BLOCK COPOLYMER

Abstract

The present application relates to a block copolymer and its use. The present application can provides a block copolymer that has an excellent self assembling property or phase separation property and therefore can be used in various applications and its use.

Claims

1. (canceled)

2. A block copolymer comprising a first block and a second block having a different chemical structure from the first block, wherein the first block exhibits a melting transition peak or isotropic transition peak in a range from −80° C. to 200° C. in differential scanning calorimetry (DSC) analysis.

3-8. (canceled)

9. The block copolymer of claim 2, wherein the block copolymer exhibits both of the melting transition peak and the isotropic transition peak and wherein a difference (Ti—Tm) between a temperature (Ti) at which the isotropic transition peak is shown and a temperature (Tm) at which the melting transition peak is shown is from 5° C. to 70° C.

10. The block copolymer of claim 2, wherein the block copolymer exhibits both of the melting transition peak and the isotropic transition peak and wherein a ratio (M/I) of an area (M) of the melting transition peak relative to an area (I) of the isotropic transition peak is from 0.1 to 500.

11. The block copolymer of claim 2, wherein the first block exhibits the melting transition peak within a range from −10° C. to 55° C.

12. The block copolymer of claim 2, wherein the first block comprises a side chain satisfying the Equation 1:
[Equation 1]
10° C.≦Tm−12.25° C.×n+149.5° C.≦10° C. wherein, Tm is the temperature at which the melting transition peak and n is the number of chain-forming atoms of the side chain.

13. The block copolymer of claim 2, of which the X in the Formula A below is 1.25 or more:
[Formula A]
X=1+(D×M)/(K×L) wherein the D is a ratio (D2/D1) of a density (D2) of the second block relative to a density (D1) of the first block, the M is a ratio (M1/M2) of a molar mass (M1) of the first block relative to a molar mass (M2) of the second block, the K is a ratio (A2/A1) of an area (A2) of a peak exhibited due to the second block in .sup.1H-NMR relative to an area (A1) of a peak exhibited due to the first block in .sup.1H-NMR and the L is a ratio (H1/H2) of a molar number (H1) of hydrogen atom in 1 mole of a repeating unit of the first block relative to a molar number (H2) of hydrogen atom in 1 mole of a repeating unit of the second block.

14. The block copolymer of claim 2, wherein the first or second block comprises an aromatic structure.

15. The block copolymer of claim 2, wherein the first block and the second block comprise an aromatic structure.

16. The block copolymer of claim 2, wherein the first block comprises an aromatic structure that does not has halogen atom and the second block comprises an aromatic structure having halogen atom.

17. The block copolymer of claim 2, wherein the first or second block comprises a side chain of which the number of chain-forming atoms is 8 or more.

18. The block copolymer of claim 2, wherein the first or second block comprises halogen atom.

19. The block copolymer of claim 2, wherein the first block comprises a side chain of which the number of chain-forming atoms is 8 or more and the second block comprises halogen atom.

20. The block copolymer of claim 2, wherein the first or second block comprises an aromatic structure to which a side chain of which the number of chain-forming atoms is 8 or more is linked.

21. The block copolymer of claim 20, wherein the side chain is linked to the aromatic structure via oxygen atom or nitrogen atom.

22. The block copolymer of claim 2, wherein the first or second block comprises an aromatic structure with which halogen atom is substituted.

23. The block copolymer of claim 2, wherein the first block comprises an aromatic structure to which a side chain of which the number of chain-forming atoms is 8 or more is linked and the second block comprises an aromatic structure with which halogen atom is substituted.

24. The block copolymer of claim 2, wherein the first block comprises a side chain of which the number of chain-forming atoms is 8 or more.

25. The block copolymer of claim 24, wherein the first block comprises a cyclic structure and the side chain is linked to the cyclic structure.

26. The block copolymer of claim 25, wherein the cyclic structure does not comprises halogen atom.

27. The block copolymer of claim 24, wherein the second block comprises at least 3 halogen atoms.

28. The block copolymer of claim 27, wherein the second block comprises a cyclic structure and the halogen atoms are substituted with the cyclic structure.

