KR100249453B1 - Alicylic derivatives for high resolution resist materials of vlsl and process for preparing the same - Google Patents

Abstract

The alicyclic derivative represented by the following formula (1) and a method for producing the same are disclosed in the present invention.

-(M _a ) _x- (M _b ) _y- (M _c ) _u- (M _d ) _v-

In the formula,

M _a is _a norbornene monomer containing a carboxy or hydroxy group ego,

M _b is a dinorbornene monomer containing a carboxy or hydroxy group ,

M _c is an electron deficient monomer ego,

M _d is a (meth) acrylic acid ester monomer ,

R ₁ and R ₂ are independently of each other H or leaving groups having 1 to 4 oxygen atoms, for example H, COOH, CH ₂ OH, COOC ₂ H ₅ , COOC (CH ₃ ) ₃ , methyl ester, tetra Hydropyranyl ester, tetrahydrofuranyl ester, 1-ethoxyethyl ester or t-butyl carbonate,

R ₃ is O, NH or N—CH ₂ CH ₃ ,

R ₄ is H or CH ₃ ,

R ₅ is CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₃ or C (CH ₃ ) ₃ ,

Based on the total moles of x + y + u + v,

x is a value having a molar ratio of 0 to 0.2, preferably 0.01 to 0.1,

y is a value having a molar ratio of 0.25 to 0.5,

u is x + y,

v is a value having a molar ratio of 0.1 to 0.33.

Such cycloaliphatic derivatives have transparency, high resolution and high sensitivity in the ArF excimer laser region, have dry etching resistance comparable to conventional novolak resins, and can be applied to conventional alkaline developers, in particular, adhesion to wafers and Developability is improved. Therefore, these alicyclic derivatives can be used to prepare high resolution resist materials for ArF excimer laser processing.

Description

Cycloaliphatic derivatives for high-resolution resist materials of ultra high-density semiconductors, and methods for their preparation

The present invention relates to an alicyclic derivative for a high resolution resist material suitable for argon fluoride (ArF) excimer laser (193 nm) ultra-fine processing in the manufacture of ultra-high density semiconductor, and more particularly, to an ArF excimer laser. Excimer lasers with transparency, high resolution and high sensitivity in the area, dry etch resistance comparable to conventional novolak resins, and with which existing alkaline developers can be applied, in particular with improved adhesion and developability to wafers The present invention relates to an alicyclic derivative for a high resolution single layer resist material suitable for ultrafine processing, and a method for producing the same.

At present, lithography has become a key technology in achieving high density of DRAM, a memory semiconductor, and especially in the manufacture of ultra-high density semiconductors (VLSI), a finer microlithography is required. There is an urgent need for high performance resist materials that can be achieved. Ultra-fine processing technology of circuit line width using deep ultraviolet (DUV), electron beam (EB), and X-rays is actively being studied, and 0.10 μm using ArF excimer laser to make ultra-high density semiconductors larger than 1 gigabit (Gb) DRAM Ultrafine circuit line width processing technology of 0.18 μm is required.

Phenolic resins such as novolac and polyhydroxystyrene are used as photoresist materials used in the conventional i-ray (365 nm) and KrF excimer laser (248 nm) microfabrication techniques. At nm, the absorption of light is so high that it cannot be used as a single layer resist material for ultrafine processing using an ArF excimer laser. In contrast, acrylic and methacrylic polymers have attracted attention as ArF excimer laser resist materials due to their low absorbance at 193 nm, but they are less resistant to dry etching. In particular, in the ArF excimer laser resist material, the improvement of adhesive properties and the use of the existing developer have become a big problem. In the case of poor adhesive properties, the resist micropattern is lifted, and during development, the developer is about 10 to 20 times higher. There is a drawback to dilution. Therefore, in recent years, an alicyclic group having a large number of carbon atoms has been introduced into the main chain or branched chain in order to increase the resistance to dry etching of the acrylic polymer.

