 seconds to about 90 seconds at a temperature range of about 90 캜 to about 120 캜 The solvent is removed and exposed using ArF or EUV (Extreme UV), E-beam or the like. Then, post-exposure baking is performed for about 60 seconds to about 90 seconds at a temperature of about 90 캜 to about 120 캜 so as to cause the exposed wafer to undergo a chemical reaction in the exposed region of the photosensitive resin film. PEB).

Thereafter, the photosensitive resin film is developed with an aqueous alkali solution. At this time, since the exposed part exhibits a very high solubility characteristic with respect to the developer, it is dissolved and removed at the time of development. As the developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) may be used. When the used exposure source is an ArF excimer laser, a line and space pattern (L / S) of about 80 nm to about 300 nm at a dose of about 20 mJ / cm 2 to about 50 mJ / Can be formed.

Using the thus-obtained photosensitive resin pattern as a mask, the underlying film quality such as a silicon oxide film is etched using a specific etching gas, for example, a plasma such as a halogen gas or a fluorocarbon gas. Subsequently, a photosensitive resin pattern remaining on the wafer is removed using a stripper to form a desired silicon oxide film pattern.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only and are not to be construed as limiting the present invention.

(( Meta ) Acrylate  Monomer synthesis)

Synthetic example  One: THP2M  synthesis

[Reaction Scheme 1]

(0.004 mol) of methacrylic acid (TCI) and pyridinium para-toluene sulfonate (PPTS) (Aldrich) were dissolved in 80 ml of dichloromethane , DCM) (TCI), 14.7 ml (0.162 mol) of 3,4-dihydro-2H-pyran (DHP) Lt; / RTI > After completion of the reaction, the reaction product was diluted with 250 ml of dichloromethane, washed once with 250 ml of brine and three times with 250 ml of DI water. The organic layer was washed with Na ₂ SO ₄ and the solvent was removed to obtain 13.14 g of tetrahydro-2H-pyran-2-yl methacrylate (THP 2M). The yield was 83%.

Synthetic example  2: THFM  synthesis

[Reaction Scheme 2]

(0.162 mol) of 3,4-dihydro-2H-pyran (DHP) (TCI) in Synthesis Example 1 was replaced by 2,3-dihydrofuran Tetrahydrofuran-2-yl methacrylate, 3-dihydrofuran, DHF) (TCI) was obtained in the same manner as in Synthesis Example 1, except that 12.239 ml (0.162 mol) THFM). The yield was 72%.

Synthetic example  3: THP4M  synthesis

[Reaction Scheme 3]

5.0 mL (0.049 mol) of tetrahydro-4-pyranol (THP) (Aldrich) and 8.2 mL (0.0587 mol) of triethylamine (Et ₃ N) Dichloromethane (DCM) (TCI) at a temperature of 50 ° C, 5.3 ml (0.0539 mol) of methacryloyl chloride (Aldrich) was added, and the mixture was stirred at room temperature for 1 day. After completion of the reaction, the reaction product was quenched with NaHCO ₃ , diluted with 100 ml of ethyl acetate, washed three times with 100 ml of saturated NaHCO ₃ , once with 150 ml of brine, twice with 150 ml of DI water Respectively. The organic layer was dried over Na ₂ SO ₄ , and the compound was purified by column chromatography (1: 19 = EA: Hex). The solvent was removed to give tetrahydro-2H-pyran- (Tetrahydro-2H-pyran-4-yl methacrylate, THP4M). The yield was 55.7%.

Synthetic example  4: PP4M  synthesis

[Reaction Scheme 4]

9.51 g (0.091 mol) of methacryloyl chloride (Aldrich) was added to 60 ml of ethanol, 10 ml of 3N hydrochloric acid was added, and the mixture was refluxed for 4 hours and stirred. Subsequently, 200 ml of dioxane was added in-situ, and tert-butyl-4-hydroxypiperidine-1-carboxylate (manufactured by TCI Corporation) (0.109 mol) of pyridine, followed by stirring at room temperature for 2 hours. Then, the solvent is dried, and then dissolved in 500 ml of chloroform. The solution is washed three times with 0.1 N hydrochloric acid (300 ml) and purified. The organic layer was then dried over Na ₂ SO ₄ and the compound was purified by column chromatography (1: 5 = EA: Hex), and the solvent was removed to obtain piperidin-4-yl methacrylate -4-yl methacrylate, PP4M). The yield was 33%.

