KR102114116B1 - Resist materials comprising highly fluorinated polymers having a solubility in highly fluorinated solvents - Google Patents

Abstract

The present invention relates to a resist material comprising a high fluorinated polymer having a solubility in a high fluorine-based solvent, and according to the present invention, a high fluorinated polymer having a solubility in a high fluorine-based solvent (PFDMA, PFUDMA, PFDDMA) is used as an electron beam resist material It can be applied in the form of a solution to the substrate, and the formed thin film has a reduced solubility due to electron beam irradiation, so that a high-resolution image can be formed, and when applied to electron beam lithography, a negative tone pattern is formed to be used as a negative resist material. Can be.

Description

Resist materials comprising highly fluorinated polymers having a solubility in highly fluorinated solvents}

The present invention relates to a high fluorinated polymer having a solubility in a high fluorine-based solvent and a resist material comprising the same, wherein the resist material can be applied in a solution form on a substrate, and the formed thin film has reduced solubility by irradiation with electron beam, The present invention provides a resist material for electron beam lithography capable of forming a high resolution image by developing conditions using a high fluorine-based solvent.

Fluorine atoms have a relatively small atomic radius and form strong chemical bonds with carbon atoms. Therefore, when a fluorine atom is introduced into a hydrocarbon molecule to replace a hydrogen atom, a stable compound can be formed without causing a large distortion in the molecular geometry. However, since the fluorine atom has strong electronegativity and weak polarizability, when hydrogen atoms in most of the hydrocarbon molecules are replaced with fluorine atoms, various features that are difficult to observe in hydrocarbons are expressed. Representatively, electrons that are strongly bound around the fluorine nucleus are inactivated by attack of nucleophile and oxidizing agent and exhibit chemical stability. In addition, due to the reduced interaction with other molecules, it has both hydrophobic and oleophobic properties, and exhibits low solubility in conventional non-fluorinated solvents.

The characteristics of such highly fluorinated molecules are embodied in the form of low molecular weight fluids and in the form of polymers, which have a great influence on our daily lives. In addition to the above characteristics, high fluorinated or fluorinated fluids are drug delivery based on high thermal stability, excellent dielectric properties, low surface tension, non-flammability, and low toxicity. It is widely applied as a propellant for inhalers for delivery, as a cleaning solvent for medical equipment and precision parts, and as a heat transfer fluid. Furthermore, in recent years, attempts have been made to utilize the lipophilic properties of fluorinated fluids and apply it to patterning thin films of organic electronic materials that are susceptible to chemical infringement. Representatively, a photoresist dissolved in a fluorinated fluid is coated on a thin film of an organic light-emitting material to form a pixel of a fine organic light-emitting diode (OLED), exposed, and then developed again with an appropriate fluorinated fluid for imaging. Studies have been reported to form templates for imagination.

The high fluorinated polymer was produced by Scholffer and Scherer in the 1930s by poly (chlorotrifluoroethylene); PCTFE], and Plunkett is a high molecular weight poly (tetrafluoroethylene) [poly (tetrafluoroethylene); PTFE] has started to receive attention in the development of poly (vinylfluoride) [poly (vinylfluoride); PVF], poly (vinylidene fluoride); PVDF], poly (trifluoroethylene) [poly (trifluoroethylene)] and various high fluorinated polymers have appeared. Among them, PTFE commercialized under the name of Teflon ^TM is used in various fields due to its excellent chemical resistance and friction properties, and it is also important to apply it as a functional additive to lubricants, plastics, paints, etc. in the form of fine powder Is one of the. PTFE-based fluoroadditives have a smaller particle size and lower molecular weight than other grades of PTFE, which are mainly used to irradiate or thermally decompose electron beams (e-beams) to high molecular weight PTFE. It is manufactured through a thermal degradation process.

