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 1 below and a polymer segment B having a unit represented by Formula 9 below: ##STR00008## in Formula 1, R.sub.1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, Q.sub.1 is a single bond, —O-L.sub.1-C(═O)— or —O-L.sub.1-, X.sub.1 is —N(R.sub.2)-L.sub.2-C(═O)—O—, O—C(═O)—, —C(═O)—O—, a urethane linker or a urea linker, where L.sub.1 is an alkylene group having 1 to 4 carbon atoms, L.sub.2 is an alkylene group having 1 to 4 carbon atoms or an alkylidene group having 2 to 4 carbon atoms and R.sub.2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and Y.sub.1 is a linear hydrocarbon chain having 8 to 20 chain-forming atoms, wherein at least one carbon atom is optionally replaced with an oxygen, nitrogen or sulfur, and at least one hydrogen atom is optionally substituted with a substituent that is not a halogen atom; ##STR00009## in Formula 9, 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 the halogen atoms contained in R.sub.1 to R.sub.5 is 1 or more.

2. The block copolymer according to claim 1, wherein the block copolymer is in a diblock form containing only the polymer segments A and B as the polymer segments.

3. The block copolymer according to claim 2, wherein the polymer segment B is connected to one end of the polymer segment A.

4. The block copolymer according to claim 1, wherein in Formula 1, R.sub.1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, Q.sub.1 is a single bond or —O-L.sub.1-C(═O)—, and X.sub.1 is —N(R.sub.2)-L.sub.2-C(═O)—O—, where L.sub.1 is a linear alkylene group having 1 to 4 carbon atoms, L.sub.2 is a methylene group or an ethylidene group and R.sub.2 is hydrogen.

5. The block copolymer according to claim 1, wherein in Formula 1, R.sub.1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, Q.sub.1 is —O-L.sub.1-, and X.sub.1 is —O—C(═O)—, —C(═O)—O—, a urethane linker or a urea linker, where L.sub.1 is a linear alkylene group having 1 to 4 carbon atoms.

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

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

8. The block copolymer according to claim 1, wherein in Formula 9, X.sub.2 is a single bond, an oxygen atom, a sulfur atom or —S(═O).sub.2— and R.sub.1 to R.sub.5 are each a halogen atom.

9. The block copolymer according to claim 1, wherein in Formula 9, the halogen atom is a fluorine atom.

10. The block copolymer according to claim 1, wherein the sum of volume fraction of the polymer segment A and volume fraction of the polymer segment B is 1, and the volume fraction of the polymer segment A is in a range of 0.10 to 0.90.

11. The block copolymer according to claim 1, wherein in Formula 9, X.sub.2 is a single bond, an oxygen atom, an alkylene group, —C(═O)—O— or —O—C(═O)—.

12. The block copolymer according to claim 1, wherein in Formula 9, the number of halogen atoms contained in R.sub.1 to R.sub.5 is 5 or more.

13. The block copolymer according to claim 1, wherein the block copolymer has a number average molecular weight (Mn) in a range of 3,000 to 300,000.

14. The block copolymer according to claim 1, wherein the block copolymer has a polydispersity (Mw/Mn) in a range of 1.01 to 1.60.

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

16. 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 to 3 are photographs of self-assembled films formed by block copolymers.

(2) FIGS. 4 to 6 are views comparing etching selectivity.

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

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

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

Preparation Example 1

(17) A compound of Formula A below was synthesized in the following manner. Boc-glycine (10.0 g, 57.1 mmol) and 1-dodecanol (11.5 g, 68.5 mmol) were placed in a flask, dissolved in methylene chloride (MC) (300 mL), and then DCC (N,N′-dicylcohexylcarbodiimide) (14.4 g, 68.5 mmol) and DMAP (p-dimethylaminopyridine) (2.8 g, 22.8 mmol) were added thereto in this order. The mixture was stirred at room temperature and reacted overnight, and then filtered to remove solids. The remaining solution was collected and subjected to column with an EA (ethyl acetate)/hexane solution (EA:hexane=1:5) to obtain a colorless liquid intermediate A1 (14.3 g, 45.3 mmol).