In the main chain of such a resist material polymer, norbornene (see Proc. SPIE, vol. 3049, 84, 1997) as an alicyclic monomer, norbornene derivative (Proc. SPIE, vol. 3049, 92 & 104) & 430, 1997), cyclodiene (see J. Photopolym. Sci. Technol, vol. 10, 535, 1997) and nortricyclene (Proc. SPIE, vol. 3049, 113, 1997). And the like) are used. In addition, the branched chain of the resist material polymer includes an adamantyl group (see US Patent No. 5399647, 1995), an isobornyl group (see Proc. SPIE, vol. 2724, 334, 1996), and a menthyl group as an alicyclic group. See J. Photopolym. Sci. Technol. Vol. 9, 457, 1996), tricyclodecanyl groups (see Proc. SPIE, vol. 3049, 126, 1997), norbornyl groups (Proc. SPIE, vol. 3049, 485, 1997) and tetracyclododecyl groups (see Proc. SPIE, vol. 3049, 55, 1997). However, since the conventional polymer containing alicyclic groups is composed of monomers having different basic properties, the content of cycloaliphatic which shows resistance to dry etching is low, so that the resistance to dry etching is reduced, as well as the aqueous alkali solution. It exhibits low solubility and poor adhesion and sensitivity to the wafer.

Therefore, the present inventors have come to the present invention as a result of intensive studies to overcome the disadvantages of the prior art.

It is an object of the present invention to provide an alicyclic derivative for a high resolution resist material suitable for ArF excimer laser ultrafine processing of ultra-high density semiconductors and a method for producing the same.

Another object of the present invention is to provide a high resolution resist material for ArF excimer laser processing comprising an alicyclic derivative according to the present invention.

The cycloaliphatic derivatives of the present invention have a structure of formula (I) having norbornene and dinorbornene, containing carboxy or hydroxy groups in the main chain.

<Formula 1>

-(M _a ) _x- (M _b ) _y- (M _c ) _u- (M _d ) _v-

In the formula,

M _a is _a norbornene monomer containing a carboxy or hydroxy group ego,

M _b is a dinorbornene monomer containing a carboxy or hydroxy group ,

M _c is an electron deficient monomer ego,

M _d is a (meth) acrylic acid ester monomer ,

R ₁ and R ₂ are independently of each other H or leaving groups having 1 to 4 oxygen atoms, for example H, COOH, CH ₂ OH, COOC ₂ H ₅ , COOC (CH ₃ ) ₃ , methyl ester, tetra Hydropyranyl ester, tetrahydrofuranyl ester, 1-ethoxyethyl ester or t-butyl carbonate,

R ₃ is O, NH or N—CH ₂ CH ₃ ,

R ₄ is H or CH ₃ ,

R ₅ is CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₃ or C (CH ₃ ) ₃ ,

Based on the total moles of x + y + u + v,

x is a value having a molar ratio of 0 to 0.2, preferably 0.01 to 0.1,

y is a value having a molar ratio of 0.25 to 0.5,

u is x + y,

v is a value having a molar ratio of 0.1 to 0.33.

The cycloaliphatic derivatives of the present invention consist of three or four different monomers to form terpolymers or quaternary copolymers.

Norbornenes containing carboxy or hydroxy groups that can be used in the present invention include carboxy norbornene (CN), norbornene methanol, t-butyloxycarbonyl (tBOC) -containing carboxy norbornene (tBCN) and the like. Can be mentioned. Examples of dinorbornene containing a carboxy or hydroxy group include carboxy dinorbornene (CDN), dinorbornene methanol, tBOC group-containing dinorbornene (tBDN), tBOC group-containing carboxy dinorbornene (tBCDN), and the like. Can be mentioned.

The norbornene or dinorbornene monomers described above include t-butyloxycarbonyl, methyl ester, tetrahydropyranyl ester, tetrahydrofuranyl ester, 1-ethoxyethyl ester, t-butyl carbonate and the like. T-butyloxycarbonyl of carboxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecene, a dinorbornene containing a leaving group having 1 to 4 oxygen atoms and containing a double tBOC group And the like can be used.

The cycloaliphatic derivative of Chemical Formula 1 according to the present invention is excellent in resistance to dry etching and transparent in the ArF excimer laser (193 nm) region because of the presence of norbornene and dinorbornene containing carboxy or hydroxy groups in the main chain. In addition, due to the functionalities of the norbornene and dinorbornene monomers themselves, the adhesion and developability to the wafer can be greatly improved.

These norbornene or dinorbornene monomers can be easily obtained from two monomers by an easy and simple one step reaction such as Diels-Alder reaction. For example, tBOC group-containing dinorbornene (tBDN) can be used to prepare t-butyl acrylate (tBA) and dicyclopentadiene (DCP) for a relatively long time at a high temperature, for example from 100 to 250 ° C, for example from 6 to 24. After reacting for a period of time and distilling under vacuum, the resultant is purified using a silica gel column to obtain a highly viscous colorless product having a monomer molar ratio of 1: 1.

In particular, the alicyclic monomer containing a leaving group having 1 to 4 oxygen atoms such as tBOC group may also serve as a chemically amplified monomer capable of generating an acid upon exposure. Therefore, the tBOC group and the like are released during exposure to generate a carboxy or hydroxy group, and due to the difference in solubility of the resist material, these materials can be dissolved using an existing alkaline developer.

If the content of the norbornene monomer in the alicyclic monomer is added too much, since it can be dissolved in the alkaline developer before deprotection, it is preferably present in a molar ratio of 0 to 0.2 with respect to the entire copolymer, and a molar ratio of 0.01 to 0.1. More preferably present.

In addition, the dinorbornene monomer is preferably present in a molar ratio of 0.25 to 0.5 with respect to the entire copolymer. If the content of dinorbornene monomer is less than 0.25 molar ratio, there is no dry etching resistance comparable to the conventional novolak resin.

Since cycloaliphatic monomers such as norbornene or dinorbornene are electron-rich monomers, polymerization alone does not occur well during radical polymerization. Therefore, in order to polymerize such electron-rich monomers, maleic anhydride, an electron deficient monomer, is required. (MA) or maleimide, such as maleimide (MI), ethyl maleimide (EMI), can be used to copolymerize monomers in a 1: 1 alternation structure. In general, it is preferable to use such N-substituted maleimide monomers because the maleimide polymerizes better than maleic anhydride and can easily introduce functional functional groups to the N-position of the maleimide. The content of the electron deficient monomer is preferably present in the same proportion as the total content of the alicyclic norbornene and dinorbornene monomers relative to the entire copolymer.

In addition, the use of the (meth) acrylic acid ester monomer in the alicyclic derivative of the present invention facilitates film coating of the product, improves transparency, and lowers the high glass transition temperature (Tg) of the alicyclic monomer, thereby adhering the product to the wafer. This is improved. The content of the (meth) acrylic acid ester monomer is preferably in a molar ratio of 0.1 to 0.33 based on the total copolymer. When the content of the (meth) acrylic acid ester monomer is less than 0.1 molar ratio with respect to the total copolymer, the above-described improvement effect does not appear according to the addition thereof, and when the content exceeds the molar ratio of 0.33, the content of the alicyclic monomer is relatively low. There is a disadvantage in that satisfactory dry etching resistance cannot be obtained.

The cycloaliphatic derivatives according to the present invention carry out the reaction of the three or four monomers according to the present invention under an inert gas atmosphere such as nitrogen and argon for 3 to 24 hours using a radical polymerization initiator by a conventional radical polymerization method. Can be prepared. Radical polymerization initiators that can be used include thermal polymerization initiators such as benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), di-t-butyl peroxide (DTBP) and 2,2-dimethoxy-2- There is a photopolymerization initiator such as phenylacetophenone (DMPA), and when using a radical polymer thermal polymerization initiator, the reaction is carried out in a temperature range of 50 to 150 ° C. Further solvents include dioxane, tetrahydrofuran (THF), propylene glycol monoethylether acetate (PGMEA), acetone and the like. The molecular weight of the copolymer by gel permeation chromatography (GPC) is suitably adjustable depending on the amount of initiator or solvent used in the reaction on the order of 3,000 to 15,000.

The cycloaliphatic derivatives of the present invention, prepared as described above, exhibit good film-forming ability and exhibit low light absorption of 0.35 to 0.5 or less per 1 μm thickness at 193 nm as measured by ultraviolet spectroscopy for ArF excimer lasers. It has been identified as a very suitable polymer for resist applications using an exposure source. In addition, these alicyclic derivatives are not soluble in alkaline developer such as trimethylammonium hydroxide (TMAH) aqueous solution (2.38% by weight) before deprotection but are soluble in organic solvents such as cyclohexanone or anisole, while After deprotection, it is well dissolved in an aqueous alkali solution, and the polarity change due to deprotection of the acid-reactive protecting group can greatly change the solubility of the polymer.

