BLOCK COPOLYMER

Abstract

The present application provides the block copolymers and their application. The block copolymer has an excellent self assembling property and phase separation and various required functions can be freely applied thereto as necessary.

Claims

1. A block copolymer comprising a block represented by Formula 6 below: ##STR00021## wherein the R.sup.1 and R.sup.2 each independently are 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.1C(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, the T is a single bond or an arylene group, the Q is a single bond or a carbonyl group and the Y is a chain having 8 or more chain-forming atoms.

2. The block copolymer according to claim 1, wherein the X is a single bond, an oxygen atom, a carbonyl group, C(O)O or OC(O).

3. The block copolymer according to claim 1, wherein the chain has 8 to 20 chain-forming atoms.

4. The block copolymer according to claim 1, wherein the chain-forming atom is a carbon, an oxygen, a nitrogen or a sulfur.

5. The block copolymer according to claim 1, wherein the chain is a linear hydrocarbon chain.

6. The block copolymer according to claim 1, further comprising a second block comprising an aromatic structure having at least one halogen atom.

7. The block copolymer according to claim 6, wherein the second block is represented by the Formula 8 below: ##STR00022## wherein 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.1C(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 comprising at least one halogen atom.

8. The block copolymer according to claim 6, wherein the second block is represented by Formula 9 below: ##STR00023## wherein 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.1C(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 R.sub.1 to R.sub.5 are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom; and the number of the halogen atom included in the R.sub.1 to R.sub.5 is 1 or more.

9. The block copolymer according to claim 8, wherein the number of the halogen atom included in the R.sub.1 to R.sub.5 is 3 or more.

10. The block copolymer according to claim 8, wherein the number of the halogen atom included in the R.sub.1 to R.sub.5 is 5 or more.

11. The block copolymer according to claim 6, wherein the halogen atom is a fluorine.

12. The block copolymer according to claim 1, wherein it exhibits a peak, of which a full width at half maximum is in a range from 0.2 nm.sup.1 to 1.5 nm.sup.1, within a q value range from 0.5 nm.sup.1 to 10 nm.sup.1 when the X ray diffraction analysis is performed.

13. The block copolymer according to claim 6, wherein a volume fraction of the block represented by the Formula 6 is in a range from 0.4 to 0.8 and a volume fraction of the second block is in a range from 0.2 to 0.6.

14. The block copolymer according to claim 6, wherein an absolute value of a difference between surface energies of the block represented by the Formula 6 and second block is in a range from 2.5 mN/m to 7 mN/m.

15. The block copolymer according to claim 1, wherein a surface energy of the block represented by the Formula 6 is in a range from 20 mN/m to 35 mN/m.

16. The block copolymer according to claim 6, wherein an absolute value of a difference between densities of the block represented by the Formula 6 and second block is 0.3 g/cm.sup.3 or more.

17. A polymer layer comprising a self assembled product of the block copolymer of claim 1.

18. A method for forming a polymer layer, comprising forming the polymer layer comprising a self assembled product of the block copolymer of claim 1.

19. A pattern-forming method comprising selectively removing the first block or the second block of the block copolymer from a laminate comprising a substrate and a polymer layer that is formed on the substrate and that comprises a self-assembled product of the block copolymer of claim 1.

Description

BRIEF DESCRIPTION OF FIGURES

[0158] FIGS. 1 to 4 are SEM images of polymer layers.

EFFECTS

[0159] The present application may provide the block copolymers and their application. The block copolymer has an excellent self assembling property and phase separation and various required functions can be freely imparted thereto as necessary.

ILLUSTRATIVE EMBODIMENTS

[0160] Hereinafter, the present application will be described in detail with reference to Examples and Comparative Examples, but the scope of the present application is not limited to the following examples.

[0161] 1. NMR Analysis

[0162] The NMR analysis was performed at the room temperature by using a NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer having a triple resonance 5 mm probe. A sample to be analyzed was used after diluting it in solvent (CDCl.sub.3) for the NMR analysis to a concentration of approximately 10 mg/ml and a chemical shift () was expressed in ppm.

ABBREVIATION

[0163] br=wide signal, s=singlet, d=doublet, dd=double doublet, t=triplet, dt=double triplet, q=quadruplet, p=quintuplet, m=multiplet

[0164] 2. GPC (Gel Permeation Chromatograph)

[0165] The number average molecular weight and the polydispersity were measured by the GPC (Gel Permeation Chromatograph). In a 5 mL vial, a block copolymer or a macroinitiator to be measured of Example or Comparative Example and then diluted to a concentration of about 1 mg/mL. Then, the standard sample for a calibration and a sample to be analyzed were filtered by a syringe filter (pore size: 0.45 m) and then analyzed. ChemStation from the Agilent technologies, Co. was used as an analysis program. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were obtained by comparing an elution time of the sample with a calibration curve and then the polydispersity (PDI) was obtained from their ratio (Mw/Mn). The measuring condition of the GPC was as below.