(18) <NMR Analysis Result>

(19) .sup.1H-NMR (CDCl3): d5.00 (s, 1H); d4.13 (t, 2H); δ3.90 (d, 2H); d1.63 (tt, 2H); d1.45 (s, 9H); d1.37-1.22 (m, 18H); d0.88 (t, 3H)

(20) The intermediate A1 (14.3 g, 45.3 mmol) was placed in a flask, dissolved in 1,4-dioxane (120 mL), and then a solution of hydrochloric acid (4N in 1,4-dioxane, 60 mL) was added thereto with stirring in an ice bath and the mixture was reacted overnight at room temperature. An excess amount of MC was added to the reaction solution, filtered and the solid was washed several times with MC to obtain a white solid intermediate A2 (8.7 g, 34.7 mmol), which was dried in a vacuum oven, and then the next reaction was performed.

(21) The intermediate A2 (8.7 g, 34.7 mmol) was placed in a flask, MC (150 mL) was added thereto and the mixture was dispersed with vigorous stirring. In an ice bath, TEA (tetraethylammonium) (10.5 g, 104.1 mmol) is slowly added thereto, and if the reactants are well mixed, then methacryloyl chloride (4.0 g, 49.5 mmol) is added slowly thereto. The flask was taken out at room temperature, and the mixture was reacted overnight and subjected to column with a mixed solution of EA/hexane to obtain a target product (Formula A below) in a gray solid phase.

(22) <NMR Analysis Result>

(23) .sup.1H-NMR (CDCl.sub.3): d6.31 (s, 1H); d5.77 (s, 2H); δ5.39 (s, 1H); d4.16 (t, 2H); d4.10 (d, 2H); d1.99 (s, 3H), d1.65 (tt, 2H), d1.37-1.22 (m, 18H); d0.88 (t, 3H)

(24) ##STR00005##

(25) In Formula A, R.sub.1 is methyl, Q.sub.1 is a single bond, X.sub.1 is —N(R.sub.2)-L.sub.2-C(═O)—O—, L.sub.2 is methylene, R.sub.2 is hydrogen, and Y.sub.1 is a dodecyl group.

Preparation Example 2

(26) A compound of Formula B below was synthesized in the following manner. Boc-glycine (10.0 g, 57.1 mmol) and 1-dodecanol (11.5 g, 68.5 mmol) were placed in a flask, dissolved in methylene chloride (MC) (300 mL), and then DCC (N,N′-dicylcohexylcarbodiimide) (14.4 g, 68.5 mmol) and DMAP (p-dimethylaminopyridine) (2.8 g, 22.8 mmol) were added thereto in this order. The mixture was stirred at room temperature and reacted overnight, and then filtered to remove solids. The remaining solution was collected and subjected to column with an EA (ethyl acetate)/hexane solution (EA:hexane=1:5) to obtain a colorless liquid intermediate B1. The intermediate B1 was placed in a flask, dissolved in 1,4-dioxane (120 mL), and then a solution of hydrochloric acid (4N in 1,4-dioxane, 60 mL) was added thereto while stirring in an ice bath and the mixture was reacted overnight at room temperature. An excess amount of MC was added to the reaction solution, filtered and the solid was washed several times with MC to obtain a white solid intermediate B2 (13.0 g, 46.5 mmol), which was dried in a vacuum oven, and then the next reaction was performed.

(27) <NMR Analysis Result>

(28) .sup.1H-NMR (DMSO-d.sub.6): d8.44 (s, 3H); d4.13 (t, 2H); δ3.76 (s, 2H); d1.58 (tt, 2H); d1.30-1.23 (m, 18H); d0.88 (t, 3H)

(29) The intermediate B2 (13.0 g, 46.5 mmol) was placed in a flask, MC (150 mL) was added thereto and the mixture was dispersed, and chloroacetyl chloride (10.5 g, 92.9 mmol) was added thereto. In an ice bath, TEA (tetraethylammonium) (14.1 g, 139.4 mmol) was slowly added with stirring and the mixture was reacted overnight at room temperature. After completing the reaction, the solids were removed by a filter, the remaining solution was collected and subjected to column with an EA/hexane (1:5) solution, and the resulting solid was washed with hexane to remove impurities, thereby obtaining a white solid intermediate B3 (11.1 g, 34.7 mmol).