(( Meta ) Acrylate series  Polymer polymerization)

Example  One

Cyclohexyl methacrylate (CHMA) (TCI),? -Butyrolactonyl methacrylate (GBLMA) (aldrich) and t-butyl methacrylate (t-butylmethacrylate, -BMA (TCI) were mixed at a molar ratio of 3: 3: 4, and 2,2'-azobis isobutyronitrile (AIBN) (manufactured by Daqing Kagaku KK) as an initiator was added to the total amount of the above monomers CHMA, GBLMA and t-BMA) were mixed together.

These are dissolved in methyl ethyl ketone (MEK) having a weight corresponding to twice the total weight of the monomers, and the resulting mixture is added dropwise to MEK having a weight corresponding to one time the total weight of the monomers heated to 80 DEG C for 3 hours . After completion of the dropwise addition, polymerization was carried out at the same temperature for 3 hours. Then, the precipitate was precipitated with n-hexane and vacuum-dried to obtain a powdery (meth) acrylate-based polymer.

Example  2

A (meth) acrylate-based polymer was obtained in the same manner as in Example 1, except that CHMA, GBLMA and t-BMA were used in a molar ratio of 3: 4: 3, respectively, in Example 1.

Example  3

(Meth) acrylate-based polymer was obtained in the same manner as in Example 1, except that CHMA, GBLMA and t-BMA were used in a molar ratio of 2: 5: 3 in Example 1, respectively.

Example  4

Except that tetrahydro-2H-pyran-2-yl methacrylate (THP2M) prepared in Synthesis Example 1 was used instead of CHMA in Example 1 (Meth) acrylate-based polymer was obtained in the same manner as in Example 1.

Example  5

The procedure of Example 1 was repeated except that tetrahydrofuran-2-yl methacrylate (THFM) prepared in Synthesis Example 2 was used instead of CHMA in Example 1 Methacrylate polymer was obtained.

Example  6

Except that tetrahydro-2H-pyran-4-yl methacrylate (THP4M) prepared in Synthesis Example 3 was used instead of CHMA in Example 1 (Meth) acrylate-based polymer was obtained in the same manner as in Example 1.

Example  7

(Meth) acrylate-based polymer was obtained in the same manner as in Example 1 except that tetrahydrofurfuryl methacrylate (THFFMA) (TCI) was used instead of CHMA in Example 1.

Example  8

The procedure of Example 1 was repeated except that piperidine-4-yl methacrylate (PP4M) prepared in Synthesis Example 4 was used instead of CHMA in Example 1 Methacrylate polymer was obtained.

Comparative Example  One

A (meth) acrylate-based polymer was obtained in the same manner as in Example 1, except that hydroxyadamantyl methacrylate (HAMA) (TCI) was used instead of CHMA in Example 1.

Comparative Example  2

Example 1 was repeated except that 2-methyladamantan-2-yl methacrylate (MAMA) (TCI) was used in place of t-BMA in Comparative Example 1. (Meth) acrylate-based polymer was obtained in the same manner.

Comparative Example  3

(Meth) acrylate-based polymer was obtained in the same manner as in Example 1 except that HAMA, GBLMA and MAMA were used in a molar ratio of 3: 4: 3 in Comparative Example 2, respectively.

Comparative Example  4

Example 1 was repeated except that 2-ethyladamantan-2-yl methacrylate (EAMA) (TCI) was used in place of t-BMA in Comparative Example 1. (Meth) acrylate-based polymer was obtained in the same manner.

Comparative Example  5

(Meth) acrylate polymer was obtained in the same manner as in Example 1, except that HAMA, GBLMA and EAMA were used in a molar ratio of 3: 4: 3 in Comparative Example 4, respectively.

Comparative Example  6

Example 1 was repeated except that 2-methyladamantan-2-yl methacrylate (MAMA) (TCI) was used instead of t-BMA in Example 1. (Meth) acrylate-based polymer was obtained in the same manner.

