Neutral layer composition

Abstract

A neutral layer composition, which is capable of forming a neutral layer that can effectively control orientation characteristics of various block copolymers is provided.

Claims

1. A neutral layer composition comprising: a random copolymer having a unit of Formula 1 below: ##STR00008## wherein, 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 that is unsubstituted or having one or more carbon atoms substituted with oxygen.

2. The neutral layer composition according to claim 1, wherein Q.sub.1 is —O-L.sub.1-C(═O)— and L.sub.1 is an alkylene group having 1 to 4 carbon atoms.

3. The neutral layer composition according to claim 1, wherein X.sub.1 is —N(R.sub.2)-L.sub.2-C(═O)—O— and L.sub.2 is an alkylene group having 1 to 4 carbon atoms or an alkylidene group having 2 to 4 carbon atoms.

4. The neutral layer composition according to claim 1, wherein Y.sub.1 is a hydrocarbon chain having 8 to 20 carbon atoms.

5. The neutral layer composition according to claim 1, wherein Y.sub.1 is an alkyl group having 8 to 20 carbon atoms.

6. The neutral layer composition according to claim 1, wherein the unit of Formula 1 in the random copolymer has a volume fraction in a range of 10% to 65%.

7. The neutral layer composition according to claim 1, wherein the random copolymer further comprises a unit represented by any one of Formula 2, 3, or 4: ##STR00009## wherein, R is hydrogen or an alkyl group and T is a single bond or a divalent hydrocarbon group containing or not containing a hetero atom; ##STR00010## wherein, R is hydrogen or an alkyl group, A is an alkylene group, R.sub.1 is hydrogen, a halogen atom, an alkyl group or a haloalkyl group, and n is a number in a range of 1 to 3; ##STR00011## wherein, R is hydrogen or an alkyl group and T is a divalent hydrocarbon group containing or not containing a hetero atom.

8. The neutral layer composition according to claim 1, wherein the random copolymer further comprises a unit of Formula 6 below: ##STR00012## wherein, X.sub.2 is a single bond, an oxygen atom or a sulfur atom, and R.sub.1 to R.sub.5 are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, wherein a number of halogen atoms contained in R.sub.1 to R.sub.5 is 3 or more.

9. The neutral layer composition according to claim 8, wherein the unit of Formula 6 in the random copolymer has a volume fraction in a range of 35% to 90%.

10. The neutral layer composition according to claim 1, wherein the random copolymer has a number average molecular weight in a range of 2,000 to 500,000.

11. A neutral layer comprising a random copolymer containing a unit of Formula 1 below: ##STR00013## wherein, 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- and 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 linear hydrocarbon that is unsubstituted or having one or more carbon atoms substituted with oxygen.

12. A method for forming a neutral layer, comprising: coating the neutral layer composition of claim 1 on a substrate to form a coated neutral layer; and fixing the coated neutral layer.

13. A laminate comprising: the neutral layer of claim 11; and a polymer membrane formed on one surface of the neutral layer and containing a block copolymer having a first block and a second block different from the first block.

14. The laminate according to claim 13, wherein the block copolymer has a sphere, cylinder, gyroid or lamellar structure.

15. The laminate according to claim 13, wherein the first block of the block copolymer comprises a unit of Formula 1 below: ##STR00014## wherein, 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 chain having 4 or more chain-forming atoms.

16. A method for manufacturing a laminate comprising: forming the neutral layer of claim 11; and forming a polymer membrane formed on one surface of the neutral layer and containing a block copolymer having a first block and a second block different from the first block in a self-assembled state.

17. A pattern forming method comprising: selectively removing the first or second block of the block copolymer in the polymer membrane of the laminate of claim 13.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an SEM photograph of a polymer membrane according to a comparative example of the present application.

(2) FIGS. 2 to 6 are SEM photographs of self-assembled structures of block copolymers formed on random copolymers of Examples 1 to 5 of the present application, respectively.

MODE FOR INVENTION

(3) Hereinafter, the present application will be described more 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) The NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. An analyte was diluted in a solvent for measuring NMR (CDCl.sub.3) to a concentration of about 10 mg/ml and used, and chemical shifts were expressed in ppm.

