Composite for neutral layer

Abstract

The present application relates to a neutral layer composition. The present application can provide a neutral layer composition capable of forming a neutral layer, which can be effectively applied in the formation of a polymeric film comprising a vertically aligned self-assembled block copolymer.

Claims

1. A laminate comprising a neutral layer; and a polymer film formed on one surface of the neutral layer and comprising a block copolymer having a first block and a second block chemically distinct from the first block, wherein the neutral layer comprises a random copolymer, and wherein the first block of the block copolymer and the random copolymer each contain a unit of Formula 1 below: ##STR00010## wherein, X is an oxygen atom, C(O), OC(O), C(O)O or a divalent linker represented by Formula 2 below, and Y is a monovalent hydrocarbon group having 3 to 30 carbon atoms; ##STR00011## wherein, T is a divalent hydrocarbon group, and m is a number within a range of 1 to 5.

2. The laminate according to claim 1, wherein the unit of Formula 1 in the random copolymer has a ratio in a range of 10% by mole to 90% by mole.

3. The laminate according to claim 1, wherein the random copolymer further comprises a unit represented by any one of Formulas 3 to 7: ##STR00012## wherein, R is hydrogen or an alkyl group, and T is a single bond or a divalent hydrocarbon group with or without a hetero atom; ##STR00013## 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; ##STR00014## wherein, R is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without a hetero atom; ##STR00015## wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and T is a divalent hydrocarbon group with or without a hetero atom; and ##STR00016## 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.3 or X.sub.3C(O), where X.sub.3 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, a halogen atom or a cross-linkable functional group, where the number of the cross-linkable functional groups contained in R.sub.1 to R.sub.5 is one or more.

4. The laminate according to claim 1, wherein the unit of Formula 1 is substituted with a cross-linkable functional group.

5. The laminate according to claim 1, wherein the random copolymer further comprises a polymerized unit derived from a (meth)acrylic acid ester compound, a polymerized unit derived from vinylpyridine, or a polymerized unit derived from a styrenic monomer.

6. The laminate according to claim 1, wherein the random copolymer further comprises a unit of Formula 9 below: ##STR00017## wherein, R.sub.1 is hydrogen or an alkyl group, and R.sub.2 is an alkyl group.

7. The laminate according to claim 1, wherein the random copolymer has a number average molecular weight in a range of 2000 to 500000.

8. The laminate according to claim 1, wherein the block copolymer embodies a sphere, cylinder, gyroid or lamellar structure.

9. A method for manufacturing the laminate according to claim 1 comprising a step of forming a neutral layer; and a polymer film formed on one surface of the neutral layer and comprising a block copolymer having a first block and a second block chemically distinct from said first block in a self-assembled state, wherein the neutral layer comprises a random copolymer, and wherein the first block of the block copolymer and the random copolymer each contain a unit of Formula 1 defined in claim 1.

10. A method for forming a pattern comprising a step of selectively removing the first or second block of the block copolymer in the polymer film of the laminate of claim 9.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 and 2 are views showing orientation results of block copolymers in Comparative Examples and Examples.

MODE FOR INVENTION

(2) 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.

(3) 1. NMR Measurement

(4) 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.

(5) <Application Abbreviations>

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

(7) 2. GPC (Gel Permeation Chromatograph)

(8) 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 macroinitiators 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.

(9) <GPC Measurement Conditions> Device: 1200 series from Agilent Technologies Column: using two PLgel mixed B from Polymer laboratories Solvent: THF Column temperature: 35 C. Sample concentration: 1 mg/mL, 200 L injection Standard samples: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

Preparation Example 1. Synthesis of Compound (A)

(10) A compound (hereinafter, compound (A)), in which in Formula A below, X is a residue of Formula B below, and in Formula B above, T is methylene, m is 1 and Y of Formula A is a dodecyl group, was synthesized by the following method. T of Formula B was linked to the benzene ring, and the oxygen atom was linked to Y, i.e., the dodecyl group. In a 500 mL flask, 4-(chloromethyl)styrene (22.1 g, 144.8 mmol) and 1-dodecanol (30.0 g, 160.1 mmol) were dissolved in 300 mL of tetrahydrofuran (THF) and then the temperature was lowered to 0 C. Sodium hydride (NaH) (7.7 g, 320.8 mmol) was divided in small portions, added thereto, and the mixture was stirred for 1 hour and then heated to 70 C. to be reacted for 24 hours. Upon completing the reaction, the reaction mixture was cooled to room temperature, and then a small amount of water was added thereto on ice water and reacted with sodium hydride remaining after the reaction, followed by removing the solid content through a filter. After removing tetrahydrofuran which is a reaction solvent, the reaction mixture was subjected to fractional extraction with dichloromethane (DCM)/secondary pure water to collect an organic layer, and then the resulting compound was subjected to column chromatography using hexane/dichloromethane as a mobile phase to obtain a transparent liquid compound (A) (23.9 g, 79.0 mmol).

(11) <NMR Analysis Result>

(12) .sup.1H-NMR (CDCl.sub.3): 7.39 (dd, 2H); 7.30 (dd, 2H); 6.71 (dd, 1H); 5.74 (d, 1H); 5.23 (d, 1H); 4.49 (s, 2H); 3.46 (t, 2H); 1.61 (p, 2H); 1.37-1.26 (m, 16H); 0.89 (t, 3H).

(13) ##STR00009##

Preparation Example 2. Synthesis of Block Copolymer (A)

(14) AIBN (azobisisobutyronitrile) and an RAFT reagent (CPDB, 2-cyanoprop-2-yl-benzodithioate) as thermal initiators were reacted with methyl methacrylate (MMA) to synthesize a macroinitiator (number average molecular weight (Mn): 8500, molecular weight distribution (Mw/Mn): 1.16). The synthesized macroinitiator and the compound (A) and AIBN (azobisisobutyronitrile) were diluted in anisole at an equivalent ratio of 1:100:0.5 (macroinitiator:compound (A):AIBN) to prepare a solution having a solid content concentration of about 30% by weight. Thereafter, the mixed liquid was reacted in a nitrogen atmosphere at 70 C. for 4 hours to obtain a block copolymer (A). The number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the block copolymer (A) were 14800 and 1.16, respectively. The block copolymer comprises the repeating unit derived from the methyl methacrylate and the repeating unit derived from the compound A, that is, the unit in which in a state where XY in Formula 1 of claim 1 is linked to the para position, X is a unit of Formula 2 of claim 1, where T is methylene and m is 1, and Y is a dodecyl group (T in Formula 2 is linked to the benzene ring, and the oxygen atom is linked to Y, i.e., the dodecyl group).

Preparation Example 3. Synthesis of Random Copolymer (B)

(15) A random copolymer (B) for a neutral layer was synthesized by using methyl methacrylate (MMA), the compound (A) and glycidyl methacrylate (GMA). MMA, the compound (A), GMA and AIBN were diluted in anisole at an equivalent ratio of 50:48:2:0.5 (MMA:compound (A):GMA:AIBN) to prepare a solution having a solid content concentration of about 60% by weight. Thereafter, the mixed liquid was reacted in a nitrogen atmosphere at 60 C. for 10 hours to obtain a random copolymer (B). The number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the random copolymer (B) were 106600 and 2.50, respectively.

Comparative Example 1

(16) Self-Assembly of the Block Copolymer (A)

(17) A self-assembled polymer film was formed using the block copolymer (A) of Preparation Example 2 and the results were confirmed. Specifically, the copolymer was dissolved in toluene at a concentration of about 1.0% by weight, 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 160 C. to form a film comprising the self-assembled block copolymer. FIG. 1 is an SEM image of the polymer film formed as described above. It can be confirmed from the drawing that the orientation of the polymer film has been not properly formed.

Example 1

(18) Self-Assembly of the Block Copolymer (A) Introducing the Neutral Layer of the Random Copolymer (B)

(19) 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 film were formed, respectively, and the results were confirmed. Specifically, the random copolymer (B) of Preparation Example 3 was first dissolved in toluene at a concentration of about 1.0% by weight, 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 160 C. to form a cross-linked neutral layer. The block copolymer (A) was dissolved in toluene at a concentration of about 1.0% by weight, 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 160 C. to form a film comprising the self-assembled block copolymer. FIG. 2 is an SEM image of the polymer film formed as described above. It can be confirmed from the drawing that a proper lamellar vertical orientation structure has been formed.