(Preparation of photosensitive resin composition)

Each of the (meth) acrylate-based polymers prepared in Examples 1 to 8 and Comparative Examples 1 to 6 and 6 parts by weight of triphenylsulfonium perfluoro (meth) acrylate based on 100 parts by weight of the (meth) acrylate- Triphenylsulfonium perfluorobutylsulfonate (SP-104, manufactured by SMC), and 25 parts by weight of Nt-butoxycarbonyl-4-hydroxypiperidine as a quincher, based on 100 parts by weight of the photoacid generator -4-hydroxypiperidine, 　 Propyleneglycol monomethylether acetate (PGMEA) in an amount of 10% by weight to prepare each photosensitive resin composition.

Evaluation 1: Pattern collapse ( lifting ) Measure

8 "bare silicon wafer was baked with hexamethyl disilazane (HMDS) at 150 DEG C for 60 seconds, and the photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 6 were baked Coated at a thickness of 4,000 ANGSTROM and soft baked (SB) at 110 DEG C for 60 seconds.

(PSM) with a phase shift mask (PSM) using NSR-S308F (LENS NA: 0.85, ILLUMINATION NA: 0.68, Conv. (Large), sigma: 0.80) : A 1-line-and-space (L / S) pattern was exposed, and post exposure baking (PEB) was performed at 110 캜 for 60 seconds. And developed with 2.38% tetramethyl ammonium hydroxide (TMAH) developer for 60 seconds in a puddling manner.

The minimum pattern size at which pattern lifting occurs at optimum energy (E _op ) and optimum depth of focus was measured, and the results are shown in Table 1 below.

Evaluation 2: Development speed ( dissolution rate , DR ) Measure

Each of the photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 6 was spin-coated on a bare silicon wafer of 8 "in thickness of 4,000 ANGSTROM, baked at 110 DEG C for 60 seconds, Then, the thickness of the wafer coated with the photosensitive resin composition was measured using a thickness meter (K-MAC). Next, the wafer coated with the photosensitive resin composition was immersed in 2.38% by weight of tetramethylammonium hydroxide (Litho Tech Japan) containing tetramethyl ammonium hydroxide (TMAH) (manufactured by Litho Tech Japan), and the developed wafer was measured for the difference between the initial thickness and the subsequent thickness, The development speed was calculated and is shown in Table 1 below.

Evaluation 3: Implant resistance measurement

Each of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 5 was applied to a bare silicon wafer of 8 inches and baked at 110 DEG C for 60 seconds and then cooled to room temperature for about 1 minute to form 300 & , A wafer coated with a photosensitive resin composition having a thickness of 1,000 Å, a thickness of 2,000 Å, a thickness of 3,000 Å and a thickness of 4,000 Å. The wafer coated with the corresponding thickness was subjected to impact energy (BF) using a VISTA 80- 8keV, 5x10 ¹³ boron / cm ² dose (dose) to the injection (implantation) were since the remaining photosensitive resin composition using the DAS2000 equipment PSK社O ₂ ashing (ashing) treatment, and cleaning enough to NXWET of Hitachi社(cleaning _Second ion mass spectrometry (SIMS) was performed using an O ₂ ⁺ Gun, IMS-6f Magnetic Sector (CAMECA), and an impact energy of 7.5 keV, 300 nA 　 current.

When the photosensitive resin composition had a high intensity of boron (B) measured in a wafer after implantation at a thickness lower than a high thickness, it was considered that boron penetrated into the wafer through the photosensitive resin film during the implant. Therefore, it was evaluated that the implant performance was better when the minimum thickness of boron in the wafer after ion implantation did not change. The minimum thickness is shown in Table 1 below.