(6) <Application Abbreviations>

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

(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). Analytes such as the block copolymers of Examples or Comparative Examples or macro initiators are introduced into a 5 mL vial and diluted in THF (tetrahydrofuran) so as to be a concentration of about 1 mg/mL. Then, the calibration standard sample and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 m) and then measured. As an 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 to calculate the molecular weight distribution (PDI) from the ratio (Mw/Mn). The measurement conditions of GPC are as follows.

(10) <GPC Measurement Conditions>

(11) Device: 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 μL injection

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

Preparation Example 1. Synthesis of Compound (A)

(17) The 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 and dissolved in methylene chloride (MC) (300 mL), followed by adding DCC (N,N′-dicyclohexylcarbodiimide) (14.4 g, 68.5 mmol) and DMAP (p-dimethylaminopyridine) (2.8 g, 22.8 mmol) sequentially. The mixture was stirred at room temperature and subjected to reaction overnight, and then filtered to remove solids. The remaining solution was collected and subjected to a column with an EA (ethyl acetate)/hexane solution (EA:hexane=1:5) to obtain a colorless liquid intermediate A1.

(18) The intermediate A1 was placed in a flask, dissolved in 1,4-dioxane (120 mL) and then a hydrochloric acid solution (4N in 1,4-dioxane, 60 mL) was added thereto while stirring in an ice bath, and the mixture was reacted at room temperature overnight. An excessive amount of MC was added to the reaction solution, which was filtered, and the solid content was washed several times with MC to obtain a white solid intermediate A2 (13.0 g, 46.5 mmol), which was dried in a vacuum oven, and then the following reaction was performed.

(19) <NMR Analysis Results>

(20) .sup.1H-NMR (CDCl.sub.3): δ8.44 (s, 3H); δ4.13 (t, 2H); δ3.76 (s, 2H); δ1.58 (tt, 2H); δ1.30-1.23 (m, 18H); δ0.88 (t, 3H).

(21) The intermediate A2 (13.0 g, 46.5 mmol) was placed in a flask, MC (150 mL) was added to disperse it, and chloroacetyl chloride (10.5 g, 92.9 mmol) was added thereto. TEA (tetraethylammonium) (14.1 g, 139.4 mmol) was slowly added with stirring in an ice bath and the mixture was reacted overnight at room temperature. After the reaction was completed, the solid content was removed by a filter, and the remaining solution was collected and subjected to a column with an EA/hexane (1:5) solution, and the obtained solid was washed with hexane to remove impurities, thereby obtaining a white solid intermediate A3 (11.1 g, 34.7 mmol).

(22) <NMR Analysis Results>

(23) .sup.1H-NMR (CDCl.sub.3): δ7.07 (s, 1H); δ4.17 (t, 2H); δ4.09 (s, 2H); δ4.08 (d, 2H); δ1.65 (tt, 2H); δ1.40-1.26 (m, 18H); δ0.88 (t, 3H)

(24) The intermediate A3 (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, to which excess water was poured, and extracted with diethyl ether. The organic layer was collected, dried over magnesium sulfate and subjected to a column after removing the solvent to obtain a compound of Formula A below as a white solid phase (11.8 g, 31.9 mmol).

(25) <NMR Analysis Results>

(26) .sup.1H-NMR (CDCl.sub.3): δ6.67 (s, 1H); δ6.23 (s, 1H); δ5.71 (s, 1H); δ4.70 (s, 2H); δ4.17 (t, 2H); δ4.09 (d, 2H), δ2.02 (s, 3H), δ1.65 (tt, 2H). δ1.34-1.26 (m, 18H); δ0.88 (t, 3H)

(27) ##STR00007##

(28) In Formula A, R.sub.1 is methyl, Q.sub.1 is —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 and L.sub.2 are methylene and R.sub.2 is hydrogen, and Y.sub.1 is a dodecyl group.