In addition, the alicyclic derivative of the present invention exhibited stable heat resistance at 220 to 250 ° C. in thermogravimetric analysis (TGA: DuPont Model 951), and deprotection such as tBOC group exceeded the above temperature to generate carboxy or hydroxy groups.

Hereinafter, an example will be described in detail with respect to the alicyclic monomer used in the present invention, the method for preparing the alicyclic derivative of the present invention, and microscopic image formation using the same, but the present invention is not limited thereto.

Preparation Example 1 Preparation of Carboxy Norbornene (CN)

54 g (0.41 mol) of dicyclopentadiene (DCP) and 30 g (0.41 mol) of acrylic acid were added to a high pressure reactor together with 100 ml of ethyl ether, and 0.05 g of hydroquinone was added, followed by stirring at 180 ° C. for 3 hours. The product was fractionally distilled under vacuum to recover purified carboxy norbornene (CN) [boiling point: 86-88 ° C./0.1 torr, yield: 73 g (87%)].

Preparation Example 2 Preparation of tBOC Group-Containing Carboxy Norbornene (tBCN)

Cyclopentadiene (CP) was prepared by cracking DCP 100 g at 180 ° C. 50 g of CP thus prepared was excessively added dropwise to a solution of 74 g of maleic anhydride (MA) in 200 ml of benzene and reacted at room temperature for 6 hours. Solid norbornene carboxylic anhydride (NCA) obtained by evaporation of benzene was recrystallized from petroleum ether [yield: 121.5 g (98%)]. 10 g (0.06 mol) of purified NCA and 6.82 g (0.06 mol) of potassium t-butoxide were dissolved in t-butanol and refluxed at 100 ° C. for 8 hours to give white crystals of carboxy norbornene (tBCN) containing tBOC group. Obtained [yield: 13.1 g (78%)].

Preparation Example 3 Preparation of Carboxydinonorbornene (CDN)

40 g (0.30 mol) of DCP and 22 g (0.30 mol) of acrylic acid were added to a high pressure reactor together with 150 ml of diethyl ether, and 0.05 g of hydroquinone was added, followed by stirring at 180 ° C. for 5 hours. The product was fractionally distilled under vacuum to recover CN (boiling point: 86-88 ° C./0.1 torr), and then purified and colorless through a silica gel column using a developing solvent of n-hexane: ethyl acetate (3: 1). High viscosity carboxy dinorbornene (CDN) was recovered [yield: 18.7 g (30%)].

Preparation Example 4 Preparation of tBOC Group-Containing Carboxydinonorbornene (tBCDN)

Dinorbornene carboxylic anhydride (DNCA) was synthesized by dropwise addition of CP 9 g to 30 g (0.18 mol) of NCA prepared in the same manner as in Preparation Example 2, and then recrystallized with petroleum ether. Subsequently, 30 g (0.18 mol) of DNCA and 20.4 g (0.18 mol) of potassium t-butoxide were dissolved in t-butanol, and refluxed at 100 ° C. for 8 hours to give white crystals of tBOC group-containing carboxy dinorbor. Nene (tBCDN) was obtained [Yield: 34 g (67%)].

Preparation Example 5 Preparation of tBOC Group-Containing Dinorbornene (tBDN)

60 g (0.45 mol) of t-butyl acrylate (tBA), 64 g (0.45 mol) of dicyclopentadiene (DCP) and 120 ml of ethyl ether were added to a high pressure reactor, 0.05 g of hydroquinone was added, followed by stirring at 180 ° C. for 18 hours. Reacted. The resulting product was fractionally distilled under vacuum to obtain 38 g of tBOC group-containing norbornene (tBN, boiling point: 96-98 ° C./10 torr) as a colorless viscous liquid, followed by n-hexane: ethyl acetate (2: 1) Purified colorless highly viscous tBOC group containing dinorbornene (tBDN) was obtained through a silica gel column using a developing solvent [yield: 40 g (33%)].