As mentioned above, it is known that chain scission easily occurs by irradiation of electron beams or gamma rays at room temperature, which has been commercially applied. However, some documents have reported that cross-linking may occur when high energy radiation is irradiated at a temperature higher than the melting point of PTFE under an inert atmosphere. In view of this, the present inventors have a chain similar to PTFE as a side chain, and a solution process is possible using a fluorinated fluid, and poly (semi-perfluoroalkyl methacryl) is relatively very easy to synthesize. Rate) [poly (semi-perfluoroalkyl methacrylate)] to analyze the chemical properties under electron beam irradiation conditions. In 2000, the M. Lazzari research team published a study on photooxidative degradation of acrylate polymers and methacrylate polymers by ultraviolet light emitted from xenon light sources. In the above study, it was confirmed that the photochemical stability was improved when a high fluorinated alkyl chain was added to the methacrylate-based polymer. However, acrylate polymers or methacrylate polymers having a high fluorinated alkyl chain high enough to be soluble in a fluorinated solvent were not synthesized and applied, and since electron beam irradiation was performed under atmospheric conditions, reactions involving oxygen radicals were involved. I could observe.

In the present invention, the electron lithography (lithography) is advanced, fluorinated methacrylate having a high fluorine content of a level that can be dissolved in a fluorinated solvent under a high-vacuum-excluded condition, what kind of chemical changes by electron beam irradiation Analysis. If the solubility of the fluorinated methacrylate thin film can be selectively changed through radiation chemistry by electron beam irradiation, it is applied with a fluorinated solvent having a very low chemical invasion property to lithographically pattern a very weak organic material. It is expected to be useful.

In accordance with the above recognition, the present invention will describe the development strategy of a high-fluorinated polymer resist that can be dissolved in a high-fluorine-based solvent and can be coated with a high-fluorine-based solution, and the synthesis of a high-fluorinated polymer electron beam resist that embodies it.

Republic of Korea Registered Patent No. 10-0740994 (registered on July 12, 2007)

An object of the present invention is to provide a resist material containing a high fluorinated polymer having a solubility in a high fluorine-based solvent and a pattern forming method using the same.

In order to achieve the above object, the present invention includes a high fluorinated polymer represented by the following Chemical Formula 1, wherein the polymer provides a highly fluorinated electron beam resist material in which a pattern process is performed with a high fluorine-based solvent.

[Formula 1]

In Formula 1, x is an integer from 0 to 10, n is an integer from 10 to 1000.

In addition, the present invention is a first step of dissolving the highly fluorinated electron beam resist material in a high fluorine-based solvent and applying it to the substrate; A second step of heating the substrate to form a resist film; A third step of irradiating an electron beam to the resist film: and a fourth step of developing the resist film with a developer and forming a pattern on a substrate.

According to the present invention, a high fluorinated polymer (PFDMA, PFUDMA, PFDDMA) having solubility in a high fluorine-based solvent can be applied as a solution to the substrate by being used as an electron beam resist material, and the formed thin film has reduced solubility by irradiation with electron beam A bar, a high-resolution image can be formed, and when applied to electron beam lithography, a negative tone pattern can be formed and used as a negative resist material.

Figure 1 (a) is a diagram showing the chemical structure of the high-fluorination solvent FC-3283, FC-770, HFE-7500, (b) is a synthetic formula of FUDMA, FDDMA monomer, (c) is PFDMA, PFUDMA, PFDDMA It is a diagram showing a synthetic formula of polymer polymerization.
2 is a view showing the molecular weight of the synthesized polymer PFDMA, PFUDMA, PFDDMA.
Figure 3 (a) is a PFDMA, (b) is PFUDMA, (c) is a diagram showing a scanning electron microscope photograph of a negative tone pattern secured by electron beam lithography of PFDDMA, (d) is PFDMA, (e) is PFUDMA, (f) is a view showing an atomic force microscope photograph of the same pattern of PFDDMA.
Figure 4 (a) is a norrish type II decomposition reaction, (b) is defluorination (defluorination) decomposition (defluorination) decomposition of a high-fluorination alkyl chain and the decomposition mechanism by electron beam irradiation that can induce the generation of cross-linking between chain It is a drawing.
5 (a) is a diagram showing Fourier transform infrared spectroscopy (FT-IR) spectra of a thin film before and after irradiation with PFDMA, (b) PFUDMA, and (c) PFDDMA.
6 is an X-ray photoelectron spectroscopy (XPS) spectrum of the PFDMA thin film before electron beam irradiation and the PFDMA thin film after electron beam irradiation, (a) is C 1s spectrum, (b) is O 1s spectrum, (c) is F 1s spectrum, (d) shows the survey spectrum.
7 is a view showing the GC-MS (EI mode) spectrum of PFDMA, PFUDMA, and PFDDMA.