[0166] <GPC Measuring Condition>

[0167] Device: a 1200 series from Agilent technologies, Co.

[0168] Column: two of PLgel mixed B from Polymer laboratories, Co. were used

[0169] Solvent: THF

[0170] Temperature of the column: 35 C.

[0171] Concentration of Sample: 1 mg/mL, 200 L injection

[0172] Standard Sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

Preparation Example 1

[0173] A compound (DPM-N2) of the Formula F below was synthesized by the below method. To a 500 mL flask, Pd/C (palladium on carbon) (1.13 g, 1.06 mmole) and 200 mL of 2-propanol were added and then ammonium formate dissolved in 20 mL of water was added, and then the Pd/C was activated by performing a reaction at the room temperature for 1 minute. Then, 4-aminophenol (1.15 g, 10.6 mmole) and lauric aldehyde (1.95 g, 10.6 mmole) were added thereto and the mixture was reacted at the room temperature for 1 minute by stirring it under nitrogen. After the reaction, the Pd/C was removed and the 2-propanol used for the reaction was removed, and then the mixture was extracted by water and methylene chloride so as to remove unreacted products. An organic layer was collected and dehydrated through MgSO.sub.4. A crude product was purified by a column chromatography (mobile phase: hexane/ethyl acetate) and thereby a colorless solid intermediate (1.98 g, 7.1 mmole) was obtained (yield: 67 weight %).

[0174] <NMR Analysis Result of the Intermediate>

[0175] .sup.1H-NMR (DMSO-d): 6.69 (dd, 2H); 6.53 (dd, 2H); 3.05 (t, 2H); 1.59 (p, 2H); 1.40-1.26 (m, 16H); 0.88 (t, 3H)

[0176] The synthesized intermediate (1.98 g, 7.1 mmole), methacrylic acid (0.92 g, 10.7 mmole), dicyclohexylcarbodiimide (DCC; 2.21 g, 10.7 mmole) and p-dimethylaminopyridine (DMPA; 0.35 g, 2.8 mmol) were put into a flask, 100 ml of methylenechloride was added, and a reaction was performed at the room temperature for 24 hours under nitrogen. After the reaction was completed, a urea salt produced during the reaction was removed through a filter, and remaining methylenechloride was also removed. Impurities were removed using hexane and DCM (dichloromethane) as mobile phases though column chromatography, and the obtained product was recrystallized in a mixed solvent (methanol:water=3:1 (weight ratio)) of methanol and water, thereby obtaining a white solid product (DPM-N2)(1.94 g, 5.6 mmole) with a yield of 79%.

[0177] <NMR Analysis Result with Respect to DPM-N2>

[0178] .sup.1H-NMR (CDCl.sub.3): 6.92 (dd, 2H); 6.58 (dd, 2H); 6.31 (dt, 1H); 5.70 (dt, 1H); 3.60 (s, 1H); 3.08 (t, 2H); 2.05 (dd, 3H); 1.61 (p, 2H); 1.30-1.27 (m, 16H); 0.88 (t, 3H)

##STR00019##

[0179] In the above, the R is a linear alkyl having 12 carbon atoms.

Preparation Example 2

[0180] A compound (DPM-C4) of the Formula G below was synthesized by the below method. To a 250 mL flask, hydroquinone (10.0 g, 94.2 mmole) and 1-bromobutane (23.5 g, 94.2 mmole) were added and dissolved in 100 mL acetonitrile, an excessive amount of potassium carbonate was added thereto and then the mixture was reacted at 75 C. for approximately 48 hours under nitrogen. After the reaction, remaining potassium carbonate and acetonitrile used for the reaction were removed. The work up was performed by adding a mixed solvent of dichloromethane (DCM) and water, and separated organic layers were collected and dehydrated through MgSO.sub.4. Subsequently, a white solid intermediate was obtained with a yield of approximately 37% using DCM through column chromatography.

[0181] The synthesized intermediate (9.8 g, 35.2 mmole), methacrylic acid (6.0 g, 69.7 mmole), dicyclohexylcarbodiimide (DCC; 10.8 g, 52.3 mmole) and p-dimethylaminopyridine (DMPA; 1.7 g, 13.9 mmol) were put into a flask, 120 ml of methylenechloride was added, and a reaction was performed at the room temperature for 24 hours under nitrogen. After the reaction was completed, a urea salt produced in the reaction was removed through a filter, and remaining methylenechloride was also removed. Impurities were removed using hexane and DCM (dichloromethane) as mobile phases though column chromatography, and the obtained product was recrystallized in a mixed solvent of methanol and water (mixed in 1:1 weight ratio), thereby obtaining a white solid product (DPM-C4).

