Block copolymer

Abstract

The present application may provide a block copolymer and a use thereof. The block copolymer of the present application has excellent self-assembly properties or phase separation characteristics, to which various functions to be required can also be freely imparted.

Claims

1. A block copolymer comprising a polymer segment A having a unit represented by Formula 4 below and polymer segments B and C different from the polymer segment A, wherein the block copolymer comprises a structure in which each of the polymer segments is connected in a form of B-A-C: ##STR00009## wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, —C(═O)—O— or —O—C(═O), and Y is a monovalent substituent comprising an aromatic ring structure to which a chain having 8 to 20 chain-forming atoms is linked, wherein the polymer segments B and C comprise a unit of Formula 7 below: ##STR00010## wherein, B is a monovalent substituent having an aromatic structure comprising one or more halogen atoms.

2. The block copolymer according to claim 1, wherein X is —C(═O)—O—.

3. The block copolymer according to claim 1, wherein each of the chain-forming atoms is independently carbon, oxygen, nitrogen or sulfur.

4. The block copolymer according to claim 1, wherein each of the chain-forming atoms is independently carbon or oxygen.

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

6. The block copolymer according to claim 1, wherein the chain of Y is linked to the ring structure via a linker.

7. The block copolymer according to claim 6, wherein the linker is an oxygen atom, a sulfur atom, —NR.sub.3—, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group, where R.sub.3 is an alkenyl group, an alkynyl group, an alkoxy group or an aryl group.

8. The block copolymer according to claim 1, wherein Y is represented by Formula 2 below:
—P-Q-Z  [Formula 2] wherein, P is an arylene group, Q is a single bond, an oxygen atom or —NR.sub.3—, where R.sub.3 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is a chain having 8 or more chain-forming atoms.

9. The block copolymer according to claim 1, wherein the unit of Formula 7 is represented by Formula 8 below: ##STR00011## wherein, 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 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 W is an aryl group containing at least one halogen atom.

10. The block copolymer according to claim 1, wherein the unit of Formula 7 is represented by Formula 9 below: ##STR00012## wherein, 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 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, 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 halogen atoms contained in R.sub.1 to R.sub.5 is 1 or more.

11. The block copolymer according to claim 1, wherein the polymer segment A has a volume fraction in a range of 0.3 to 0.5.

12. A polymer film comprising a self-assembled structure of the block copolymer of claim 1.

13. The polymer film according to claim 12, wherein the block copolymer has a number average molecular weight of 70,000 g/mol or less and a thickness of 40 nm or less.

14. A method for forming a polymer film, comprising forming on a substrate a polymer film comprising the self-assembled block copolymer of claim 1.

15. A patterning method comprising a process of selectively removing any one of polymer segments of a self-assembled structure of the block copolymer of claim 1 from a laminate having a substrate and a polymer film which is formed on the substrate and comprises the block copolymer.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 and 2 are images of the self-assembled polymer films of Examples 1 and 2, respectively.

(2) FIG. 3 is an image of the self-assembled polymer film of Comparative Example 1.

MODE FOR INVENTION

(3) Hereinafter, the present application will be described in detail by way of examples according to the present application and comparative examples, but the scope of the present application is not limited by the following examples.

(4) 1. NMR Measurement

(5) NMR analyses were performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. The analytes were diluted in a solvent for NMR measurement (CDCl.sub.3) to a concentration of about 10 mg/ml, and chemical shifts were expressed in ppm.

(6) <Application Abbreviation>

(7) br=broad signal, s=singlet, d=doublet, dd=double doublet, t=triplet, dt=double triplet, q=quartet, p=quintet, m=multiplet.

(8) 2. GPC (gel permeation chromatograph)

(9) The number average molecular weight (Mn) and the molecular weight distribution were measured using GPC (gel permeation chromatography). Into a 5 mL vial, an analyte such as block copolymers of Examples or Comparative Examples or a giant initiator is put and diluted in THF (tetrahydrofuran) to be a concentration of about 1 mg/mL or so. Then, a standard sample for calibration and a sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. As the analytical program, ChemStation from Agilent Technologies was used, and the elution time of the sample was compared with the calibration curve to obtain the weight average molecular weight (Mw) and the number average molecular weight (Mn), respectively, and the molecular weight distribution (PDI) was calculated by the ratio (Mw/Mn) thereof. The measurement conditions of GPC are as follows.

(10) <GPC Measurement Condition>

(11) Instrument: 1200 series from Agilent Technologies

(12) Column: using two PLgel mixed B from Polymer Laboratories

(13) Solvent: THF

(14) Column temperature: 35° C.

(15) Sample concentration: 1 mg/mL, 200 L injection

(16) Standard sample: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

Preparation Example 1

(17) A compound (DPM-C12) of Formula A below was synthesized in the following manner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were placed in a 250 mL flask, dissolved in 100 mL of acetonitrile, and then an excess amount of potassium carbonate was added thereto and reacted at 75° C. for about 48 hours under a nitrogen atmosphere. The potassium carbonate remaining after the reaction and the acetonitrile used for the reaction were also removed. A mixed solvent of DCM (dichloromethane) and water was added thereto to work up the mixture, and the separated organic layer was dehydrated with MgSO.sub.4. Subsequently, the product was purified by DC (dichloromethane) in CC (column chromatography) to obtain an intermediate in a white solid phase in a yield of about 37%.

(18) <NMR Analysis Result of Intermediate>

(19) .sup.1H-NMR (CDCl.sub.3): d6.77 (dd, 4H); δd4.45 (s, 1H); d3.89 (t, 2H); d1.75 (p, 2H); d1.43 (p, 2H); d1.33-1.26 (m, 16H); d0.88 (t, 3H).

(20) The synthesized intermediate (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), DCC (dicyclohexylcarbodiimide) (10.8 g, 52.3 mmol) and DMAP (p-dimethylaminopyridine) (1.7 g, 13.9 mmol) were placed in the flask and 120 mL of methylene chloride was added thereto, and then reacted at room temperature for 24 hours in a nitrogen atmosphere. After the reaction, the salt (urea salt) generated during the reaction was filtered off and the remaining methylene chloride was also removed. Impurities were removed using hexane and DCM (dichloromethane) as the mobile phase in CC (column chromatography) and the resulting product was recrystallized in a mixed solvent of methanol and water (mixed at a weight ratio of 1:1) to obtain the target product (DPM-C12) (7.7 g, 22.2 mmol) in a white solid phase in a yield of 63%.

(21) <NMR analysis result of DPM-C12>

(22) .sup.1H-NMR (CDCl.sub.3): d7.02 (dd, 2H); δd6.89 (dd, 2H); d6.32 (dt, 1H); d5.73 (dt, 1H); d3.94 (t, 2H); δd2.05 (dd, 3H); d1.76 (p, 2H); δd1.43 (p, 2H); 1.34-1.27 (m, 16H); d0.88 (t, 3H).

(23) ##STR00008##

(24) In Formula A, R is a linear alkyl group having 12 carbon atoms.

Preparation Example 2. Synthesis of Triblock Copolymer (A1)

(25) 5.0 g of the compound (DPM-C12) of Preparation Example 1 and 63.9 mg of an RAFT (reversible addition-fragmentation chain transfer) reagent (dCPD-TTC, didodecyl ((2S, 2′S)-(ethane-1,2-diylbis(azanediyl))bis(2-cyano-5-oxopentane-5,2-diyl)) dicarbonotrithioate), 23.7 mg of AIBN (azobisisobutyronitrile) and 11.87 g of anisole were placed in a 25 mL flask (Schlenk flask) and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then an RAFT (reversible addition-fragmentation chain transfer) polymerization reaction was performed at 70° C. for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pink macro initiator. The number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the macro initiator were 15.7 Kg/mol and 1.22, respectively.

(26) 0.2 g of the macro initiator, 1.89 g of pentafluorostyrene, 0.8 mg of AIBN (azobisisobutyronitrile) and 0.70 g of anisole were placed in a 10 mL flask (Schlenk flask), stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then an RAFT (reversible addition-fragmentation chain transfer) polymerization reaction was performed at 70° C. for 7 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pale yellow triblock copolymer (A1). The number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the block copolymer were 57.1 Kg/mol and 1.30, respectively. The block copolymer was in the form of the triblock copolymer in which polymer segments B and C derived from pentafluorostyrene were linked to both sides of the polymer segment A derived from the compound (DPM-C12) of Preparation Example 1.

(27) In addition, the volume fraction of the polymer segment A (when the total volume fraction was taken as ′) in the block copolymer was about 0.34.

Preparation Example 3. Synthesis of Triblock Copolymer (A2)

(28) 5.0 g of the compound (DPM-C12) of Preparation Example 1 and 61.0 mg of an RAFT (reversible addition-fragmentation chain transfer) reagent (dCPD-TTC, didodecyl ((2S, 2′S)-(ethane-1,2-diylbis(azanediyl))bis(2-cyano-5-oxopentane-5,2-diyl)) dicarbonotrithioate), 22.8 mg of AIBN (azobisisobutyronitrile) and 11.85 g of anisole were placed in a 25 mL flask (Schlenk flask) and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then an RAFT (reversible addition-fragmentation chain transfer) polymerization reaction was performed at 70° C. for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pink macro initiator. The number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the macro initiator were 14.1 Kg/mol and 1.23, respectively.