29. The block copolymer of claim 2, wherein the first block comprises a unit represented by Formula 1 below: ##STR00010## wherein, R is a hydrogen or an alkyl group having 1 to 4 carbon atom(s), X is a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X.sub.1— or —X.sub.1—C(═O)—, where the X.sub.1 is an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group, and Y is a monovalent substituent including a ring structure to which the side chain having 8 or more chain-forming atoms is linked.

30. The block copolymer of claim 2, wherein the second block comprises a unit represented by Formula 3 below: ##STR00011## wherein 3, the X.sub.2 is a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X.sub.1— or —X.sub.1—C(═O)—, where the X.sub.1 is a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group, and the W is an aryl group including at least one halogen atom.

31. A polymer layer including the block copolymer of claim 2, wherein the block copolymer is self assembled.

32. A process for preparing a polymer layer, including forming a polymer layer including the block copolymer of claim 2 on a substrate, wherein the block copolymer is self assembled.

33. A pattern forming method including selectively eliminating the first or second block from a polymer layer including the block copolymer of claim 2 on a substrate, wherein the block copolymer is self assembled.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0138] FIGS. 1 and 2 are drawings of GISAXS diffraction patterns.

[0139] FIGS. 3 to 10 show SEM images of polymer layers.

[0140] FIGS. 11 to 15 are drawings showing results of GIWAXS.

[0141] FIG. 16 show an illustrate process during which the K value in the Formula A is calculated.

[0142] FIGS. 17 to 19 are drawings of GISAXS diffraction patterns.SAXS diffraction patterns.

EFFECT

[0143] The present application can provides a block copolymer that has an excellent self assembling property or phase separation property and therefore can be used in various applications and its use.

DETAILED DESCRIPTION OF EMBODIMENTS

[0144] Hereinafter, the present application will be described in further detail with reference to examples according to the present application, but the scope of the present application is not limited to the following examples.

[0145] 1. NMR Analysis

[0146] NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer having a triple resonance 5 mm probe. A subject for analysis was diluted with a solvent (CDCl.sub.3) for measuring NMR at a concentration of about 10 mg/ml, and chemical shift was expressed in ppm.

[0147] <Abbreviations>

[0148] br=broad signal, s=singlet, d=doublet, dd=doublet of doublets, t=triplet, dt=doublet of triblets, q=quartet, p=quintet, m=multiplet.

[0149] 2. Gel Permeation Chromatography (GPC)

[0150] A number average molecular weight (Mn) and a distribution of molecular weight were measured by GPC. A subject for analysis such as a block copolymer or macro initiator of Example or Comparative Example was put into 5 ml vial, and diluted with tetrahydrofuran (THF) to have a concentration of about 1 mg/mL. Afterward, a standard sample for Calibration and a sample for analysis were measured after passing through a syringe filter (pore size: 0.45 μm). As an analysis program, ChemStation produced by Agilent technologies was used, and an elution time for the sample was compared with a calibration curve, thereby obtaining a weight average molecular weight (Mw) and a number average molecular weight (Mn), and a ratio (Mw/Mn) was used to calculate a polydispersity index (PDI). Conditions for measuring GPC are as follows.

[0151] <Conditions for measuring GPC>

[0152] Device: 1200 series produced by Agilent technologies

[0153] Column: Two PLgel mixed B produced by Polymer laboratories

[0154] Solvent: THF

[0155] Column temperature: 35° C.

[0156] Sample concentration: 1 mg/mL, 200 L injection

[0157] Standard sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0158] 3. GISAXS (Grazing Incidence Small Angle X Ray Scattering)

[0159] The GISAXS analysis was performed in a 3C beam line of the Pohang Light Source. A coating solution was prepared by dissolving a block copolymer to be evaluated in fluorobenzene so as for a solid content to be 0.7 weight %, the coating solution was spin coated on a substrate so as to having a thickness of about 5 nm. The coating area was controlled to be about 2.25 cm.sup.2 (coated area: width=1.5 cm, length=1.5 cm). The coated layer was dried for about 1 hour at the room temperature and then subjected to the thermal annealing at about 160° C. for about 1 hour so as for the phase separation structure to be realized. Therefore, the layer in which the phase separation structure was realized was formed. The formed layer was irradiated with X ray so as for an incident angle to be from about 0.12 degrees to 0.23 degrees, which corresponded to an angle between a critical angle of the layer and a critical angle of the substrate, and then the X ray diffraction pattern scattered from the layer was obtained by using a 2D marCCD. At this time, a distance from the layer to the detector was selected so as for the self assembled pattern in the layer to be effectively observed within a range from about 2 m to 3 m. As the substrate, a substrate (a silicone substrate that was treated with piranha solution and that has a wetting angle of about 5 degrees with respect to purified water at the room temperature) having the hydrophilic surface or a substrate (a silicone substrate that was treated with HMDS (hexamethyldisilazane) and that has a wetting angle of about 60 degrees with respect to purified water at the room temperature) having the hydrophobic surface was used.

[0160] 4. Method for XRD Analysis

[0161] XRD analysis was performed by measuring a scattering intensity according to a scattering vector (q) by irradiating a sample with an X ray using a Pohang light source 4C beam line. As a sample, a powder-type block copolymer was obtained by purifying a synthesized block copolymer without specific pretreatment and drying the block copolymer in a vacuum oven for about one day, and put into a cell for XRD measurement. In XRD pattern analysis, an X ray having a vertical size of 0.023 mm and a horizontal size of 0.3 mm was used, and a 2D marCCD was used as a detector. A 2D diffraction pattern obtained by scattering was obtained an image. Information such as a scattering vector and a FWHM were obtained by analyzing the obtained diffraction pattern by numerical analysis method using the least square method. For the analysis, an origin program was applied, a part showing the least intensity in an XRD diffraction pattern was set as a baseline to make the intensity 0, a profile of the XRD pattern peak was fitted by Gaussian fitting, and the scattering vector and the FWHM was obtained from the fitted result. In the Gauss fitting, the R square was set to at least 0.96 or more.

[0162] 5. Measurement of Surface Energy

[0163] Surface energy was measured using a drop-shape analyzer (DSA100, KRUSS). A coating solution was prepared by diluting a material for detection (polymer) with fluorobenzene at a solid content concentration of about 2 wt %, and the prepared coating solution was applied on a silicon wafer by spin coating to have a thickness of about 50 nm and a coating area of 4 cm.sup.2 (width: 2 cm, length: 2 cm). The coating layer was dried at room temperature for about 1 hour, and then thermal-annealed at about 160° C. for about 1 hour. Deionized water having a known surface tension was dropped on the film undergoing the thermal annealing, and a mean value of five contact angles obtained by repeating measurement of contact angles five times. Likewise, diiodomethane having a known surface tension was dropped on the film undergoing the thermal annealing, and a mean value of five contact angles obtained by repeating measurement of contact angles five times. Surface energy was obtained by substituting a Strom value with respect to the surface tension of the solvent through the Owens-Wendt-Rabel-Kaelble method using the obtained mean values of the contact angles for the deionized water and diiodomethane. The value of surface energy for each block of the block copolymer was obtained by the above-described method applied to a homopolymer prepared only using a monomer for forming the block.

[0164] 6. GIWAXS (Grazing Incidence Wide Angle X Ray Scattering)

[0165] The GIWAXS analysis was performed in a 3C beam line of the Pohang Light Source. A coating solution was prepared by dissolving a copolymer to be evaluated in toluene so as for a solid content to be 1 weight %, the coating solution was spin coated on a substrate so as to having a thickness of about 30 nm. The coating area was controlled to be about 2.25 cm.sup.2 (coated area: width=1.5 cm, length=1.5 cm). The coated layer was dried for about 1 hour at the room temperature and then subjected to the thermal annealing at about 160° C. for about 1 hour so as to form a layer. The formed layer was irradiated with X ray so as for an incident angle to be from about 0.12 degrees to 0.23 degrees, which corresponded to an angle between a critical angle of the layer and a critical angle of the substrate, and then the X ray diffraction pattern scattered from the layer was obtained by using a 2D marCCD. At this time, a distance from the layer to the detector was selected so as for the crystal or liquid crystal structure in the layer to be effectively observed within a range from about 0.1 m to 0.5 m. As the substrate, a silicone substrate that was treated with piranha solution and that has a wetting angle of about 5 degrees with respect to purified water at the room temperature was used.