Thus the alicyclic monomers of each of the chemical structure produced was confirmed by infrared (IR, Mattson Genesis Series) and proton nuclear magnetic resonance ⁽¹ H-NMR) spectroscopy (Varian Gemini 2000, 200 MHz) .

IR analysis showed that the ester absorption band of the tBOC group at 1727 cm ⁻¹ , the CO absorption band of the tBOC group at 1150 cm ⁻¹ , the methyl absorption band of the tBOC group at 1366 cm ⁻¹ , norbornene at 1450 cm ⁻¹ , and The methylene absorption band of dinorbornene and the double bond absorption band of norbornene and dinorbornene at 3050 cm ⁻¹ were shown, respectively. In addition, the ¹ H-NMR analysis showed that the two protons of the double bonds were singlet at 5.85 ppm, singlet at 2.77 ppm methine, and multiline at 1.80-2.55 ppm methylene, and mixed peaks of methine, methylene and methyl at 0.58-1.80 It appeared as polyline at ppm. From this, it was confirmed that the alicyclic monomer was well synthesized.

<Example 1>

Preparation of alicyclic derivative P (CN-tBDN-MA-MMA)

0.05 g (0.39 mmol) CN monomer, 0.9 g (3.47 mmol) tBDN monomer, 0.38 g (3.85 mmol) maleic anhydride (MA), 0.38 g (3.85 mmol) methyl methacrylate (MMA) and initiator benzoyl in the polymerization vessel 27.9 mg (0.12 mmol) of peroxide (BPO) was added thereto, dissolved in 4 ml of dioxane, and then sealed under vacuum by freezing and thawing under argon gas. The sealed polymerization vessel was reacted for 18 hours in a constant temperature bath at 80 ° C. The reaction solution thus obtained was precipitated in methanol, filtered and dried to synthesize P (CN-tBDN-MA-MMA), which is an alicyclic moiety copolymer.

The conversion of P (CN-tBDN-MA-MMA) obtained was 80%, and IR analysis showed that the double bond peaks of norbornene and dinorbornene disappeared at around 3050 cm ⁻¹ compared to CN and tBDN and instead of 1780 and The C = O peak of MA at 1860 cm ⁻¹ and the ester absorption band of MMA at 1730 cm ⁻¹ showed that the molecular copolymer was well synthesized. Molecular weight of P (CN-tBDN-MA-MMA) by GPC (Waters 510) was 10,000 and the film was well formed, and the absorbance at 193 nm by UV spectrometer (Jasco V-530) was 0.35 per 1 μm thickness. Very high transparency was shown.

<Example 2>

Preparation of cycloaliphatic derivative P (tBCN-tBDN-MI-tBA)

0.09 g (0.39 mmol) tBCN monomer, 0.9 g (3.47 mmol) tBDN monomer, 0.37 g (3.85 mmol) maleimide (MI), 0.5 g (3.85 mmol) acrylic acid t-butyl (tBA) and initiator azobis 18.9 mg (0.115 mmol) of isobutyronitrile (AIBN) were added, dissolved in 4 ml of tetrahydrofuran (THF), and sealed under vacuum by freezing and thawing under argon gas. The sealed polymerization vessel was reacted for 24 hours in a constant temperature bath at 60 ° C. The reaction solution thus obtained was precipitated in methanol, filtered and dried to synthesize P (tBCN-tBDN-MI-tBA), which is an alicyclic moiety copolymer.

The conversion rate of the obtained P (tBCN-tBDN-MI-tBA) was 60%, and IR analysis showed similar peak characteristics to P (CN-tBDN-MA-MMA) of Example 1. The molecular weight of P (tBCN-tBDN-MI-tBA) by GPC (Waters 510) was well formed by 5,000, and the absorbance at 193 nm by UV spectrometer (Jasco V-530) was 0.45 per 1 μm thickness. High transparency was shown.