Preparation Example 2. Synthesis of Block Copolymer (A)

(29) 3 g of the compound of Formula A in Preparation Example 1, 3.3 mg of 1,1′-azobis(cyclohexane-1-carbonitrile), 33.3 mg of CPCDB (2-cyano-2-propyl 4-cyanobenzodithioate) (33.3 mg) as an RAFT agent (reversible addition-fragmentation chain transfer agent) and 12.1 g of anisole were placed in a flask, stirred at room temperature for 1 hour under a nitrogen atmosphere and then subjected to RAFT polymerization in a silicone oil vessel at 95° C. for about 1 hour. After the polymerization, the reaction solution was precipitated twice in 400 mL of methanol, and then filtered under reduced pressure and dried to synthesize a polymer of the compound of Formula A above, in which the RAFT reagent was bonded to the terminal, as a macro initiator (number average molecular weight Mn: 13,500, molecular weight distribution PDI: 1.17).

(30) 0.5 g of the macro initiator, 2.16 g of pentafluorostyrene and 0.9 mg of 1,1′-azobis(cyclohexane-1-carbonitrile) were dissolved in 2.66 g of trifluorotoluene in a flask, stirred at room temperature for 1 hour under a nitrogen atmosphere and then subjected to RAFT polymerization in a silicone oil vessel at 95° C. for about 20 hours. After the polymerization, the reaction solution was precipitated twice in 400 mL of methanol and then filtered under reduced pressure to synthesize a target block copolymer (number average molecular weight Mn: 40,300, molecular weight distribution PDI: 1.21).

Preparation Example 3. Synthesis of Random Copolymer (B)

(31) 0.52 g of the compound of Formula A in Preparation Example 1, 33 mg of AIBN (azobisisobutyronitrile), 1.48 g of pentafluorostyrene, 142 mg of GMA (glycidyl methacrylate) and 2.17 g of tetrahydrofuran were placed in a flask, stirred at room temperature for 1 hour under a nitrogen atmosphere and then subjected to free radical polymerization (FRP) in a silicone oil vessel at 60° C. for about 12 hours. After the polymerization, the reaction solution was precipitated twice in 400 mL of methanol, and then filtered under reduced pressure and dried to synthesize a random copolymer of the compound of Formula A above (number average molecular weight Mn: 37,400, molecular weight distribution PDI: 1.98).

Preparation Example 4. Synthesis of Random Copolymer (C)

(32) 0.68 g of the compound of Formula A in Preparation Example 1, 33 mg of AIBN (azobisisobutyronitrile), 1.39 g of pentafluorostyrene, 142 mg of GMA (glycidyl methacrylate) and 2.25 g of tetrahydrofuran were placed in a flask, stirred at room temperature for 1 hour under a nitrogen atmosphere and then subjected to free radical polymerization (FRP) in a silicone oil vessel at 60° C. for about 12 hours. After the polymerization, the reaction solution was precipitated twice in 400 mL of methanol, and then filtered under reduced pressure and dried to synthesize a random copolymer of the compound of Formula A above (number average molecular weight Mn: 35,700, molecular weight distribution PDI: 1.98).

Preparation Example 5. Synthesis of Random Copolymer (D)

(33) 1.70 g of the compound of Formula A in Preparation Example 1, 32 mg of AIBN (azobisisobutyronitrile), 5.82 g of pentafluorostyrene, 0.1 g of HEMA (2-hydroxymethyl methacrylate) and 7.52 g of tetrahydrofuran were placed in a flask, stirred at room temperature for 1 hour under a nitrogen atmosphere and then subjected to free radical polymerization (FRP) in a silicone oil vessel at 60° C. for about 12 hours. After the polymerization, the reaction solution was precipitated twice in 400 mL of methanol, and then filtered under reduced pressure and dried to synthesize a random copolymer of the compound of Formula A above (number average molecular weight Mn: 31,800, molecular weight distribution PDI: 1.91).

Preparation Example 6. Synthesis of Compound (B)

(34) The compound (B) was synthesized in the same manner as in Preparation Example 1, except that 1-octanol was used instead of 1-dodecanol. NMR analysis results for the compound were shown below. As the compound (B), a compound was synthesized, in which in Formula A of Preparation Example 1, R.sub.1 is methyl, Q.sub.1 is —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 and L.sub.2 are methylene and R.sub.2 is hydrogen, and Y.sub.1 is an octyl group.

(35) <NMR Analysis Results>

(36) .sup.1H-NMR (CDCl.sub.3): δ6.67 (s, 1H); δ6.24 (s, 1H); δ5.71 (s, 1H); δ4.70 (s, 2H); δ4.17 (t, 2H); δ4.09 (d, 2H), δ2.02 (s, 3H), δ1.65 (tt, 2H). δ1.34-1.26 (m, 10H); δ0.88 (t, 3H)

Preparation Example 7. Synthesis of Compound (C)

(37) The compound (C) was synthesized in the same manner as in Preparation Example 1, except that 1-hexadecanol was used instead of 1-dodecanol. The compound (C) is a compound, in which in Formula A of Preparation Example 1, R.sub.1 is methyl, Q.sub.1 is —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 and L.sub.2 are methylene and R.sub.2 is hydrogen, and Y.sub.1 is an hexadecyl group. NMR analysis results for the compound were shown below.

(38) <NMR Analysis Results>

(39) .sup.1H-NMR (CDCl.sub.3): δ6.67 (s, 1H); δ6.24 (s, 1H); δ5.71 (s, 1H); δ4.70 (s, 2H); δ4.17 (t, 2H); δ4.09 (d, 2H), δ2.02 (s, 3H), δ1.65 (tt, 2H). δ1.34-1.26 (m, 26H); δ0.88 (t, 3H)

Preparation Example 8. Synthesis of Random Copolymer (E)

(40) 0.44 g of the compound (B) of Preparation Example 6, 33 mg of AIBN (azobisisobutyronitrile), 1.48 g of pentafluorostyrene, 142 mg of GMA (glycidyl methacrylate) and 2.09 g of tetrahydrofuran were placed in a flask, stirred at room temperature for 1 hour under a nitrogen atmosphere and then subjected to free radical polymerization (FRP) in a silicone oil vessel at 60° C. for about 12 hours.

(41) After the polymerization, the reaction solution was precipitated twice in 400 mL of methanol, and then filtered under reduced pressure and dried to synthesize a random copolymer (E) containing the unit of the compound (B) (number average molecular weight (Mn): 33,700 molecular weight distribution PDI): 1.92).

Preparation Example 9. Synthesis of Random Copolymer (F)

(42) 0.60 g of the compound (C) of Preparation Example 7, 33 mg of AIBN (azobisisobutyronitrile), 1.48 g of pentafluorostyrene, 142 mg of GMA (glycidyl methacrylate) and 2.25 g of tetrahydrofuran were placed in a flask, stirred at room temperature for 1 hour under a nitrogen atmosphere and then subjected to free radical polymerization (FRP) in a silicone oil vessel at 60° C. for about 12 hours. After the polymerization, the reaction solution was precipitated twice in 400 mL of methanol, and then filtered under reduced pressure and dried to synthesize a random copolymer (F) (number average molecular weight Mn: 40,300 molecular weight distribution PDI: 2.02).

Comparative Example 1. Self-Assembly of Block Copolymer (A)

(43) A self-assembled polymer membrane was formed using the block copolymer (A) of Preparation Example 2 and the results were confirmed. Specifically, the copolymer was dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating liquid was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds and then subjected to thermal annealing at about 200° C. to form a membrane comprising the self-assembled block copolymer. FIG. 1 is an SEM image of the polymer membrane formed as described above. It can be confirmed from the drawing that the orientation of the polymer membrane has been not properly formed.

Example 1. Self-Assembly of the Block Copolymer (A) Introducing the Neutral Layer of the Random Copolymer (B)

(44) Using the random copolymer (B) of Preparation Example 3 and the block copolymer (A) of Preparation Example 2, a cross-linked neutral layer and a self-assembled polymer membrane were formed, respectively, and the results were confirmed. Specifically, the random copolymer (B) of Preparation Example 3 was first dissolved in fluorobenzene at a concentration of about 0.5 wt %, and the prepared coating liquid was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, and then subjected to thermal cross-linking at about 200° C. to form a cross-linked neutral layer. The block copolymer (A) was dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating solution was spin-coated on the neutral layer at a rate of 3000 rpm for 60 seconds, and then subjected to thermal annealing at about 200° C. to form a membrane comprising the self-assembled block copolymer. FIG. 2 is an SEM image of the polymer membrane formed as described above. It can be confirmed from the drawing that a proper lamellar vertical orientation structure has been formed.

Example 2. Self-Assembly of the Block Copolymer (A) Introducing the Neutral Layer of the Random Copolymer (C)

(45) Using the random copolymer (C) of Preparation Example 4 and the block copolymer (A) of Preparation Example 2, a cross-linked neutral layer and a self-assembled polymer membrane were formed, respectively, and the results were confirmed. Specifically, the random copolymer (C) of Preparation Example 4 was first dissolved in fluorobenzene at a concentration of about 0.5 wt %, and the prepared coating liquid was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, and then subjected to thermal cross-linking at about 200° C. to form a cross-linked neutral layer. The block copolymer (A) was dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating solution was spin-coated on the neutral layer at a rate of 3000 rpm for 60 seconds, and then subjected to thermal annealing at about 200° C. to form a membrane comprising the self-assembled block copolymer. FIG. 3 is an SEM image of the polymer membrane formed as described above. It can be confirmed from the drawing that a proper lamellar vertical orientation structure has been formed.

Example 3. Self-Assembly of the Block Copolymer (A) Introducing the Neutral Layer of the Random Copolymer (D)

(46) Using the random copolymer (D) of Preparation Example 5 and the block copolymer (A) of Preparation Example 2, a cross-linked neutral layer and a self-assembled polymer membrane were formed, respectively, and the results were confirmed. Specifically, the random copolymer (D) of Preparation Example 5 was first dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating liquid was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, and then subjected to thermal cross-linking at about 200° C. to form a cross-linked neutral layer. The block copolymer (A) was dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating solution was spin-coated on the neutral layer at a rate of 3000 rpm for 60 seconds, and then subjected to thermal annealing at about 200° C. to form a membrane comprising the self-assembled block copolymer. FIG. 4 is an SEM image of the polymer membrane formed as described above. It can be confirmed from the drawing that a proper lamellar vertical orientation structure has been formed.

Example 4. Self-Assembly of the Block Copolymer (A) Introducing the Neutral Layer of the Random Copolymer (E)

(47) Using the random copolymer (E) of Preparation Example 8 and the block copolymer (A) of Preparation Example 2, a cross-linked neutral layer and a self-assembled polymer membrane were formed, respectively, and the results were confirmed. Specifically, the random copolymer (E) of Preparation Example 8 was first dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating liquid was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, and then subjected to thermal cross-linking at about 200° C. to form a cross-linked neutral layer. The block copolymer (A) was dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating solution was spin-coated on the neutral layer at a rate of 3000 rpm for 60 seconds, and then subjected to thermal annealing at about 200° C. to form a membrane comprising the self-assembled block copolymer. FIG. 5 is an SEM image of the polymer membrane formed as described above. It can be confirmed from the drawing that a proper lamellar vertical orientation structure has been formed.

Example 5. Self-Assembly of the Block Copolymer (A) Introducing the Neutral Layer of the Random Copolymer (F)

(48) Using the random copolymer (F) of Preparation Example 9 and the block copolymer (A) of Preparation Example 2, a cross-linked neutral layer and a self-assembled polymer membrane were formed, respectively, and the results were confirmed. Specifically, the random copolymer (F) of Preparation Example 9 was first dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating liquid was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, and then subjected to thermal cross-linking at about 200° C. to form a cross-linked neutral layer. The block copolymer (A) was dissolved in fluorobenzene at a concentration of about 1.0 wt %, and the prepared coating solution was spin-coated on the neutral layer at a rate of 3000 rpm for 60 seconds, and then subjected to thermal annealing at about 200° C. to form a membrane comprising the self-assembled block copolymer. FIG. 6 is an SEM image of the polymer membrane formed as described above. It can be confirmed from the drawing that a proper lamellar vertical orientation structure has been formed.

(49) Referring to FIGS. 2 to 6, it can be confirmed that in the case of Examples 1 to 5, as the neutral layer composition comprising the random copolymer forms the neutral layer, the self-assembly structure of the block copolymer formed on the membrane containing the random copolymer is vertically oriented. On the other hand, referring to FIG. 1, it can be confirmed that in the case of the comparative example, the block copolymer does not exhibit uniform orientation characteristics when the membrane containing the block copolymer is formed on the substrate without neutral layer treatment.