BLOCK COPOLYMER

Abstract

The present application relates to a block copolymer and uses thereof. The present application can provide a block copolymer—which exhibits an excellent self-assembling property and thus can be used effectively in a variety of applications—and uses thereof.

Claims

1-8. (canceled)

9. A block copolymer comprising a first block and a second block, wherein the first block satisfies one or more of Conditions 1 to 4 below, and the first block and the second block have different chemical structures from each other and an absolute value of a difference in surface energies of 10 mN/m or less, wherein, Condition 1: A peak whose full width at half maximum ranges from 5 degrees to 70 degrees is observed in azimuthal angle ranges, in a diffraction pattern of a grazing-incidence wide-angle X-ray scattering (GIWAXS) spectrum, of −90 degrees to −70 degrees and 70 degrees to 90 degrees (the azimuthal angle is determined by setting an angle of out-of-plane diffraction pattern of the GIWAXS spectrum as 0 degrees), wherein a scattering vector ranges from 12 nm.sup.−1 to 16 nm.sup.−1: Condition 2: A melting transition peak or an isotropic transition peak is produced in a range of −80° C. to 200° C. during DSC analysis: Condition 3: A peak whose full width at half maximum ranges from 0.2 to 0.9 nm.sup.−1 is observed when a scattering vector (q) ranges from 0.5 nm.sup.−1 to 10 nm during X-ray diffraction (XRD) analysis: Condition 4: The first block includes a side chain, wherein a number (n) of chain-forming atoms in the side chain and a scattering vector (q) during XRD analysis satisfy Mathematical Expression 1 below:
3 nm.sup.−1 to 5 nm.sup.−1=nq/(2×π)  [Mathematical Expression 1] where in the Mathematical Expression 1, n represents a number of the chain-forming atoms included in the side chain, and q represents a smallest scattering vector (q) whose peak is detectable or a scattering vector (q) that is observed to have a peak with a largest peak area, during XRD analysis on the block copolymer.

10. The block copolymer of claim 9, wherein the first block produces both the melting transition peak and the isotropic transition peak according to the Condition 2, wherein a difference (Ti−Tm) between a temperature (Ti) at which the isotropic transition peak is produced and a temperature (Tm) at which the melting transition peak is produced is 5° C. to 70° C.

11. The block copolymer of claim 9, wherein the first block produces both the melting transition peak and the isotropic transition peak according to the Condition 2, wherein a ratio (M/I) of an area (M) of the melting transition peak to an area (I) of the isotropic transition peak ranges from 0.1 to 500.

12. The block copolymer of claim 9, wherein the first block produces the melting transition peak between −10° C. and 55° C., according to the Condition 2.

13. The block copolymer of claim 9, wherein the first block includes a side chain and satisfies Mathematical Expression 1 below, according to the Condition 2:
10° C.≦Tm−12.25° C.×n+149.5° C.≦10° C.  [Mathematical Expression 1] where in the Mathematical Expression 1, Tm represents a temperature at which the melting transition peak appears, and n represents the number of chain-forming atoms included in the side chain.

14. The block copolymer of claim 9, wherein X of Mathematical Expression 2 below is 1.25 or more:
X=1+(D×M)/(K×L)  [Mathematical Expression 2] where in the Mathematical Expression A, D represents a ratio (D2/D1) of a density (D2) of the second block to a density (D1) of the first block; M represents a ratio (M1/M2) of a molar mass (M1) of the first block to a molar mass (M2) of the second block; K represents a ratio (A2/A1) in a .sup.1H-NMR spectrum of an area (A2) of a peak that is produced based on the second block to an area (A1) of a peak that is produced based on the first block; and L represents a ratio (H1/H2) of a number (H1) of hydrogen atoms in 1 mole of a repeat unit of the first block to a number (H2) of hydrogen atoms in 1 mole of a repeat unit of the second block.

15. The block copolymer of claim 9, wherein the first block or the second block includes an aromatic structure.

16. The block copolymer of claim 9, wherein each of the first block and the second block includes an aromatic structure.

17. The block copolymer of claim 9, wherein the first block includes an aromatic structure without a halogen atom, and the second block includes an aromatic structure that includes one or more halogen atoms.

18. The block copolymer of claim 9, wherein the first block or the second block includes a side chain that includes 8 or more chain-forming atoms.

19. The block copolymer of claim 9, wherein the first block or the second block includes one or more halogen atoms.

20. The block copolymer of claim 9, wherein the first block includes a side chain with 8 or more chain-forming atoms, and the second block includes one or more halogen atoms.

21. The block copolymer of claim 9, wherein the first block or the second block includes an aromatic structure to which a side chain with 8 or more chain-forming atoms is connected.

22. The block copolymer of claim 21, wherein the side chain is connected to the aromatic structure by an oxygen atom or a nitrogen atom.

23. The block copolymer of claim 9, wherein the first block 1 or the second block includes an aromatic structure that is substituted in part by one or more halogen atoms.

24. The block copolymer of claim 9, wherein the first block includes an aromatic structure to which a side chain that includes 8 or more chain-forming atoms is connected, and the second block includes an aromatic structure that includes a halogen atom.

25. The block copolymer of claim 9, wherein the first block includes a side chain that includes 8 or more chain-forming atoms.

26. The block copolymer of claim 25, wherein the first block includes a ring structure that is substituted in part by a side chain.

27. The block copolymer of claim 26, wherein the ring structure does not include a halogen atom.

28. The block copolymer of claim 25, wherein the second block includes 3 or more halogen atoms.

29. The block copolymer of claim 28, wherein the second block includes a ring structure that is substituted in part by the halogen atoms.

30. The block copolymer of claim 9, wherein the first block includes a structural unit represented by Structural Formula 1 below: ##STR00011## where in the Structural Formula 1, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons; X represents 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)—, wherein the X.sub.1 represents an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group; and Y represents a monovalent substituent that includes a ring structure to which a chain including 8 or more chain-forming atoms is connected.

31. The block copolymer of claim 9, wherein the second block includes a structural unit represented by Structural Formula 3 below: ##STR00012## where in the Structural Formula 3, X.sub.2 represents 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)—, wherein the X.sub.1 represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group; and W represents an aryl group that includes at least one halogen atom.

32. A polymer film comprising the block copolymer of claim 9, wherein the block copolymer is self-assembled.

33. A method of forming a polymer film comprising: forming a polymer film that includes the block copolymer of claim 9 on a substrate, wherein the block copolymer is self-assembled.

34. A method of forming a pattern, the method comprising: removing the first block or second block of the block copolymer of claim 9 from a polymer film that is formed on a substrate and includes the block copolymer, wherein the block copolymer is self-assembled.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0140] FIGS. 1 and 2 each shows a GISAXS diffraction pattern.

[0141] FIGS. 3 to 11 each shows a SEM image of a polymer film.

[0142] FIGS. 12 to 17 each shows the results of GIWAXS analysis.

[0143] FIG. 18 exemplifies a method of calculating the value of K in Mathematical Expression A.

[0144] FIGS. 19 to 21 each shows a GISAXS diffraction pattern.

EFFECT

[0145] The present application can provide a block copolymer—which exhibits an excellent self-assembling property or phase separation property and, thus, can be used effectively in a variety of applications—and uses thereof.

DETAILED DESCRIPTION OF EMBODIMENTS

[0146] The present application is described in more detail hereinafter through examples and comparative examples according to the present application, but the scope of the present application is not limited to the examples which are proposed hereinafter.

[0147] 1. NMR Measurement

[0148] NMR analysis was carried out at room temperature by using a NMR spectrometer that includes a Varian Unity Inova (500 MHz) spectrometer with a 5-mm triple resonance probe. The analysis subject material was diluted with a solvent (CDCl.sub.3) for an NMR measurement to a concentration of about 10 mg/ml for use, and the chemical shift was expressed in ppm.

[0149] <Applied Abbreviations>

[0150] br=broad signal, s=singlet, d=doublet, dd=doublet of doublets, t=triplet, dt=doublet of triplets, q=quartet, p=quintet, m=multiplet.

[0151] 2. Gel Permeation Chromatography (GPC)

[0152] The number average molecular weight (Mn) and molecular weight distribution were measured by GPC. The analysis subject material such as a macroinitiator or the block copolymer of the examples or of the comparative examples was put in a 5-mL vial and diluted with tetrahydrofuran (THF) to a concentration of about 1 mg/mL. Then, a standard specimen for calibration and the specimen to be analyzed were filtered with a syringe filter (pore size: 0.45 μm) and subsequently analyzed. ChemStation (Agilent Technologies Inc.) was used as the analytical program, each of the Mw and Mn was obtained by comparing the elution time of the specimen with the calibration curve, and then a molecular weight distribution (polydispersity index, PDI) was calculated as a ratio Mw/Mn. The measuring condition of GPC is as follows:

[0153] <GPC Measuring Conditions>

[0154] Device: 1200 Series of Agilent Technologies Inc.

[0155] Column: Two PLgel MIXED-B of Polymer Laboratories

[0156] Solvent: THF

[0157] Column temperature: 35° C.

[0158] Sample concentration: 1 mg/mL, 200 L is injected

[0159] Standard specimen: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0160] 3. GISAXS (Grazing-Incidence Small-Angle X-Ray Scattering)

[0161] GISAXS analysis was carried out by using a 3C beamline of Pohang accelerator. A coating solution was prepared by dissolving a block copolymer, which is the subject to be analyzed, in fluorobenzene to a solid concentration of about 0.7 wt %, and it was spin-coated on a base material at a thickness of about 5 nm. The coating area was adjusted to about 2.25 cm.sup.2 (width: 1.5 cm, length: 1.5 cm). The coated polymer film was dried at room temperature for about 1 hour, and then again thermal-annealed at a temperature of about 160° C. for about 1 hour to induce the formation of a phase-separated structure. Subsequently, a film having a phase-separated structure was formed. After having an X-ray incident on the film at an incident angle of about 0.12 degrees to 0.23 degrees, which is an angle greater than either one of the critical angle of the film and the critical angle of the base material and smaller than the other, an X-ray diffraction pattern that is scattered from the film was obtained by a detector (2D marCCD). In this case, the distance from the film to the detector was set within the range between about 2 m and 3 m in which the self-assembled pattern of the film was well observed. As the base material, a base material that has a hydrophilic surface (a silicon substrate that was treated by piranha solution to have a room-temperature wetting angle of about 5 degrees against purified water) or a base material that has a hydrophobic surface (a silicon substrate that was treated by hexamethyldisilazane (HMDS) to have a room-temperature wetting angle of about 60 degrees against purified water) was used.

[0162] 4. XRD Analysis Method

[0163] XRD analysis was carried out by transmitting X-rays emitted from a 4C beamline of Pohang accelerator through a specimen and measuring the scattering intensity that changes in response to the scattering vector q. A polymer that had been synthesized without being pre-treated in a particular manner was purified, then dried in a vacuum oven for about one day to be formed into a powder, and placed in a cell for XRD measurement to be used as the specimen. For XRD pattern analysis, an X-ray whose vertical size is 0.023 mm and horizontal size is 0.3 mm was used, and a 2D marCCD detector was used. The 2D diffraction pattern that is scattered from the specimen was obtained in the form of an image. The obtained diffraction pattern was analyzed by a numerical analytical method that applies least-squares regression to obtain information such as the scattering vector and FWHM. An Origin program was used for the above analysis, and the part that corresponds to the minimum intensity in an XRD diffraction pattern was set as the baseline and the minimum intensity was set as zero, then the peak profile of the above XRD pattern was subject to Gaussian fitting, and the aforementioned scattering vector and FWHM were obtained from the fitted result. When the above Gaussian fitting was performed, the R-square value was set to be at least 0.96.

[0164] 5. Surface Energy Measurement

[0165] A surface energy may be measured by using the Drop Shape Analyzer DSA100 (manufactured by KRUSS GmbH). The material (i.e. a polymer) to be measured was dissolved in fluorobenzene to a solid concentration of about 2 wt % to prepare a coating solution, which was spin-coated on a substrate at a thickness of about 50 nm and a coating area of 4 cm.sup.2 (width: 2 cm, length: 2 cm). The coated layer was dried at room temperature for about 1 hour and then thermal-annealed at 160° C. for about 1 hour. The process of measuring a contact angle by dropping deionized water, whose surface tension is well known in the art, on the above thermal-annealed film was repeated for 5 times, and the 5 measured values of a contact angle were averaged. Similarly, the process of measuring a contact angle by dropping diiodomethane, whose surface tension is well-known in the art, on the above thermal-annealed film was repeated for 5 times, and the 5 measured values of a contact angle were averaged. Subsequently, the surface energies were obtained by using the averaged values of the contact angle, which were measured respectively with deionized water and diiodomethane, and substituting the numerical value (Strom value) that corresponds to the surface tension of a solvent into the equations according to the Owens-Wendt-Rabel-Kaelble method. The numerical value that corresponds to the surface energy of each block of a block copolymer was obtained by using the above-described method on a homopolymer that was made up of only the monomers that constitute the above block.

[0166] 6. GIWAXS (Grazing-Incidence Wide-Angle X-Ray Scattering)

[0167] GIWAXS analysis was carried out by using a 3C beamline of Pohang accelerator. A coating solution was prepared by dissolving a block copolymer, which is the subject to be analyzed, in toluene to a solid concentration of about 1 wt %, and it was spin-coated on a base material at a thickness of about 30 nm. The coating area was adjusted to about 2.25 cm.sup.2 (width: 1.5 cm, length: 1.5 cm). The coated polymer film was dried at room temperature for about 1 hour, and then again thermal-annealed at a temperature of about 160° C. for about 1 hour to form a film. After having an X-ray incident on the film at an incident angle of about 0.12 degrees to 0.23 degrees, which is an angle greater than either one of the critical angle of the film and the critical angle of the base material and smaller than the other, an X-ray diffraction pattern that is scattered from the film was obtained by a detector (2D marCCD). In this case, the distance from the film to the detector was set within the range between about 0.1 m and 0.5 m in which the crystalline or liquid-crystalline structure of the film was well observed. A silicon substrate that was treated by piranha solution to have a room-temperature wetting angle of about 5 degrees against purified water was used as the base material.

[0168] The scattering intensity in the azimuthal angle (i.e. the azimuthal angle when an angle measured in the upward direction of the diffraction pattern (i.e. the angle of out-of-plane diffraction pattern) is set as 0 degrees) range of −90 degrees to 90 degrees in a diffraction pattern of a GIWAXS spectrum—where the scattering vector ranged from 12 nm.sup.−1 to 16 nm.sup.−1—was plotted as a graph, and the FWHM was measured through Gaussian fitting of the graph. In the case where only a half of a peak was observed from Gaussian fitting, the twice the FWHM value of the obtained (observed) peak was defined as the FWHM of the peak.

[0169] 7. DSC Analysis

[0170] DSC analysis was carried out by using DSC800 (PerkinElmer Inc). An endothermic curve was obtained by a method that applies the above apparatus, in which the subject specimen to be analyzed was heated under a nitrogen atmosphere at a rate of 10° C. per minute from 25° C. to 200° C., cooled at a rate of −10° C. per minute from 200° C. to −80° C., and then again heated at a rate of 10° C. per minute from −80° C. to 200° C. The obtained endothermic curve was analyzed to estimate the temperature (i.e. melting transition temperature, Tm) at which a melting transition peak appears, the temperature (i.e. isotropic transition temperature, Ti) at which an isotropic transition peak appears, and the area of each peak. Here, each of the above temperatures was determined by the temperature that corresponds to the summit of each peak. The area per unit mass of each peak can be determined by dividing the peak area by the mass of the specimen, and such a calculation is possible through a program that is provided by the DSC apparatus.

[0171] 8. Measurement of X by Equation A

[0172] Each of the variables of Mathematical Expression A-D, M, K and L—can be obtained as follows:

[0173] First of all, D can be obtained by putting a specimen to be analyzed (i.e. a homopolymer that is prepared with only the monomer that constitutes the block 1 or a homopolymer that is prepared with only the monomer that constitutes the block 2) in a solvent (i.e. ethanol) whose mass and density in air are known, obtaining the density of each block through the mass of the specimen, and calculating the ratio of the masses of different types of specimen.

[0174] Also, M can be obtained as the ratio of molar masses of monomers that make up blocks in a block copolymer. For example, in the case of each block copolymer of an example, the molar mass of the monomer of Preparation Example 1, which is the monomer that constitutes the block 1 that will be described below in the present specification, is 346.5 g/mol, the molar mass of pentafluorostyrene that constitutes the block 2 is 194.1 g/mol, and, from the ratio, the value of M can be calculated to be about 1.79.

[0175] In addition, L can be obtained as the ratio of number of hydrogen atoms in the monomers that make up blocks in a block copolymer. For example, in the case of each block copolymer of an example, the number of hydrogen atoms in the monomer of Preparation Example 1, which is the monomer that constitutes the block 1, is 34, the number of hydrogen atoms in pentafluorostyrene that constitutes the block 2 is 3, and, from the ratio, the value of L can be calculated to be about 11.3.

[0176] Lastly, K can be calculated through the area of a spectrum that is obtained by the aforementioned NMR analysis method. In this case, when the peaks—each of which is obtained from each block in a block copolymer—do not overlap each other, the area of the peak derived from each block is simply analyzed, and K can be obtained as the ratio of the peak areas.

[0177] In contrast, when the peaks derived from different blocks of a block copolymer overlap each other at least partly, the overlapped part should be taken into consideration when obtaining the value of K. For example, the accompanying FIG. 18 is an illustrative NMR spectrum of a block copolymer that contains a structural unit, which is derived from the compound represented by Structural Formula A that is prepared according to Preparation Example 1 and applied in the following examples and comparative examples, and a structural unit derived from pentafluorostyrene. In FIG. 18, the part that is marked as e and the part that is marked as d refer to the peaks that come from the block 2 (that is, the aforementioned structural unit that is derived from pentafluorostyrene), and the rest (a, b, c, f, g, h, i and j) are the peaks that come from a structural unit that is derived from the compound (represented by Structural Formula A) of Preparation Example 1. As can be seen in the graph, the peaks marked as e and g and the peaks marked as d and f overlap each other; in which case, the overlapping of the peaks should be taken into consideration when obtaining the value of K.

[0178] In this case, the method of obtaining the value of K by taking the overlapping of the peaks into account is well known in the art; the value can be obtained, for example, by using an NMR interpretation program such as a MestReC program.

Preparation Example 1. Synthesis of Monomer A

[0179] The compound DPM-C12 represented by the following Structural Formula A was synthesized by the following method: hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were introduced into a 250-mL flask, dissolved in 100 mL of acetonitrile; then, an excessive amount of potassium carbonate was added to the above solution and allowed to react at about 75° C. for about 48 hours under a nitrogen atmosphere; upon completion of the reaction, the reaction products were filtered to be removed of the remaining potassium carbonate and acetonitrile that was used for the reaction; then the substances were worked up through an addition of a mixed solvent of dichloromethane (DCM) and water, and the separated organic layer was collected and dehydrated with MgSO.sub.4; subsequently, the substances were purified by column chromatography (CC) with DCM to obtain a white solid target material (i.e. 4-(dodecyloxy)-phenol) with a yield of about 37%.

[0180] <NMR Analysis Results>

[0181] .sup.1H-NMR (CDCl.sub.3): δ6.77 (dd, 4H); δ4.45 (s, 1H); δ3.89 (t, 2H); δ1.75 (p, 2H); δ1.43 (p, 2H); δ1.33-1.26 (m, 16H); δ0.88 (t, 3H).

[0182] The synthesized 4-(dodecyloxy)-phenol (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 introduced into a flask, 120 mL of methylene chloride was added, and then allowed to react at room temperature for 24 hours under a nitrogen atmosphere; upon completion of the reaction, the reaction products were filtered to be removed of a urea salt that was produced during the reaction and also of the remaining methylene chloride; then, the substances were removed of impurities by column chromatography (CC) that uses hexane and dichloromethane (DCM) as the mobile phase, the obtained products were recrystallized in a mixed solvent of methanol and water (mixed in a weight ratio of 1:1) to obtain a white solid target material (7.7 g, 22.2 mmol) with a yield of 63%.

[0183] <NMR Analysis Results>

[0184] .sup.1H-NMR (CDCl.sub.3): δ7.02 (dd, 2H); δ6.89 (dd, 2H); δ6.32 (dt, 1H); δ5.73 (dt, 1H); δ3.94 (t, 2H); δ2.05 (dd, 3H); δ1.76 (p, 2H); δ1.43 (p, 2H); 1.34-1.27 (m, 16H); δ0.88 (t, 3H).

##STR00005##

[0185] In Structural Formula A, R represents a linear-chain alkyl group with 12 carbons.

Preparation Example 2. Synthesis of Monomer G

[0186] The compound represented by the following Structural Formula G was synthesized by the method of Preparation Example 1, except that 1-bromobutane was used instead of 1-bromododecane. The results of NMR analysis on the above compound are as follows.

[0187] <NMR Analysis Results>

[0188] .sup.1H-NMR (CDCl.sub.3): δ7.02 (dd, 2H); δ6.89 (dd, 2H); δ6.33 (dt, 1H); δ5.73 (dt, 1H); δ3.95 (t, 2H); δ2.06 (dd, 3H); δ1.76 (p, 2H); δ1.49 (p, 2H); δ0.98 (t, 3H).

##STR00006##

[0189] In Structural Formula G, R represents a linear-chain alkyl group with 4 carbons.

Preparation Example 3. Synthesis of Monomer B

[0190] The compound represented by the following Structural Formula B was synthesized by the method of Preparation Example 1, except that 1-bromooctane was used instead of 1-bromododecane. The results of NMR analysis on the above compound are as follows.

[0191] <NMR Analysis Results>

[0192] .sup.1H-NMR (CDCl.sub.3): δ7.02 (dd, 2H); δ6.89 (dd, 2H); δ6.32 (dt, 1H); δ5.73 (dt, 1H); δ3.94 (t, 2H); δ2.05 (dd, 3H); δ1.76 (p, 2H); δ1.45 (p, 2H); 1.33-1.29 (m, 8H); δ0.89 (t, 3H).

##STR00007##

[0193] In Structural Formula B, R represents a linear-chain alkyl group with 8 carbons.

Preparation Example 4. Synthesis of Monomer C

[0194] The compound represented by the following Structural Formula C was synthesized by the method of Preparation Example 1, except that 1-bromodecane was used instead of 1-bromododecane. The results of NMR analysis on the above compound are as follows.

[0195] <NMR Analysis Results>

[0196] .sup.1H-NMR (CDCl.sub.3): δ7.02 (dd, 2H); δ6.89 (dd, 2H); δ6.33 (dt, 1H); δ5.72 (dt, 1H); δ3.94 (t, 2H); δ2.06 (dd, 3H); δ1.77 (p, 2H); δ1.45 (p, 2H); 1.34-1.28 (m, 12H); δ0.89 (t, 3H).

##STR00008##

[0197] In Structural Formula C, R represents a linear-chain alkyl group with 10 carbons.

Preparation Example 5. Synthesis of Monomer D

[0198] The compound represented by the following Structural Formula D was synthesized by the method of Preparation Example 1, except that 1-bromotetradecane was used instead of 1-bromododecane. The results of NMR analysis on the above compound are as follows.

[0199] <NMR Analysis Results>

[0200] .sup.1H-NMR (CDCl.sub.3): δ7.02 (dd, 2H); δ6.89 (dd, 2H); δ6.33 (dt, 1H); δ5.73 (dt, 1H); δ3.94 (t, 2H); δ2.05 (dd, 3H); δ1.77 (p, 2H); δ1.45 (p, 2H); 1.36-1.27 (m, 20H); δ0.88 (t, 3H.)

##STR00009##

[0201] In Structural Formula D, R represents a linear-chain alkyl group with 14 carbons.

Preparation Example 6. Synthesis of Monomer E

[0202] The compound represented by the following Structural Formula E was synthesized by the method of Preparation Example 1, except that 1-bromohexadecane was used instead of 1-bromododecane. The results of NMR analysis on the above compound are as follows.

[0203] <NMR Analysis Results>

[0204] .sup.1H-NMR (CDCl.sub.3): δ7.01 (dd, 2H); δ6.88 (dd, 2H); δ6.32 (dt, 1H); δ5.73 (dt, 1H); δ3.94 (t, 2H); δ2.05 (dd, 3H); δ1.77 (p, 2H); δ1.45 (p, 2H); 1.36-1.26 (m, 24H); δ0.89 (t, 3H)

##STR00010##

[0205] In Structural Formula E, R represents a linear-chain alkyl group with 16 carbons.

[0206] Results of GIWAXS and DSC Analyses

[0207] 6 types of homopolymers were prepared by using the monomers each of which was prepared according to one of Preparation Examples 1 to 6, and the analyzed results of GIWAXS and DSC on each homopolymer are summarized and provided in the following Table 1. Here, the homopolymers were prepared by the method of using each type of monomer to synthesize a macroinitiator according to the following examples or comparative examples. The results of GIWAXS analyses of the preparation examples are provided in FIGS. 12 to 17. Each of FIGS. 12 to 17 corresponds respectively to an image that shows the result of GIWAXS analysis of each of Preparation Examples 1 to 6.

[0208] In FIG. 12, the R-square of Gaussian fitting was about 0.264, in FIG. 16, the R-square was about 0.676, and in FIG. 17, the R-square was about 0.932.

TABLE-US-00001 TABLE 1 Preparation Examples 1 2 3 4 5 6 Tg — 33 29 — — — 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 8 10 14 16 atoms Tg: Glass transition temperature (Unit: ° C.) Tm: Melting transition temperature (Unit: ° C.) Ti: Isotropic transition temperature (Unit: ° C.) M/I: Ratio of melting transition peak area (M) to isotropic transition peak area (I) FWHM1: FWHM of peak at azimuthal angle range of −90 degrees to −70 degrees in GIWAXS diffraction pattern, where scattering vector ranges from 12 nm.sup.−1 to 16 nm.sup.−1 (Unit: degrees) FWHM2: FWHM of peak at azimuthal angle range of 70 degrees to 90 degrees in GIWAXS diffraction pattern, where scattering vector ranges from 12 nm.sup.−1 to 16 nm.sup.−1 (Unit: degrees) Chain-forming atoms: number of chain-forming atoms in block1 (= number of carbon atoms in R of structural formula of each preparation example)

Example 1

[0209] 1.785 g of monomer A of Preparation Example 1, 38 mg of a Reversible Addition-Fragmentation chain Transfer (RAFT) reagent (cyanoisopropyl dithiobenzoate), 14 mg of a radical initiator (azobisisobutyronitrile, AIBN) and 4.765 mL of benzene were introduced into a 10-mL Schlenk flask, stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then a RAFT polymerization reaction was carried out at 70° C. for 4 hours. Upon completion of polymerization, the reaction solution was precipitated in 250 mL of an extraction solvent (methanol) and then dried by filtration under reduced pressure to prepare a pink macroinitiator. The yield of the macroinitiator was about 83.1 wt %, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) 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 introduced into a 10-mL Schlenk flask, stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then a RAFT polymerization reaction was carried out at 115° C. for 4 hours. Upon completion of polymerization, the reaction solution was precipitated in 250 mL of an extraction solvent (methanol) and then dried by filtration under reduced pressure to prepare a light-pink block copolymer. The yield of the block copolymer was about 27.1 wt %, and the Mn and Mw/Mn were 18,900 and 1.19, respectively. The above block copolymer contains the block 1 (that is derived from monomer A prepared according to Preparation Example 1) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). The results of GISAXS measurement that was performed, in the aforementioned manner, on a hydrophilic surface (the surface whose room-temperature wetting angle against purified water is 5 degrees) of the block copolymer are provided in FIG. 1, and the results of GISAXS measurement on a hydrophobic surface (the surface whose room-temperature wetting angle against purified water is 60 degrees) are provided in FIG. 2. It is indicated in FIGS. 1 and 2 that an in-plane diffraction pattern was produced from GISAXS in any case.

Example 2

[0210] A block copolymer was prepared according to the method of Example 1 by using the macroinitiator and pentafluorostyrene as the monomers, except that monomer B from Preparation Example 3 was used instead of monomer A from Preparation Example 1. The block copolymer contains the block 1 (that is derived from monomer B of Preparation Example 3) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). GISAXS was conducted on the block copolymer by the method described in Example 1, and an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

Example 3

[0211] A block copolymer was prepared according to the method of Example 1 by using the macroinitiator and pentafluorostyrene as the monomers, except that monomer C from Preparation Example 4 was used instead of monomer A from Preparation Example 1. The block copolymer contains the block 1 (that is derived from monomer C of Preparation Example 4) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). GISAXS was conducted on the block copolymer by the method described in Example 1, and an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

Example 4

[0212] A block copolymer was prepared according to the method of Example 1 by using the macroinitiator and pentafluorostyrene as the monomers, except that monomer D from Preparation Example 5 was used instead of monomer A from Preparation Example 1. The block copolymer contains the block 1 (that is derived from monomer D of Preparation Example 5) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). GISAXS was conducted on the block copolymer by the method described in Example 1, and an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

Example 5

[0213] A block copolymer was prepared according to the method of Example 1 by using the macroinitiator and pentafluorostyrene as the monomers, except that monomer E from Preparation Example 6 was used instead of monomer A from Preparation Example 1. The block copolymer contains the block 1 (that is derived from monomer E of Preparation Example 6) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). GISAXS was conducted on the block copolymer by the method described in Example 1, and an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

Comparative Example 1

[0214] A block copolymer was prepared according to the method of Example 1 by using the macroinitiator and pentafluorostyrene as the monomers, except that monomer G from Preparation Example 2 was used instead of monomer A from Preparation Example 1. The block copolymer contains the block 1 (that is derived from monomer G of Preparation Example 2) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). GISAXS was conducted on the block copolymer by the method described in Example 1, but an in-plane diffraction pattern was not observed on any of the hydrophilic surface and the hydrophobic surface.

Comparative Example 2

[0215] A block copolymer was prepared according to the method of Example 1 by using the macroinitiator and pentafluorostyrene as the monomers, except that 4-methoxyphenyl methacrylate was used instead of monomer A from Preparation Example 1. The block copolymer contains the block 1 (that is derived from 4-methoxyphenyl methacrylate) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). GISAXS was conducted on the block copolymer by the method described in Example 1, but an in-plane diffraction pattern was not observed on any of the hydrophilic surface and the hydrophobic surface.

Comparative Example 3

[0216] A block copolymer was prepared according to the method of Example 1 by using the macroinitiator and pentafluorostyrene as the monomers, except that dodecyl methacrylate was used instead of monomer A from Preparation Example 1. The block copolymer contains the block 1 (that is derived from dodecyl methacrylate) and the block 2 (that is derived from the aforementioned pentafluorostyrene monomer). GISAXS was conducted on the block copolymer by the method described in Example 1, but an in-plane diffraction pattern was not observed on any of the hydrophilic surface and the hydrophobic surface.

[0217] The results of GPC measurement on the macroinitiators and prepared block copolymers of the above examples and comparative examples are summarized and provided in the following Table 2.

TABLE-US-00002 TABLE 2 Examples Comparative Examples 1 2 3 4 5 1 2 3 MI Mn 11400 9300 8500 8700 9400 9000 7800 8000 PDI 1.15 1.16 1.14 1.18 1.15 1.17 1.13 1.16 BCP Mn 18900 19900 17100 17400 18900 18800 18700 16700 PDI 1.19 1.18 1.17 1.18 1.17 1.20 1.16 1.20 MI: Macroinitiator BCP: Block copolymer Mn: Number average molecular weight PDI: Molecular weight distribution

[0218] The properties of the block copolymers prepared as the above were evaluated in the aforementioned manner, and the results are summarized and provided in the following Table 3.

TABLE-US-00003 TABLE 3 Comparative Examples Examples 1 2 3 4 5 1 2 3 Ref Block SE 30.83 31.46 27.38 26.924 27.79 37.37 48.95 19.1 38.3 1 De 1 1.04 1.02 0.99 1.00 1.11 1.19 0.93 1.05 Block SE 24.4 24.4 24.4 24.4 24.4 24.4 24.4 24.4 41.8 2 De 1.57 1.57 1.57 1.57 1.57 1.57 1.57 1.57 1.18 Difference 6.43 7.06 2.98 2.524 3.39 12.98 24.55 5.3 3.5 in SE Difference 0.57 0.53 0.55 0.58 0.57 0.46 0.38 0.64 0.13 in De Chain- 12 8 10 14 16 4 1 12 — forming atoms n/D 3.75 3.08 3.45 4.24 4.44 2.82 1.98 — — SE: Surface energy (Unit: mN/m) De: Density (Unit: g/cm.sup.3) Difference in SE: Absolute value of difference in surface energies of block 1 and block 2 Difference in De: Absolute value of difference in densities of block 1 and block 2 Chain-forming atoms: number of chain-forming atoms in block 1 n/D: numerical value calculated by Equation 1 (nq/(2 × π)) (n: number of chain-forming atoms, q represents numerical value of scattering vector at which peak with largest peak area is observed in scattering vector range of 0.5 nm.sup.−1 to 10 nm.sup.−1) Ref: polystyrene-poly(methyl methacrylate) block copolymer (block 1: polystyrene block, block 2: poly(methyl methacrylate) block

[0219] The analyzed results of XRD pattern of the macroinitiator (i.e. the block 1) that was used in the preparation of each of the above block copolymers are summarized and provided in the following Table 4 (in the case of Comparative Example 3, not a single peak was observed in the scattering vector range of 0.5 nm.sup.−1 to 10 nm.sup.−1).

TABLE-US-00004 TABLE 4 Examples Comparative 1 2 3 4 5 1 2 3 Value of q peak 1.96 2.41 2.15 1.83 1.72 4.42 3.18 — (Unit: nm.sup.−1) FWHM 0.57 0.72 0.63 0.45 0.53 0.97 1.06 — (Unit: nm.sup.−1)

Test Example 1. Evaluation of Self-Assembling Property

[0220] The coating solution prepared by dissolving the block copolymer of an example or comparative example in fluorobenzene to a solid concentration of 0.7 wt % was spin-coated (coating area: width×length=1.5 cm×1.5 cm) on a silicon wafer to a thickness of about 5 nm, dried at room temperature for about 1 hour, and then thermal-annealed at a temperature of about 160° C. for about 1 hour to form a self-assembled film. A scanning electron microscopic (SEM) image was taken of the film. Each of FIGS. 3 to 7 corresponds respectively to a SEM image of each film of Examples 1 to 5. As indicated in the images, each of the block copolymers of examples had a self-assembled film that was effectively formed in a line pattern. In contrast, in the case of comparative examples, the phase separation was not induced at a sufficient level. For example, FIG. 8 shows the result of SEM of Comparative Example 3, which indicates that the phase separation was not effectively induced.

Test Example 2. Evaluation of Self-Assembling Property

[0221] A polymer film was formed, by the method described in Test Example 1 on the block copolymer that had been prepared in Example 1. Each polymer film was formed on each of a silicon substrate which had been treated with piranha solution to have a room-temperature wetting angle of 5 degrees against purified water, a silicon oxide substrate in which the above wetting angle is about 45 degrees, and a HMDS-treated silicon substrate in which the above wetting angle is about 60 degrees. FIGS. 9 to 11 show SEM images of polymer films having the above wetting angle of 5 degrees, 45 degrees and 60 degrees, respectively. The images indicate that the block copolymers are capable of effectively realizing phase-separated structures, regardless of the surface property of the substrate.

Test Example 3

[0222] Block copolymers BCP1 to BCP4 were prepared by the method described in Example 1, except that the values of X in Mathematical Expression A were adjusted by controlling the molar ratio between monomers and macroinitiators, or the like.

TABLE-US-00005 TABLE 3 Values of X in Mathematical Expression 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: Ratio D2/D1 of density D2 of block 2 to density D1 of block 1 M: Ratio M1/M2 of molar mass (346.5 g/mol, M1) of monomer of Structural Formula A from Preparation Example 1 (which is monomer that constitutes block 1) to molar mass (194.1 g/mol, M2) of pentafluorostyrene (which is monomer that constitutes block 2) K: Ratio A2/A1 of area A2 of peak that is obtained, during .sup.1H-NMR, based on block 2 to area A1 of peak that is based on block 1 L: Ratio H1/H2 of number (34, H1) of hydrogen atoms in monomer of Structural Formula A from Preparation Example 1 (which is monomer that constitutes block 1) to number (3, H2) of hydrogen atoms in pentafluorostyrene (which is monomer that constitutes block 2)

[0223] The coating solution prepared by dissolving each of the above block copolymers in fluorobenzene to a solid concentration of 0.7 wt % was spin-coated (coating area: width×length=1.5 cm×1.5 cm) on a silicon wafer to a thickness of about 5 nm, dried at room temperature for about 1 hour, and then thermal-annealed at a temperature of about 160° C. for about 1 hour to form a film. GISAXS was performed on the above film, and the measured results were produced as images. FIGS. 19 to 21 show the results on BCP1, BCP2 and BCP3, respectively. It is indicated in the images that GISAXS in-plane diffraction patterns were observed in the above block copolymer. However, in the case of BCP4, any clear result was not identified.