<Example 3>

Preparation of alicyclic derivative P (CDN-tBDN-MA-EA)

In the polymerization vessel 0.08 g (0.39 mmol) of CDN monomer, 0.9 g (3.47 mmol) of tBDN monomer, 0.38 g (3.85 mmol) of maleic anhydride (MA), 0.19 g (1.93 mmol) of ethyl acrylate (EA) and initiator di-t 8.9 mg (0.035 mmol) of -butyl peroxide (DTBP) were added and dissolved in 5 ml of propylene glycol monoethylether acetate (PGMEA), and then sealed under vacuum by freezing and thawing under argon gas. The sealed polymerization vessel was reacted for 12 hours in a constant temperature bath at 130 ° C. The reaction solution thus obtained was precipitated in methanol, filtered and dried to synthesize P (CDN-tBDN-MA-EA), which is an alicyclic moiety copolymer.

The conversion of P (CDN-tBDN-MA-EA) obtained was 65%, and IR analysis showed similar peak characteristics to P (CN-tBDN-MA-MMA) of Example 1. Molecular weight of P (CDN-tBDN-MA-EA) by GPC (Waters 510) was 8,000 and the film was well formed, and the absorbance at 193 nm by UV spectrometer (Jasco V-530) was 0.4 per 1 μm thickness. High transparency was shown.

<Example 4>

Preparation of cycloaliphatic derivative P (tBCDN-tBDN-EMI-nBA)

In the polymerization vessel, 0.12 g (0.39 mmol) of tBCDN monomer, 0.9 g (3.47 mmol) of tBDN monomer, 0.48 g (3.85 mmol) of ethyl maleimide (EMI), 0.25 g (1.93 mmol) of n-butyl acrylate (nBA) and initiator 2 8.9 mg (0.035 mmol) of, 2-dimethoxy-2-phenylacetophenone (DMPA) was added thereto, dissolved in 4 ml of acetone, and sealed under vacuum by freezing and thawing under argon gas. The sealed polymerization vessel was irradiated with UV for 6 hours. The reaction solution thus obtained was precipitated in methanol, filtered and dried to synthesize P (tBCDN-tBDN-EMI-nBA), which is an alicyclic moiety copolymer.

The conversion of P (tBCDN-tBDN-EMI-nBA) obtained was 70%, and IR analysis showed peak characteristics similar to P (CN-tBDN-MA-MMA) of Example 1. Molecular weight of P (tBCDN-tBDN-EMI-nBA) by GPC (Waters 510) was 13,000 and the film was well formed, and the absorbance at 193 nm by UV spectrometer (Jasco V-530) was 0.5 per 1 μm thickness. Relatively high transparency.

<Example 5>

Preparation of Alicyclic Derivative P (tBCDN-EMI-nBA)

The title compound P (tBCDN-EMI-nBA) was obtained in the same manner as in Example 4 except that tBDN used in Example 4 was not used. The obtained compound showed similar properties to the compound P (tBCDN-tBDN-EMI-nBA) of Example 4.

As a result of elemental analysis of the cycloaliphatic derivatives of the present invention, the molar ratio of norbornene and dinorbornene monomer to electron deficient monomer was found to be about 1: 1.

<Example 6>

Micro Image Formation

P (CN-tBDN-MA-MMA) prepared in Example 1 was dissolved in cyclohexanone at 5 to 20% by weight, and triphenylsulfonium triflate, a known photoacid generator, was dissolved in P (CN-tBDN- MA-MMA), dissolved at 0.5 to 5% by weight, and filtered through a 0.45 μm filter to form a chemically amplified resist solution. The resist solution was spun onto a silicon wafer to produce a thin film having a thickness of 0.5 to 1 μm. The sample wafer was preheated on a hot plate at 100 ° C. for 1 to 3 minutes and exposed through a photomask using an ArF excimer laser exposure apparatus, followed by 30 seconds to 2 minutes at a specific constant temperature ranging from 80 to 150 ° C. Post heat treatment. The various products thus produced were immersed in an aqueous trimethylammonium hydroxide (TMAH) aqueous alkali solution (2.38 wt%) for 10 to 60 seconds to develop an exposed portion of a submicron positive resist microimage.

According to the present invention, an alicyclic derivative for a high resolution resist material for ultrafine processing of an ultra-high density semiconductor can be prepared, and such an alicyclic derivative has transparency, high resolution, and high sensitivity in an ArF excimer laser region, and is a conventional novolak. It has dry etching resistance comparable to resin, and it is possible to apply an existing alkaline developer, and in particular, adhesion and developability to a wafer are improved. Therefore, these alicyclic derivatives can be used to prepare high resolution resist materials for ArF excimer laser processing.