(30) <NMR Analysis Result>

(31) .sup.1H-NMR (CDCl.sub.3): d7.07 (s, 1H); d4.17 (t, 2H); δ4.09 (s, 2H); d4.08 (d, 2H); d1.65 (tt, 2H); d1.40-1.26 (m, 18H); d0.88 (t, 3H)

(32) The intermediate B3 (11.1 g, 34.7 mmol) and methacrylic acid (12.0 g, 138.8 mmol) are placed in a flask and dissolved in dimethylformamide (DMF) (200 mL) with stirring, and then potassium carbonate (28.8 g, 208.2 mmol) and potassium iodide (0.58 g, 3.48 mmol) are added thereto. The mixture was reacted at 80° C. for 2 hours, an excess amount of water was poured thereto, and the mixture was extracted with diethyl ether. The organic layer was collected and dried by magnesium sulfate, and after removing the solvent, the product was subjected to column to obtain a compound of Formula B below as a white solid phase (11.8 g, 31.9 mmol).

(33) <NMR Analysis Result>

(34) .sup.1H-NMR (CDCl.sub.3): d6.67 (s, 1H); d6.23 (s, 1H); δ5.71 (s, 1H); d4.70 (s, 2H); d4.17 (t, 2H); d4.09 (d, 2H), d2.02 (s, 3H), d1.65 (tt, 2H). d1.34-1.26 (m, 18H); d0.88 (t, 3H)

(35) ##STR00006##

(36) In Formula B, R.sub.1 is methyl, Q.sub.1 is —O-L.sub.1-C(═O)—, X.sub.1 is —N(R.sub.2)-L.sub.2-C(═O)—O—, where L.sub.1 and L.sub.2 are each methylene and R.sub.2 is hydrogen, and Y.sub.1 is a dodecyl group.

Preparation Example 3

(37) A compound (DPM-C12) of Formula C 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%.

(38) <NMR Analysis Result of Intermediate>

(39) .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).

(40) 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%.

(41) <NMR Analysis Result of DPM-C12>

(42) .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).

(43) ##STR00007##

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

Example 1

(45) 0.5 g of the compound of Formula A in Preparation Example 1, 2.6 mg of AIBN (azobisisobutyronitrile), 7.1 mg of CPBD (2-cyano-2-propyl benzodithioate) as an RAFT agent (reversible addition-fragmentation chain transfer agent) and 1.172 mL of anisole were placed in a flask and stirred at room temperature for 1 hour under a nitrogen atmosphere, and then an RAFT polymerization was performed in a silicone oil vessel at 70° C. for about 6 hours. After the polymerization, the reaction solution was precipitated twice in 300 mL of methanol, and then filtered under reduced pressure and dried to synthesize a polymer of the compound of Formula A in which the RAFT reagent was bonded to the end thereof as a macro initiator (number average molecular weight Mn: 10,500, molecular weight distribution PDI: 1.20).

(46) In a flask, 0.1768 g of the macro initiator, 1.961 g of pentafluorostyrene, and 2.0 mg of AIBN (azobisisobutyronitrile) were dissolved in 0.716 mL of anisole and stirred at room temperature for 1 hour under a nitrogen atmosphere, and then an RAFT polymerization reaction was performed in a silicone oil vessel at 115° C. for about 4 hours. After the polymerization, the reaction solution was precipitated twice in 250 mL of methanol and then filtered under reduced pressure to prepare a target block copolymer (number average molecular weight Mn: 28,100, molecular weight distribution PDI: 1.16).

Example 2

(47) 2 g of the compound of Formula B in Preparation Example 2, 11 mg of AIBN (azobisisobutyronitrile), 29.9 mg of CPBD (2-cyano-2-propyl benzodithioate) as an RAFT agent (reversible addition-fragmentation chain transfer agent) and 8.040 mL of anisole were placed in a flask and stirred at room temperature for 1 hour under a nitrogen atmosphere, and then an RAFT polymerization was performed for about 4 hours. After the polymerization, the reaction solution was precipitated twice in 300 mL of methanol, and then filtered under reduced pressure and dried to synthesize a polymer of the compound of Formula B in which the RAFT reagent was bonded to the end thereof as a macro initiator (number average molecular weight Mn: 14,500, molecular weight distribution PDI: 1.18).