The inventors of the present invention developed a resist containing a high fluorinated polymer soluble in a high fluorinated solvent, and applied it to electron beam lithography, confirming that a negative tone pattern was formed, and completed the present invention.

Accordingly, the present invention includes a high fluorinated polymer represented by the following Chemical Formula 1, and the polymer provides a highly fluorinated electron beam resist material in which a pattern process is performed with a high fluorine-based solvent.

[Formula 1]

In Formula 1, x is an integer from 0 to 10, n is an integer from 10 to 1000.

The high fluorinated polymer is poly (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate) (PFDMA), poly (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorodecyl methacrylate) (PFUDMA) and poly (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacrylate) It may be selected from the group consisting of (PFDDMA), but is not limited thereto.

The high fluorinated polymer is 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorodecyl methacrylate (FUDMA ), 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacrylate (FDDMA) and 3 One selected from the group consisting of, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (FDMA) The above monomers may be included, but are not limited thereto.

The high fluorinated polymer can be dissolved in a high fluorine-based solvent.

The high fluorine-based solvent is 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane (3 -ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane; HFE-7500), perfluorotripropylamine; FC- 3283) and perfluoro-N-alkyl morpholines (FC-770), but is not limited thereto.

The high fluorinated polymer may have a number average molecular weight (Mn) of 8,000 to 13,000, but is not limited thereto.

In addition, the present invention is a first step of dissolving the highly fluorinated electron beam resist material in a high fluorine-based solvent and applying it to the substrate; A second step of heating the substrate to form a resist film; A third step of irradiating an electron beam to the resist film: and a fourth step of developing the resist film with a developer and forming a pattern on a substrate.

It should be noted that the substrate of the first process may be a silicon substrate, but is not limited thereto.

It is noted that the heat treatment of the second process may be performed at 60 to 80 ° C. for 30 seconds to 2 minutes, but is not limited thereto.

The electron beam of the third process may be irradiated with a dose of 0.5 to 15 C / m ² , but it is not limited thereto.

Hereinafter, the present invention will be described in more detail through examples. These examples are only intended to illustrate the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .

Example 1: 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorodecyl methacrylate (4, Synthesis of 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl methacrylate (FUDMA)

Methyl methacrylate (3.14 g, 31.37 mmol), 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11- Heptadecafluoro undecen-1-ol (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro undecen-1- ol) (3.00 g, 6.27 mmol), dibutyltin dilaurate (0.97 g, 1.25 mmol), 2,6-di-tert-butyl-4-methylphenol (2,6-di-tert -butyl-4-methylphenol) (0.009 g, 0.044 mmol), toluene (10 cm ³ ) as a solvent was placed in a 100 cm ³ round bottom flask. Subsequently, the inside of the flask was replaced with an N ₂ stream, heated to 120 ° C. and stirred overnight. After cooling to room temperature, the mixture was extracted with diethyl ether, washed with water and dried over anhydrous MgSO ₄ . The obtained compound was subjected to column chromatography (silica gel, dichloromethane: hexane = 1: 3) to obtain FUDMA (2.50 g, 78%) as a colorless liquid.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.93 (s, 3 H), 1.96-2.03 (m, 2 H), 2.11-2.26 (m, 2 H), 4.21 (t, J = 6 Hz, 2 H), 5.57 (s, 1 H), 6.09 (s, 1 H).