Claims (7)

Alicyclic derivative represented by the following formula (1). <Formula 1> -(M _a ) _x- (M _b ) _y- (M _c ) _u- (M _d ) _v- In the formula, M _a is _a norbornene monomer containing a carboxy or hydroxy group ego, M _b is a dinorbornene monomer containing a carboxy or hydroxy group , M _c is an electron deficient monomer ego, M _d is a (meth) acrylic acid ester monomer , R ₁ and R ₂ are independently of each other H or leaving groups having 1 to 4 oxygen atoms, for example H, COOH, CH ₂ OH, COOC ₂ H ₅ , COOC (CH ₃ ) ₃ , methyl ester, tetra Hydropyranyl ester, tetrahydrofuranyl ester, 1-ethoxyethyl ester or t-butyl carbonate, R ₃ is O, NH or N—CH ₂ CH ₃ , R ₄ is H or CH ₃ , R ₅ is CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₃ or C (CH ₃ ) ₃ , Based on the total moles of x + y + u + v, x is a value having a molar ratio of 0 to 0.2, preferably 0.01 to 0.1, y is a value having a molar ratio of 0.25 to 0.5, u is x + y, v is a value having a molar ratio of 0.1 to 0.33. The compound of claim 1, wherein R ₁ and R ₂ are each independently H, COOH, CH ₂ OH, COOC (CH ₃ ) ₃ , COOC ₂ H ₅ , methyl ester, tetrahydropyranyl ester, tetrahydrofuranyl ester, Alicyclic derivative which is 1-ethoxyethyl ester or t-butyl carbonate. The electron deficient monomer according to claim 1 or 2, wherein the electron deficient monomer is selected from maleic anhydride and maleimide, and the (meth) acrylic acid ester monomer is selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate and t-butyl acrylate. Alicyclic derivative. The cycloaliphatic derivative according to claim 1 or 2, wherein the cycloaliphatic derivative has a molecular weight of 3,000 to 15,000. M as norbornene monomers containing carboxy or hydroxy groups_aM as dinorbornene monomers containing carboxyl, carboxy or hydroxy groups_bAs an electron deficient monomer_c And M as a (meth) acrylic acid ester monomer._dMethod of producing a cycloaliphatic derivative represented by the formula (1) comprising radical polymerization in a solvent under an inert gas atmosphere for 3 to 24 hours using a radical polymerization initiator in the temperature range of 50 to 150 ℃. <Formula 1> -(M _a ) _x- (M _b ) _y- (M _c ) _u- (M _d ) _v- In the formula, M _a is _a norbornene monomer containing a carboxy or hydroxy group ego, M _b is a dinorbornene monomer containing a carboxy or hydroxy group , M _c is an electron deficient monomer ego, M _d is a (meth) acrylic acid ester monomer , R ₁ and R ₂ are independently of each other H or leaving groups having 1 to 4 oxygen atoms, for example H, COOH, CH ₂ OH, COOC ₂ H ₅ , COOC (CH ₃ ) ₃ , methyl ester, tetra Hydropyranyl ester, tetrahydrofuranyl ester, 1-ethoxyethyl ester or t-butyl carbonate, R ₃ is O, NH or N—CH ₂ CH ₃ , R ₄ is H or CH ₃ , R ₅ is CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₃ or C (CH ₃ ) ₃ , Based on the total moles of x + y + u + v, x is a value having a molar ratio of 0 to 0.2, preferably 0.01 to 0.1, y is a value having a molar ratio of 0.25 to 0.5, u is x + y, v is a value having a molar ratio of 0.1 to 0.33. The compound of claim 5, wherein R ₁ and R ₂ are independently of each other H, COOH, CH ₂ OH, COOC (CH ₃ ) ₃ , COOC ₂ H ₅ , methyl ester, tetrahydropyranyl ester, tetrahydrofuranyl ester, A process for producing an alicyclic derivative which is 1-ethoxyethyl ester or t-butyl carbonate. A high resolution resist material for ArF excimer laser processing made of the cycloaliphatic derivative according to claim 1.