(Meth) acrylate-based polymer composition ratio Weight average molecular weight (g / mol) Dispersion degree E _op (mJ) SIMS (A) The developing speed (DR)
(nm / s) Minimum lifetime pattern size (nm) Example 1 CHMA: GBLMA: t-BMA
(3: 3: 4) 8,100 1.6 24 300 82.4 130 Example 2 CHMA: GBLMA: t-BMA
(3: 4: 3) 7,700 1.6 23 300 91.2 130 Example 3 CHMA: GBLMA: t-BMA
(2: 5: 3) 8,300 1.6 24 300 93.2 130 Example 4 THP2M: GBLMA: t-BMA
(3: 3: 4) 8,800 1.6 23 500 85.5 130 Example 5 THFM: GBLMA: t-BMA
(3: 3: 4) 8,700 1.6 22 500 87.7 130 Example 6 THP4M: GBLMA: t-BMA
(3: 3: 4) 8,100 1.6 23 500 83.1 130 Example 7 THFFMA: GBLMA: t-BMA
(3: 3: 4) 7,900 1.8 28 500 96.0 130 Example 8 PP4M: GBLMA: t-BMA
(3: 3: 4) 8,400 1.7 35 500 74.5 130 Comparative Example 1 HAMA: GBLMA: t-BMA
(3: 3: 4) 8,500 1.6 25 500 42.3 150 Comparative Example 2 HAMA: GBMA: MAMA
(3: 3: 4) 8,800 1.6 21 500 1.3 200 Comparative Example 3 HAMA: GBMA: MAMA
(3: 4: 3) 8,600 1.6 20 500 2.1 200 Comparative Example 4 HAMA: GBLMA: EAMA
(3: 3: 4) 8,800 1.6 18 500 3.4 220 Comparative Example 5 HAMA: GBLMA: EAMA
(3: 4: 3) 8,400 1.6 18 500 2.3 220 Comparative Example 6 CHMA: GBLMA: MAMA
(3: 3: 4) 8,900 1.6 24 500 22.5 200

Rating 4: Scum ( scum ) evaluation

The photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 6 were each spin-coated on a bare silicon wafer of 8 "in thickness of 5,000 angstroms and soft-baked at 110 DEG C for 60 seconds.

The coated wafers were subjected to a phase shift mask (PSM) using a NSR-S308F (LENS NA: 0.85, ILLUMINATION NA: 0.68, Conv. (Large), sigma: 0.80) , A 150 nm trench pattern was exposed, and post exposure baking (PEB) was performed at 110 deg. C / 60s. And developed with 2.38% tetramethyl ammonium hydroxide (TMAH) developer for 60 seconds in a puddling manner.

A scum at the end of the trench pattern was observed using a CD-SEM. The edge of the pattern was developed, but scum performance was evaluated to such an extent that internal scum remained. In other words, it was judged that although the inside of the fine trench pattern melted well, the scum was less generated even though it was evaluated as a thick film thickness.

1A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E _op )) obtained using the photosensitive resin composition according to Example 1. FIG. 1B is a CD-SEM photograph of a 150 nm pattern ⁽² mJ / cm 2 than the optimal energy (E _op) FIG. 1C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm ² ) of the optimum energy (E _op ) obtained using the photosensitive resin composition according to Example 1. FIG. ) Is a CD-SEM photograph.

2A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 1. FIG. 2B is a CD-SEM photograph of a 150 nm pattern ⁽² mJ / cm 2 than the optimal energy (E _op) FIG. 2C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm ² ) of the optimum energy (E _op ) obtained using the photosensitive resin composition according to Comparative Example 1 ) Is a CD-SEM photograph.

3A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E _op )) obtained using the photosensitive resin composition according to Comparative Example 2, and FIG. 3B is a CD-SEM photograph of a 150 nm pattern ⁽² mJ / cm 2 than the optimal energy (E _op) FIG. 3C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm ² ) of the optimum energy (E _op ) obtained using the photosensitive resin composition according to Comparative Example ² ) Is a CD-SEM photograph.

Referring to FIG. 1A, the pattern of Example 1 using the (meth) acrylate-based polymer according to one embodiment is clear to the inside, and the patterns are formed in a straight line, have. On the other hand, referring to FIGS. 2A and 3A, it can be seen that the patterns of Comparative Examples 1 and 2 are not formed well due to scum.

Referring to Figure 1b, and 1c, 2b and 2c, and 3b and 3c, the more clearly the best energy each ² mJ / cm 2 and 4 mJ / cm ² less exposure by more (E _op) to know the scum performance Respectively. At this time, it can be seen that the pattern of Example 1 is superior to the patterns of Comparative Examples 1 and 2 in the form of scum and pattern.

The depth of focus (DOF) margin, the exposure latitude (EL), and the exposure latitude (EL) of the first comparative example 1 and the second comparative example 2 were 130 nm, Margin and the like can be excellently implemented.

4 is a graph showing the relationship between the depth of focus (DOF) margin at the 150 nm pattern (optimum energy (E _op ): 36 mJ / cm ² ) obtained using the photosensitive resin composition according to Example 1 and the This is a CD-SEM photo showing

The focal depth margin refers to an acceptable focal range of the patterned product that is implemented even when the focal point at the optimal energy (E _op ) is outside the best focus. The allowable focus range typically represents +/- 10% of the CD size.

Referring to FIG. 4, the best focus is -0.05 .mu.m, and the depth of focus margin is 0.25 .mu.m (-0.15 .mu.m to 0.1 .mu.m). In addition, both the center and the edge of the pattern are cleanly developed, and the scum surface is also clear.

5 is a graph showing the exposure latitude (EL) margin of a 150 nm pattern (optimum energy (E _op ): 36 mJ / cm ² ) obtained using the photosensitive resin composition according to Example 1, It is a CD-SEM photograph.

The exposure allows the margin is, the focus optimal conditions (best focus) light exposure (exposure energy) this indicates an acceptable exposure range of the pattern resulting implemented even if outside the optimum energy (E _op), optimum energy to the allowable energy range from (E _op ). The permissible exposure range usually represents +/- 10% of the CD size.

Referring to FIG. 5, the allowable exposure margin is 22% (8 mJ from 32 mJ to 40 mJ). Also, it can be confirmed that both the center and the edge of the pattern are cleanly developed from the underexposed portion to the overdose portion, so that the scum surface is also clean.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (13)

(Meth) acrylate-based polymer comprising repeating units represented by the following general formulas (1) to (3)
.
[Chemical Formula 1]

(In the formula 1,
R < ^{1 >} is hydrogen or a methyl group,
R ¹⁰ is a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C2 to C20 heterocycloalkyl group,
and n is an integer of 0 to 3.)
(2)

(In the formula (2)
R ² includes hydrogen or a methyl group,
R ²⁰ comprises an ester group and includes a substituted or unsubstituted C3 to C20 cycloalkyl group.
(3)

(3)
R ³ includes hydrogen or a methyl group,
R ³⁰ includes a t-butyl group, a triethylcarbyl group, a t-amyl group or an acetal group.)
The method according to claim 1,
Wherein the repeating unit represented by the formula (1) comprises any one of the repeating units represented by the following formulas (4) to (23).
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

The method according to claim 1,
R ¹⁰ in the formula (1) is the substituted or unsubstituted C2 to C20 heterocycloalkyl group,
Wherein the heterocycloalkyl group contains a hetero atom of oxygen (O) or nitrogen (N).
The method according to claim 1,
R ²⁰ in the general formula (2) may be a γ-butyrolactonyl group, a valerolactonyl group, a 1,3-cyclohexanecarbolactonyl group, a 2,6 (2,6-norbornanecarbolacton-5-yl) group or 7-oxa-2,6-norbornanecarbolacton- -5-yl) group.
The method according to claim 1,
The (meth) acrylate-based polymer has a weight average molecular weight of 3,000 to 20,000 g / mol.
The method according to claim 1,
Wherein the (meth) acrylate-based polymer has a dispersion degree of 1.3 to 2.5.
The method according to claim 1,
The (meth) acrylate-
10 to 40 mol% of the repeating unit represented by the above formula (1);
20 to 60 mol% of the repeating unit represented by the formula (2); And
The repeating unit represented by the above formula (3) is preferably 20 to 50 mol%
Wherein the photosensitive resin composition is a photosensitive resin composition.
8. The method according to any one of claims 1 to 7,
The photosensitive resin composition
Photo acid generator (PAG); And
menstruum
Further comprising a photopolymerization initiator.
9. The method of claim 8,
Wherein the (meth) acrylate-based polymer is contained in an amount of 5 to 15% by weight based on the total amount of the photosensitive resin composition.
9. The method of claim 8,
The photoacid generator may include triarylsulfonium perfluoroalkylsulfonate, triarylsulfonium triflate, diaryliodonium triflate, triarylsulfonium nonaplate, diaryliodonium nonaplate, succinimidyl tri Plate, 2,6-dinitrobenzylsulfonate, or a combination thereof.
9. The method of claim 8,
Wherein the photoacid generator is contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the (meth) acrylate-based polymer.
9. The method of claim 8,
Wherein the photosensitive resin composition further comprises 0.1 to 5 parts by weight of an organic amine based on 100 parts by weight of the (meth) acrylate-based polymer.
13. The method of claim 12,
Wherein the organic amine includes triethylamine, triisobutylamine, trioctylamine, triisodecylamine, triethanolamine, hydroxypiperidine, or a combination thereof.

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