Example 2: 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacrylate (5, Synthesis of 5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacrylate (FDDMA)

Methyl methacrylate (5.08 g, 50.79 mmol), 5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorododecene-1 -Ol (5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorododecan-1-ol) (5.00 g, 10.15 mmol), dibutyl tin Dilauric acid (1.28 g, 2.03 mmol), 2,6-di-tert-butyl-4-methylphenol (0.015 g, 0.071 mmol), toluene (15 cm ³ ) as a solvent was placed in a 250 cm ³ round bottom flask. . Subsequently, the inside of the flask was replaced with an N ₂ stream, heated to 120 ° C. and stirred overnight. After cooling to room temperature, the mixture was extracted with diethyl ether, washed with water, and dried over anhydrous MgSO ₄ . The obtained compound was subjected to column chromatography (silica gel, dichloromethane: hexane = 1: 3) to obtain FDDMA (4.20 g, 75%) as a colorless liquid.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.65-1.81 (m, 4H), 1.93 (s, 3 H), 2.03-2.20 (m, 2 H), 4.17 (t, J = 6 Hz, 2 H), 5.56 (s, 1 H), 6.08 (s, 1 H).

Example 3: Poly (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate [poly Synthesis of (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate; PFDMA]

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (3,3, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylat; FDMA) (10.0 g), 2,2-azobisisobutyronitrile (2,2-azobisisobutyronitrile; AIBN) (0.3 g) was added, and air in the tube was replaced with an N ₂ stream. In N ₂ gas was added in a bubbled (bubbling) treated benzotrifluoride (benzotrifluoride) (10 cm ³⁾ under an N ₂ gas tube condition. After stirring for 12 hours at a temperature of 80 ℃, the polymer solution in the tube was precipitated in hexane (300 cm ³ ), filtered and recovered. Then, it was dried to obtain PFDMA (7.2 g), a high-fluorinated polymer. The obtained polymer had a number average molecular weight (Mn) of 10,600 g / mol and a weight average molecular weight (Mw) of 16,300 g / mol.

Example 4: Poly (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorodecyl methacrylate) [poly (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl methacrylate); Synthesis of PFUDMA]

PFUDMA was also prepared by a free radical polymerization method such as FDMA. The obtained polymer had a number average molecular weight (Mn) of 10,400 g / mol and a weight average molecular weight (Mw) of 16,400 g / mol.

Example 5: Poly (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacrylate [ Synthesis of poly (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-Heptadecafluorododecyl methacrylate); PFDDMA]

PFDDMA was also produced by a free radical polymerization method such as FDMA. The obtained polymer had a number average molecular weight (Mn) of 10,700 g / mol and a weight average molecular weight (Mw) of 15,900 g / mol.

Example 6: Electron beam lithography

PFDMA, PFUDMA, and PFDDMA solutions (5 wt%) dissolved in HFE-7500 on a silicon (Si) substrate were spin-coated at 3000 rpm for 60 seconds, respectively, and then heated at 70 ° C. for 1 minute to form a thin film (120 nm). Formed. After irradiating the electron beam with a dose of 1-11 C / m ² under an 80 keV acceleration voltage, the nanoparticles were processed for 30 seconds with PFDMA (FC-770), PFUDMA (FC-3283), and PFDDMA (FC-3283). A pattern was formed.

Experimental Example: High Fluorinated Polymer and Electron Beam Lithography Analysis

The present invention is a poly (methyl methacrylate) [poly (methyl methacrylate) capable of forming a positive pattern through the main chain cutting reaction of the polymer under electron beam conditions; PMMA], and tried to develop an electron beam resist material that can be used in the lithography process using a perfluorocarbon and a hydrofluoroether-based high fluorine-based solvent (FIG. 1A). That is, a highly fluorinated polymer electron beam resist material is synthesized to enable formation of a thin film and development of a pattern using a high fluorine-based solvent having very low chemical activity, and then tracking the operating mechanism under electron beam irradiation conditions. An attempt was made to develop a resist material that exhibits better sensitivity and resolution.

To this end, a commercially available, high-fluorinated solvent having excellent solubility as a monomer using FDMA, AIBN as a radical initiator, and benzotrifluoride as a polymerization solvent in a solution phase random copolymerization process to a PFDMA polymer Converted (Figure 1c). The molecular weight measurement of the PFDFMA polymer was confirmed to be Mn = 10,600 and PDI = 1.54 under the conditions of applying a high fluorine-based solvent AK-225G as a mobile phase and PMMA as a standard (FIG. 2).

Thereafter, an electron beam lithography experiment was conducted to confirm that a positive pattern was formed under electron beam irradiation. However, unlike the prediction, it was confirmed that the PFDMA polymer thin film formed a negative pattern after the development process using the high-fluorine-based solvent FC-770 (FIGS. 3A and 3D). This is because the PFDMA polymer is not a main chain cleavage reaction caused by free radicals induced during electron beam irradiation, but is also caused by another free radical reaction, a Norrish type II decomposition reaction, and a double bond between carbon and oxygen forming an ester bond in the polymer chain It breaks and a double radical is formed, and a six-membered transition state is formed, which is caused by the desorption of a highly fluorinated alkene chain accompanied by the movement of a hydrogen atom. Expected (Figure 4a). Hydrogen from a semi-perfluoroalkyl chain through a transition state of a hexagonal ring form after forming a double radical by an electron beam of high energy with a carbon-oxygen π-bond having a relatively small bond strength. And 1 H , 1 H , and 2 H -perfluorodecane chains are desorbed and carboxylic acid appears to be formed. When the carboxylic acid is formed, the polymer has a high polarity and solubility in a high fluorine-based solvent is lowered.

In order to confirm the decomposition mechanism of the methacrylate polymer by electron beam irradiation in more detail, _two monomers (FUDMA, FDDMA) having a similar structure to PFDMA but having one more methylene (-CH _2- ) unit (FUDMA, FDDMA) were selected. And attempted to observe its patterning results under electron beam irradiation. FUDMA and FDDMA were synthesized in a commercially unavailable relationship. Both new monomers were synthesized in high yield through a transesterification reaction between a semi-perfluoroalkyl alcohol and a methyl ester functional group in MMA. At this time, the transesterification reaction was carried out in toluene using dibutyltin dilaurate, a Lewis acid catalyst, instead of using a strong acid catalyst. Similar to the obtained PFDMA, AIBN was converted into a polymer through a random copolymerization process in solution phase using a radical initiator and benzotrifluoride as a polymerization solvent (FIG. 1C). The molecular weights of the prepared polymers were confirmed to be Mn = 10,400, PDI = 1.5 for PFUDMA, and Mn = 10,700, PDI = 1.49 for PFDDMA, confirming that the polymers were prepared with molecular weight and molecular weight distribution similar to PFDMA. There was (Fig. 2).

As a result of conducting an electron beam irradiation experiment after forming a thin film for the new polymers PFUDMA and PFDDMA, it was confirmed that a negative pattern was formed as in PFDMA (FIGS. 3B, 3C, 3E, and 3F). From the above results, the present inventors predicted that a chemical reaction similar to PFDMA would occur in PFUDMA and PFDDMA under electron beam irradiation conditions, and tried to verify it by applying a precise analysis technique.

First, by using Fourier transform infrared spectroscopy (FT-IR), the difference in the chemical structure of the polymer thin film before electron beam irradiation and the thin film finished until the development process after electron beam irradiation was confirmed. As a result, as shown in Figure 5, PFDMA, PFUDMA and PFDDMA, C = O (1738 cm ^-1 ) of the ester functional group before and after irradiation of all three polymers, CF (1149, 1203, 1232 cm ^-1 of the high fluorinated chain) ) Was confirmed to be measured with similar strength at the same location. When the Norrish Type II decomposition reaction occurs under the aforementioned electron beam irradiation and a change in solubility is caused, a carboxylic acid is generated in the polymer structure (FIG. 4A), and thus a new C = O binding peak should be observed, but this was not detected.

Therefore, a situation in which the probability of occurrence of the Norrish Type II decomposition reaction by electron beam irradiation was suspected was developed, and to confirm this, chemical composition analysis using X-ray photoelectron spectroscopy (XPS) was performed on PFDMA polymer thin films before and after electron beam irradiation. As a result, as shown in FIG. 6A, it was confirmed that the binding energies of C-C (285.78), C-O (288.08), and C-F (291.78) bonds were similar before and after electron beam irradiation. In addition, as shown in Figure 6b, it was confirmed that both the C = O (291.88) and C-O-C (288.08) bonds of the ester functional group exhibit very similar binding energies. Therefore, from the above results, it was unsuccessful to secure evidence that chemical composition changes occurred by Norrish type II decomposition reaction before and after electron beam irradiation.