[0166] Scattering intensity at an azimuthal angle from −90 degrees to 90 degrees (an azimuthal angle when an upper direction (out of plane diffraction pattern) is set to be 0 degree) in diffraction pattern from 12 nm.sup.−1 to 16 nm.sup.−1 in the GIWAXS was plotted and a full width at half maximum (FWHM) was obtained from the graph via the Gauss fitting. In a case where only a half of a peak during the Gauss fitting was observed, a value twice as much as the obtained FWHM was designated as the FWHM.

[0167] 7. DSC Analysis

[0168] The DSC analysis was performed by using PerkinElmer DSC800 device. It was performed by obtaining an endothermic curve by heating the sample to be analyzed from 25° C. to 200° C. at a heating speed of 10° C. per a minute, then cooling it from 200° C. to −80° C. at a cooling speed of −10° C. per a minute and then heating it from −80° C. to 200° C. at a heating speed of 10° C. per a minute under nitrogen atmosphere by using the device. By analyzing the obtained endothermic curve, a temperature (the melting transition temperature, Tm) at which the melting transition peak was observed was obtained and an area of the peak was calculated. The temperature corresponding to a summit of the peak was selected. A mass per unit area of each peak was obtained by dividing an area of each peak by a mass of the sample and the above calculation can be performed by a program provided in the DSC device.

[0169] 8 Measurement of the X in the Formula A

[0170] The variables D, M, K and L applied in the formula A can be obtained as below.

[0171] The D value can be obtained by putting a sample to be measured (a homopolymer prepared only by monomers forming the first block or a homopolymer prepared only by monomers forming the second block) in solvent (ethanol) of which mass and density in air are known and then density of each block can be obtained via its mass and calculating their ratio.

[0172] Further, the M value can be obtained from a ratio of molar masses of monomers forming each block of the block copolymer. For example, in a case of each block copolymer in Examples, since the molar mass of the monomer forming the first block in Preparation Example 1 as described below is 346.5 g/mol and the molar mass of the pentafluorostyrene forming the second block is 194.1 g/mol and therefrom the M can be calculated as about 1.79 from their ratio.

[0173] Further, the L can be obtained from molar number of hydrogen atom of monomers forming each block of the block copolymer. For example, in a case of each block copolymer in Examples, since the molar number of the hydrogen atom of the monomer forming the first block in Preparation Example 1 as described below is 34 and the molar number of the hydrogen atom in the pentafluorostyrene forming the second block is 3 and therefrom the L can be calculated as about 11.3 from their ratio.

[0174] Finally, the K can be calculated from an area of spectrum obtained from the NMR method as described above. In a case where a peak due to one block of the block copolymer is not overlapped with a peak due to the other block of the block copolymer, an area of each peak due to each block can be simply obtained and the K can be obtained from their ratio.

[0175] However, in a case where a peak due to one block of the block copolymer is overlapped with a peak due to the other block of the block copolymer, the K should be calculated with considering the above. For example, FIG. 14 is an illustrative NMR spectrum of the block copolymer that was applied in the below Example and Comparative Example and that includes a unit derived from the compound of chemical formula A in Preparation Example 1 and a unit derived from pentafluorostyrene. The portions represented by the “e” and “d” are peaks derived from the second block, i.e., the unit derived from the pentafluorostyrene and other portions represented by the “a,” “b,” “c,” “f,” “g,” “h,” “i” and “j” are peaks derived from the unit derived from the compound of chemical formula A in Preparation Example 1. As can be confirmed from the drawing, the peaks represented by the “e” and “g” are overlapped with the peaks represented by the “d” and “f,” and, in this case, the K should be obtained considering the overlapped portions.

[0176] The method for obtaining the K with considering the overlapped portions is known, and, for example, it can be obtained by using a NMR analysis program such as MestReC.