(48) In a flask, 0.35 g of the macro initiator, 2.811 g of pentafluorostyrene, and 2.0 mg of AIBN (azobisisobutyronitrile) were dissolved in 3.176 mL of anisole and stirred at room temperature for 1 hour under a nitrogen atmosphere, and then an RAFT polymerization reaction was performed in a silicone oil vessel at 70° C. for about 6 hours. After the polymerization, the reaction solution was precipitated twice in 250 mL of methanol and then filtered under reduced pressure to prepare a target block copolymer (number average molecular weight Mn: 37,600, molecular weight distribution PDI: 1.27).

Comparative Example 1

(49) 2 g of the compound of Formula C in Preparation Example 3, 64 mg of CPBD (2-cyano-2-propyl benzodithioate) as an RAFT agent (reversible addition-fragmentation chain transfer agent), 23 mg of AIBN (azobisisobutyronitrile) and 5.34 mL of anisole were placed in a flask and stirred at room temperature for 1 hour under a nitrogen atmosphere, and then an RAFT polymerization was performed at 70° C. for about 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, and then filtered under reduced pressure and dried to synthesize a pink macro initiator (number average molecular weight Mn: 9,000, molecular weight distribution PDI: 1.16).

(50) In a flask, 0.3 g of the macro initiator, 2.7174 g of pentafluorostyrene, and 2.1 mg of AIBN (azobisisobutyronitrile) were dissolved in 1.306 mL of anisole and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then a polymerization reaction was performed at 115° C. for about 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol and then filtered under reduced pressure to prepare a pale pink target block copolymer (number average molecular weight Mn: 16,300, molecular weight distribution PDI: 1.13).

Test Example 1

Confirmation of Self-Assembly Pattern

(51) A coating liquid, in which the block copolymers synthesized in Examples 1 and 2 and Comparative Example 1 were each diluted in toluene to an appropriate concentration, was coated on a silicon wafer substrate at a speed of 3000 rpm for 60 seconds by using a spin coater to form a polymer thin film. Such a thin film was heat-treated at 220° C. for 1 hour to express a nanostructure on the surface of the thin film. FIGS. 1 and 2 are images of self-assembly patterns expressed for Examples 1 and 2, respectively, and FIG. 3 is an image of self-assembly patterns expressed for Comparative Example 1.

Test Example 2

Confirmation of Etching Selectivity

(52) The etching selectivity of the block copolymers of Examples 1 and 2 and Comparative Example 1 was evaluated. The etching selectivity was evaluated by preparing the respective blocks of each block copolymer of Examples 1 and 2 and Comparative Example 1 in a homopolymer form, forming a polymer film with the homopolymer, and then comparing the remaining thickness of the polymer film for each etching time while performing the etching under the same condition (RF power 25 W, pressure 10 mTorr) using an etching apparatus (Plasmalab system 100). FIGS. 4 to 6 show the results, and in FIGS. 4 to 6, the X-axis is the etching time and the Y-axis is the remaining thickness of the polymer film. The initial thickness of all polymer films was controlled to about 100 nm. Referring to FIG. 4, the etching rates of the homopolymer (Polymer A) of the compound of Formula A and the homopolymer film (PPFS) of PFS (pentafluorostyrene) are compared, and in FIG. 5, the etching rates of the homopolymer (Polymer B) of the compound of Formula B and the homopolymer film (PPFS) of PFS (pentafluorostyrene) are compared, and in FIG. 6, the etching rates of the homopolymer (Polymer C) of the compound of Formula C and the homopolymer film (PPFS) of PFS (pentafluorostyrene) are compared. It can be confirmed from the drawings that the etching rate of each block in the block polymers of Examples varies greatly over the etching time, but in the case of Comparative Example 1, no great difference in the etching rate occurs according to the etching time.