That is, it was not confirmed through experiments with FT-IR and XPS that PFDMA and similar polymers would form a negative pattern through the decomposition reaction of free radicals caused by electron beams. Accordingly, as another cause of the solubility of the PFDMA polymer thin film being reduced through electron beam irradiation, the high-fluorinated alkyl chain itself is decomposed by high-energy electrons to reduce the fluorine content (defluorination), and by the generation of accompanying free radicals A reaction in which crosslinking between high fluorinated alkyl chains occurred was expected (FIG. 4B). The likelihood of the reaction mechanism can be inferred from the formation of a positive pattern by reducing the solubility of CYTOPTM (AsahiGlassCo.) Thin films, which are commercially available fluorine polymers, by electron beam irradiation.

In order to directly observe the decomposition reaction of the highly fluorinated alkyl chain by electron beam irradiation, decomposition of the high fluorinated polymer was induced by applying an electron ionization (EI) method, one of gas chromatography (GC) techniques. Under electron ionization conditions, it is possible to irradiate an electron beam to a polymer sample. At this time, when a decomposition reaction occurs, a decomposition product is detected through a mass spectrometer (MS), so that the decomposition reaction of the high-fluorinated polymer can be confirmed.

For mutual comparison, analysis was conducted on three types of polymers: PFDMA, PFUDMA and PFDDMA. As a result, as shown in FIG. 7, peaks of 112, 86, and 69 m / z were commonly observed in all three polymers by electron ionization conditions. As can be seen in Fig. 4b 112 m / z peaks of de-fluorination degradation products [C ₃ F _4] ^- to, 86 m / z peaks are [C ₄ F _2] ^- to, 69 m / z is [CF _3] ^- it had to be matched to the molecular weight. In addition to the defluorination decomposition reaction, free radicals are generated in the high-fluorinated alkyl chain, and cross-linking occurs between them, confirming that the solubility of the high-fluorinated alkyl methacrylate including PFDMA is significantly reduced.

In addition, in addition to the mechanism for forming a negative pattern by electron beam irradiation, a lithography experiment was performed using high fluorinated methacrylate, and it was confirmed that a negative tone pattern was formed.

The specific parts of the present invention have been described in detail above, and it is obvious that for those skilled in the art, these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereto. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

The scope of the present invention is indicated by the following claims, and all modifications or variations derived from the meaning and scope of the claims and their equivalent concepts should be interpreted to be included in the scope of the present invention.

Claims (9)

It includes a high fluorinated polymer represented by the formula (1), the polymer is a high fluorine-based solvent, a negative pattern process is in progress,
The high fluorinated polymer is poly (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate) (PFDMA), poly (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorodecyl methacrylate) (PFUDMA) and poly (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacrylate) Highly fluorinated electron beam resist material selected from the group consisting of (PFDDMA):
[Formula 1]

In Formula 1, x is an integer from 0 to 10, n is an integer from 10 to 1000. delete The method of claim 1, wherein the high fluorinated polymer is 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadeca fluoride. Sil methacrylate (FUDMA), 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacryl Rate (FDDMA) and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (FDMA) High fluorinated electron beam resist material comprising at least one monomer selected from the group consisting of. The highly fluorinated electron beam resist material according to claim 1, wherein the highly fluorinated polymer is dissolved in a high fluorine-based solvent. The method of claim 1, wherein the high fluorine-based solvent is 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoro Methyl-hexane (3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane; HFE-7500), perfluorotripropyl Highly fluorinated electron beam resist material selected from the group consisting of amines (perfluorotripropylamine; FC-3283) and perfluoro-N-alkyl morpholines (FC-770). The highly fluorinated electron beam resist material according to claim 1, wherein the highly fluorinated polymer has a number average molecular weight (Mn) of 8,000 to 13,000. delete A first step of dissolving the highly fluorinated electron beam resist material according to any one of claims 1, 3 to 6 in a high fluorine-based solvent and applying it to the substrate;
A second step of heating the substrate to form a resist film;
A third step of irradiating the resist film with electron beams: and
And a fourth step of developing the resist film with a developer and forming a pattern on the substrate. The method of claim 8, wherein the heat treatment in the second process is performed at 60 to 80 ° C. for 30 seconds to 2 minutes.

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