Preparation Example 1. Synthesis of Monomer (A)

[0177] A compound of Formula A (DPM-C12) was synthesized by the following method. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were put into a 250 mL flask, dissolved in 100 mL acetonitrile, treated with an excessive amount of potassium carbonate to allow a reaction at 75° C. for about 48 hours under a nitrogen condition. After the reaction, remaining potassium carbonate was filtered to remove, and the acetonitrile used in the reaction was also removed. Here, a mixed solvent of dichloromethane (DCM) and water was added to work up, and a separated organic layer was dehydrated with MgSO.sub.4. Therefore, a white solid product (4-dodecyloxyphenol; 9.8 g, 35.2 mmol) was obtained with an yield of about 37% through column chromatography using DCM.

[0178] <NMR Analysis Result>

[0179] .sup.1H-NMR (CDCl.sub.3): δ 6.77 (dd, 4H); 54.45 (s, 1H); δ 3.89 (t, 2H); δ 1.75 (p, 2H); δ 1.43 (p, 2H); δ1.33-1.26 (m, 16H); δ 0.88 (t, 3H).

[0180] Synthesized 4-dodecyloxyphenol (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), dicyclohexylcarbodiimide (DCC; 10.8 g, 52.3 mmol) and p-dimethylaminopyridine (DMAP; 1.7 g, 13.9 mmol) were put into a flask, and treated with 120 mL of methylenechloride to allow a reaction at room temperature for 24 hours under nitrogen. After the reaction was completed, a salt produced in the reaction (urea salt) was removed using a filter, and remaining methylenechloride was also removed. Debris was removed through column chromatography using hexane and dichloromethane (DCM) as moving phases, and then a product thereby was recrystallized in a mixed solvent of methanol and water (1:1 mixture), thereby obtaining a white solid product (7.7 g, 22.2 mmol) with an yield of 63%.

[0181] <NMR Analysis Result>

[0182] .sup.1H-NMR (CDCl.sub.3): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t, 2H); δ 2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.43 (p, 2H); 1.34-1.27 (m, 16H); δ 0.88 (t, 3H).

##STR00005##

[0183] In Formula A, R is a linear alkyl group having 12 carbon atoms.

Preparation Example 2. Synthesis of Monomer (G)

[0184] A compound of Formula G was synthesized by the method according to Preparation Example 1, except that 1-bromobutane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0185] <NMR Analysis Result>

[0186] .sup.1H-NMR (CDCl.sub.3): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.73 (dt, 1H); δ 3.95 (t, 2H); δ 2.06 (dd, 3H); δ 1.76 (p, 2H); δ 1.49 (p, 2H); δ 0.98 (t, 3H).

##STR00006##

[0187] In Formula B, R is a linear alkyl group having 8 carbon atoms.

Preparation Example 3. Synthesis of Monomer (C)

[0188] A compound of Formula C was synthesized by the method according to Preparation Example 1, except that 1-bromodecane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0189] <NMR Analysis Result>

[0190] .sup.1H-NMR (CDCl.sub.3): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.72 (dt, 1H); δ 3.94 (t, 2H); δ 2.06 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.34-1.28 (m, 12H); δ 0.89 (t, 3H.)

##STR00007##

[0191] In Formula C, R is a linear alkyl group having 10 carbon atoms.

Preparation Example 4. Synthesis of Monomer (D)

[0192] A compound of Formula D was synthesized by the method according to Preparation Example 1, except that 1-bromotetradecane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0193] <NMR Analysis Result>

[0194] .sup.1H-NMR (CDCl.sub.3): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t, 2H); δ 2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.27 (m, 20H); δ 0.88 (t, 3H.)

##STR00008##

[0195] In Formula D, R is a linear alkyl group having 14 carbon atoms.

Preparation Example 5. Synthesis of Monomer (E)

[0196] A compound of Formula E was synthesized by the method according to Preparation Example 1, except that 1-bromohexadetane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0197] <NMR Analysis Result>

[0198] .sup.1H-NMR (CDCl.sub.3): δ 7.01 (dd, 2H); δ 6.88 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t, 2H); δ 2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.26 (m, 24H); δ 0.89 (t, 3H)

##STR00009##

[0199] In Formula E, R is a linear alkyl group having 16 carbon atoms.

[0200] Results of GIWAXS and DSC Analysis

[0201] The result of the GIWAXS and DSC analysis performed with respect to 5 homopolymers were prepared by using monomers in Preparation Examples 1 to 5 is stated in Table 1 below. The homopolymers were prepared by the same method as that for preparing the macroinitiator described in the Example and Comparative Example below. Further, the result of the GIWAXS analysis with respect to each homopolymer is shown in FIGS. 11 to 15. FIGS. 11 to 15 show the result of the GIWAXS of homopolymers prepared by monomers in Preparation Examples 1 to 5 respectively.

[0202] The R square of the Gauss fitting in FIG. 11 was about 0.264, the R square of the Gauss fitting in FIG. 14 was about 0.676 and the R square of the Gauss fitting in FIG. 15 was about 0.932.

TABLE-US-00001 TABLE 1 Preparation Example 1 2 3 4 5 Tg — 33 — — — Tm −3 — — 23 46 Ti 15 — 44 60 60 M/I 3.67 — — 5.75 71.86 FWHM1 48 — — 13 23 FWHM2 58 — — 12 26 Chain-forming 12  4 10 14 16 atoms Tg: glass transition temperature(° C.) Tm: melting transition temperature(° C.) Ti: isotropic transition temperature(° C.) M/I: a ratio of an area (M) of the melting transition peak relative to an area (I) of the isotropic transition peak FWHM1: a full width at half maximum (unit: degrees) at an azimuthal angle from −90 to −70 degrees FWHM2: a full width at half maximum (unit: degrees) at an azimuthal angle from 70 to 90 degrees Chain-forming atoms: a number of the chain-forming atoms in the first block (=the number of carbon atoms in the “R” of the chemical formula in each Preparation Example)

Example 1

[0203] 1.785 g of the monomer (A) of Preparation Example 1, 38 mg of a reversible addition-fragmentation chain transfer (RAFT) reagent, cyanoisopropyldithiobenzoate, 14 mg of a radical initiator, azobisisobutyronitrile (AIBN), and 4.765 ml of benzene were put into a 10 mL Schlenk flask, and stirred at room temperature for 30 minutes under a nitrogen atmosphere to allow an RAFT polymerization reaction at 70° C. for 4 hours. After the polymerization, a reaction solution was precipitated in 250 ml of methanol as an extraction solvent, and dried through decreased pressure filtration, thereby preparing a pink macroinitiator. The yield of the macroinitiator was about 83.1 weight %, and the number average molecular weight (Mn) and distribution of molecular weight (Mw/Mn) of the macroinitiator were 11,400 and 1.15, respectively. 0.3086 g of the macroinitiator, 1.839 g of a pentafluorostyrene monomer and 0.701 ml of benzene were put into a 10 mL Schlenk flask, and stirred at room temperature for 30 minutes under a nitrogen atmosphere to allow an RAFT polymerization reaction at 115° C. for 4 hours. After the polymerization, a reaction solution was precipitated in 250 ml of methanol as an extraction solvent, and dried through decreased pressure filtration, thereby preparing a light pink block copolymer. The yield of the block copolymer was about 27.1 weight %, and the number average molecular weight (Mn) and distribution of molecular weight (Mw/Mn) of the block copolymer were 18,900 and 1.19, respectively. The block copolymer includes a first block derived from the monomer (A) of Preparation Example 1 and a second block derived from the pentafluorostyrene monomer. The result of the GISAXS measuring performed with respect to a surface, as a hydrophilic surface, of which a wetting angle at room temperature was 5 degrees by the method as described above is shown in FIG. 1 and the result of the GISAXS measuring performed with respect to a surface, as a hydrophobic surface, of which a wetting angle at room temperature was 60 degrees by the method as described above is shown in FIG. 2. From FIGS. 1 and 2, it can be confirmed that the in plane phase diffraction patterns can be observed in any case.

Example 2

[0204] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Example 1, except that the monomer (C) of Preparation Example 3, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (C) of Preparation Example 3 and a second block derived from the pentafluorostyrene monomer. The GISAXS analysis was performed by the same method as in Example 1 and the in plane phase diffraction patterns were confirmed both on the hydrophilic and the hydrophobic surface.

Example 3

[0205] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Example 1, except that the monomer (D) of Preparation Example 4, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (D) of Preparation Example 4 and a second block derived from the pentafluorostyrene monomer. The GISAXS analysis was performed by the same method as in Example 1 and the in plane phase diffraction patterns were confirmed both on the hydrophilic and the hydrophobic surface.

Example 4

[0206] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Example 1, except that the monomer (E) of Preparation Example 5, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (E) of Preparation Example 4 and a second block derived from the pentafluorostyrene monomer. The GISAXS analysis was performed by the same method as in Example 1 and the in plane phase diffraction patterns were confirmed both on the hydrophilic and the hydrophobic surface.

Comparative Example 1

[0207] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Example 1, except that the monomer (G) of Preparation Example 2, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (G) of Preparation Example 2 and a second block derived from the pentafluorostyrene monomer. The GISAXS analysis was performed by the same method as in Example 1; however the in plane phase diffraction patterns were not confirmed on the hydrophilic and the hydrophobic surface.

Comparative Example 2

[0208] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Example 1, except that the 4-methoxyphenyl methacrylate, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the 4-methoxyphenyl methacrylate and a second block derived from the pentafluorostyrene monomer. The GISAXS analysis was performed by the same method as in Example 1; however the in plane phase diffraction patterns were not confirmed on the hydrophilic and the hydrophobic surface.

Comparative Example 3

[0209] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Example 1, except that the dodecyl methacrylate, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the dodecyl methacrylate and a second block derived from the pentafluorostyrene monomer. The GISAXS analysis was performed by the same method as in Example 1; however the in plane phase diffraction patterns were not confirmed on the hydrophilic and the hydrophobic surface.

[0210] GPC results for the macroinitiators and the block copolymers prepared in the above Preparation Examples are summarized and listed in Table 2.

TABLE-US-00002 TABLE 2 Example Comparative Example 1 2 3 4 1 2 3 MI Mn 11400 8500 8700 9400 9000 7800 8000 PDI 1.15 1.14 1.18 1.15 1.17 1.13 1.16 BCP Mn 18900 17100 17400 18900 18800 18700 16700 PDI 1.19 1.17 1.18 1.17 1.20 1.16 1.20 MI: macroinitiator BCP: block copolymer Mn: number average molecular weight PDI: polydispersity index

[0211] The result of evaluating properties of each block copolymer is stated in Table 3 below.

TABLE-US-00003 TABLE 3 Comparative Example Example 1 2 3 4 1 2 3 Ref The SE 30.83 27.38 26.924 27.79 37.37 48.95 19.1 38.3 first De 1 1.02 0.99 1.00 1.11 1.19 0.93 1.05 Block The SE 24.4 24.4 24.4 24.4 24.4 24.4 24.4 41.8 second De 1.57 1.57 1.57 1.57 1.57 1.57 1.57 1.18 block SE 6.43 2.98 2.524 3.39 12.98 24.55 5.3 3.5 difference De 0.57 0.55 0.58 0.57 0.46 0.38 0.64 0.13 difference Chain 12 10 14 16 4 1 12 — forming atom n/D 3.75 3.45 4.24 4.44 2.82 1.98 — — SE: the surface energy (unit: mN/m) De: density (g/cm.sup.3) SE difference: an absolute value of a difference between the surface energies of the first and second block De difference: an absolute value of a difference between the densities of the first and second block n/D: the value calculated by the Equation 2 (nq/(2 × π)) (n is the number of chain-forming atoms of the side chain, q is the scattering vector (q) showing the peak having the largest peak area within scattering vector range from 0.5 nm.sup.−1 to 10 nm.sup.−1. Ref.: polystyrene-polymethylmethacrylate block copolymer (the first block: polystyrene block, the second block: polymethylmethacrylate block)

[0212] Results for analyzing XRD patterns for the macroinitiator used for preparing each block copolymer by the above-described methods are summarized and listed in Table 4. In a case of the Comparative Example 3, no peak was observed within a range of scattering vectors from 0.5 nm.sup.−1 to 10 nm.sup.−1.

TABLE-US-00004 TABLE 2 Comparative Example Example 1 2 2 3 1 2 3 q peak value 1.96 2.15 1.83 1.72 4.42 3.18 — (unit: nm.sup.−1) FWHM (unit: nm.sup.−1) 0.57 0.63 0.45 0.53 0.97 1.06 —

Experiment Example 1. Evaluation of Self Assembling Properties

[0213] A coating solution prepared by diluting the block copolymer of Examples or Comparative Examples in fluorobenzene so as to have 0.7 weight % of solid content was spin coated on a silicon wafer (coating area: width×length=1.5 cm×1.5 cm) so as to have a thickness of about 5 nm, the coated coating solution was dried under a room temperature for about an hour and then was subjected to a thermal annealing at 160° C. for about an hour so as to form a self assembled layer. The SEM (Scanning Electron Microscope) analysis was performed to each of the formed layers. FIGS. 3 to 6 are the SEM images of the layers formed by the block copolymers of Examples 1 to 3. As confirmed from the figures, in a case of the block copolymer, a polymer layer that was self assembled in a line shape was effectively formed. However, in a case of Comparative Example, an appropriate phase separation was not realized. For example, FIG. 7 is a SEM result of Comparative Example 3 and it can be confirmed that an effective phase separation was not realized.

Experiment Example 2. Evaluation of Self Assembling Properties

[0214] By using the block copolymer in Example 1, a polymer layer was formed by the same method as in the Experiment Example 1. The polymer layer was formed on a silicon substrate which was treated with piranha solution and of which a wetting angle at room temperature was 5 degrees; on a silicon oxide substrate of which a wetting angle at room temperature was 45 degrees or on a silicon substrate which was treated with HMDS (hexamethyldisilazane) and of which a wetting angle at room temperature was 60 degrees. FIGS. 8 to 10 are SEM images of polymer layers formed on the surfaces of which the wetting angles were 5 degrees, 45 degrees and 60 degrees respectively. From them, it can be confirmed that the block copolymer can form effective phase separation structure regardless of surface property of the substrate.

Experiment Example 3

[0215] Block copolymers (BCP1 to BCP4) were prepared by the same method as in Example 1, except that the X value in Formula A could be changed as below by controlling the molar ratio of the macroinitiator and monomer.

TABLE-US-00005 TABLE 5 The X in formula A D M K L BCP1 2.18 1.57 1.79 0.21 11.3 BCP2 1.85 1.57 1.79 0.29 11.3 BCP3 1.75 1.57 1.79 0.33 11.3 BCP4 1.26 1.57 1.79 0.95 11.3 D: a ratio (D2/D1) of a density (D2) of the second block relative to a density (Dl) of the first block M: a ratio (M1/M2) of a molar mass (346.5 g/mol, Ml) of the monomer of the chemical formula A of Preparation Example 1 forming the first block relative to a molar mass (194.1 g/mol, M2) of the pentafluorostyrene forming the second block K: a ratio (A2/A1) of an area (A2) of a peak exhibited due to the second block in .sup.1H-NMR relative to an area (A1) of a peak exhibited due to the first block in .sup.1H-NMR L: a ratio (H1/H2) of a molar number (34, H1) of hydrogen atom in the monomer of the chemical formula A of Preparation Example 1 forming the first block relative to a molar number (3, H2) of hydrogen atom in the pentafluorostyrene forming the second block

[0216] A coating solution prepared by diluting each of the above block copolymers in fluorobenzene so as to have 0.7 weight % of solid content was spin coated on a silicon wafer (coating area: width×length=1.5 cm×1.5 cm) so as to have a thickness of about 5 nm, the coated coating solution was dried under a room temperature for about an hour and then was subjected to a thermal annealing at 160° C. for about an hour so as to form a polymer layer. The GISAXS analysis was performed to the formed layer and the results are shown in drawings. FIGS. 18 to 20 are the results of BCP1, BCP2 and BCP3. From the drawings, it can be confirmed that the block copolymer can exhibit the in plane diffraction pattern on the GISAXS however, in a case of BCP4, a clear result cannot be confirmed.