(29) 0.2 g of the macro initiator, 1.73 g of pentafluorostyrene, 0.6 mg of AIBN (azobisisobutyronitrile) and 1.0 g of anisole were placed in a 10 mL flask (Schlenk flask), stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then an RAFT (reversible addition-fragmentation chain transfer) polymerization reaction was performed at 70° C. for 5 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pale yellow triblock copolymer (A2). The number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the block copolymer were 41.3 Kg/mol and 1.31, respectively. The block copolymer was in the form of the triblock copolymer in which polymer segments B and C derived from pentafluorostyrene were linked to both sides of the polymer segment A derived from the compound (DPM-C12) of Preparation Example 1.

(30) In addition, the volume fraction of the polymer segment A (when the total volume fraction was taken as ′) in the block copolymer was about 0.46.

Preparation Example 4. Synthesis of Diblock Copolymer (A3)

(31) 5.0 g of the compound (DPM-C12) of Preparation Example 1 and 106.5 mg of an RAFT (reversible addition-fragmentation chain transfer) reagent (CPDB, 2-cyano-2-propyl benzodithioate), 39.5 mg of AIBN (azobisisobutyronitrile) and 12 g of anisole were placed in a 25 mL flask (Schlenk flask) and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then an RAFT (reversible addition-fragmentation chain transfer) polymerization reaction was performed at 70° C. for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pink macro initiator. The number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the macro initiator were 17.9 Kg/mol and 1.27, respectively.

(32) 0.2 g of the macro initiator, 2.60 g of pentafluorostyrene, 0.9 mg of AIBN (azobisisobutyronitrile) and 0.93 g of anisole were placed in a 10 mL flask (Schlenk flask), stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then an RAFT (reversible addition-fragmentation chain transfer) polymerization reaction was performed at 70° C. for 5 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pale pink block copolymer (A3). The number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the block copolymer were 55.8 Kg/mol and 1.36, respectively. The block copolymer was in the form of the diblock copolymer in which polymer segment B derived from pentafluorostyrene was linked to one side of the polymer segment A derived from the compound (DPM-C12) of Preparation Example 1.

Example 1

(33) A self-assembled polymer film was formed using the triblock copolymer (A1) synthesized in Preparation Example 2, and the result was confirmed. Specifically, the copolymer was dissolved in fluorobenzene to a concentration of about 0.8 wt %, and spin-coated on a silicon wafer having a trench pattern (width 150 nm, depth 70 nm) to a thickness of about 32 nm (coating area: width 1.5 cm, height 1.5 cm). Thereafter, it was dried at room temperature for about 1 hour, again subjected to thermal annealing at a temperature of about 180° C. for about 1 hour and self-assembled. Thereafter, an SEM (scanning electron microscope) was photographed on the polymer film to evaluate self-assembly efficiency. FIG. 1 is the results for Example 1. From the drawing, it could be confirmed that an appropriate line pattern was formed in the case of Example 1.

Example 2

(34) A self-assembled polymer film was formed using the triblock copolymer (A2) synthesized in Preparation Example 3, and the result was confirmed. Specifically, the copolymer was dissolved in fluorobenzene to a concentration of about 0.8 wt %, and spin-coated on a silicon wafer having a trench pattern (width 150 nm, depth 70 nm) to a thickness of about 32 nm (coating area: width 1.5 cm, height 1.5 cm). Thereafter, it was dried at room temperature for about 1 hour, again subjected to thermal annealing at a temperature of about 180° C. for about 1 hour and self-assembled. Thereafter, an SEM (scanning electron microscope) was photographed on the polymer film to evaluate self-assembly efficiency. FIG. 2 is the results for Example 2. From the drawing, it could be confirmed that an appropriate line pattern was formed in the case of Example 1.

Comparative Example 1

(35) A self-assembled polymer film was formed using the diblock copolymer (A3) synthesized in Preparation Example 4, and the result was confirmed. Specifically, the copolymer was dissolved in fluorobenzene to a concentration of about 0.8 wt %, and spin-coated on a silicon wafer having a trench pattern (width 150 nm, depth 70 nm) to a thickness of about 32 nm (coating area: width 1.5 cm, height 1.5 cm). Thereafter, it was dried at room temperature for about 1 hour, again subjected to thermal annealing at a temperature of about 180° C. for about 1 hour and self-assembled. Thereafter, an SEM (scanning electron microscope) was photographed on the polymer film to evaluate self-assembly efficiency. FIG. 3 is the results for Comparative Example 1. From the drawing, it could be confirmed that, in the case of Comparative Example 1, even though it had molecular weight characteristics similar to those of the triblock copolymer of Example 1, an appropriate pattern was not formed and effective phase separation was not achieved.