[0182] <NMR Analysis Result with Respect to DPM-C4>

[0183] .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.33 (dt, 1H); 5.73 (dt, 1H); 3.95 (t, 2H); 2.06 (dd, 3H); 1.76 (p, 2H); 1.49 (p, 2H); 0.98 (t, 3H)

##STR00020##

[0184] In the above, the R is a linear alkyl having 4 carbon atoms.

Example 1

[0185] In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyl dodecyl trithiocarbonate) and the compound (DPM-N1) of Preparation Example 1 were dissolved in a weight ratio of 26:1:0.5 (DPM-N1:RAFT reagent:AIBN) (Concentration: 70 weight %), and then a macroinitiator (a number average molecular weight: 9700, polydispersity: 1.2) was prepared by reacting the mixture for 4 hours at 70 C. under nitrogen. Then, in benzene, the synthesized macroinitiator, pentafluorostyrene (PFS) and AIBN (azobisisobutyronitrile) were dissolved in a weight ratio of 1:600:0.5 (the macroinitiator:PFS:AIBN) (Concentration: 30 weight %), and then a block copolymer (a number average molecular weight: 17300, polydispersity: 1.2) was prepared by reacting the mixture for 6 hours at 115 C. under nitrogen. The block copolymer includes the first block derived from the compound of Preparation Example 1 and the second block derived from the pentafluorostyrene.

Comparative Example 1

[0186] 2.0 g of the compound (DPM-C4) of the preparation example 2, 64 mg of RAFT (reversible addition fragmentation chain transfer) reagent (cyanoisopropyl dithiobenzoate), 23 mg of AIBN (azobisisobutyronitrile) and 5.34 mL of benzene were put into a 10 mL flask (Schlenk flask), and then the mixture was stirred for 30 minutes under the room temperature and under a nitrogen and then the RAFT (reversible addition fragmentation chain transfer) polymerization was performed. After the polymerization, the reacted solution was precipitated in 250 mL of methanol that is an extraction solvent, and then was subjected to a vaccum filtration and dried, a pink macroinitiator was obtained.

[0187] 3.0 g of the macroinitiator, 2.7174 g of pentafluorostyrene and 1.306 mL of benzene were put into a 10 mL flask (Schlenk flask), and then the mixture was stirred for 30 minutes under the room temperature and under a nitrogen and then the RAFT (reversible addition fragmentation chain transfer) polymerization was performed for 4 hours under 115 C. After the polymerization, the reacted solution was precipitated in 250 mL of methanol that is an extraction solvent, and then was subjected to a vaccum filtration and dried, a pale pink block copolymer was obtained. The block copolymer includes the first block derived from the compound (DPM-C4) of Preparation Example 2 and the second block derived from the pentafluorostyrene.

Comparative Example 2

[0188] A block copolymer was prepared by the same method as in Comparative Example 1 except that a macroinitiator prepared by using 4-methoxyphenyl methacrylate instead of the compound (DPM-C4) of Preparation Example 2 and pentafluorostyrene were used. The block copolymer includes the first block derived from the 4-methoxyphenyl methacrylate and the second block derived from the pentafluorostyrene.

Comparative Example 3

[0189] A block copolymer was prepared by the same method as in Comparative Example 1 except that a macroinitiator prepared by using dodecyl methacrylate instead of the compound (DPM-C4) of Preparation Example 2 and pentafluorostyrene were used. The block copolymer includes the first block derived from the 4-methoxyphenyl methacrylate and the second block derived from the pentafluorostyrene.

Test Example 1

[0190] Self assembled polymer layers were prepared by using block copolymers of Example 1 and Comparative Examples 1 to 3 and the results were observed. Specifically, each block copolymer was dissolved in solvent to a concentration of 1.0 weight % and then was spin-coated on a silicone wafer for 60 seconds by a speed of 3000 rpm. Then, self assembling was performed by a solvent annealing or a thermal annealing. The used solvents and aging methods were stated in the Table 1 below. Then, the self assembling properties were evaluated by subjecting each polymer layer to a SEM (scanning electron microscope) or AFM (atomic force microscopy) analysis. FIG. 1 is a result of Example 1, and FIGS. 2 to 4 are results of Comparative Examples 1 to 3, respectively.

TABLE-US-00001 TABLE 1 The coating solution Annealing The used The concentration of Annealing solvent the block copolymer Annealing method condition Ex. 1 Toluene 1.0 weight % Thermal Annealing 200 C., 1 hour Com. Ex. 1 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Com. Ex. 2 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Com. Ex. 3 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour