Polymer composition
Methods for forming a laminate are provided. The method provides a highly aligned block copolymer without orientation defects, coordination number defects distance defects and the like on a substrate, thereby providing a laminate which can be effectively applied to the production of various patterned substrates, and a method for producing a patterned substrate using the same.
1. A polymer composition comprising:
a block copolymer which comprises a polymer segment A containing a first monomer unit and a polymer segment B having an absolute value of a surface energy difference with the polymer segment A of 10 mN/m or less and the polymer segment B containing a second monomer unit; and
a random copolymer containing the first monomer unit and the second monomer unit, wherein the second monomer unit in the random copolymer has a volume fraction of 0.3 to 0.7 , and a sum of volume fractions of the first monomer unit and the second monomer unit in the random copolymer is 1,
wherein the random copolymer is contained in a ratio of 1 vol % to 50 vol % based on a total volume of the block copolymer and the random copolymer, and
wherein the first monomer unit is a unit represented by formula 1 below:
wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, a sulfur atom, —S(═O) 2 —, a carbonyl group, an alkylene group, an alkenylene group, —C(═O)—X 1 — or —X 1 —C(═O)—, where X 1 is an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group, and Y is a monovalent substituent comprising a ring structure to which a side chain having 8 or more chain-forming atoms is linked,
wherein the second monomer unit is a unit represented by formula 2 below:
wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X 2 is a single bond, an oxygen atom, a sulfur atom, —S(═O) 2 —, an alkylene group, an alkenylene group, —C(═O)—X 1 — or —X 1 —C(═O)—, where X 1 is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group, and W is an aryl group containing at least one halogen atom.
2. The polymer composition according to claim 1 , wherein the polymer segment A satisfies at least one of the following conditions 1 to 3:
condition 1: the polymer segment A exhibits a melting transition peak or an isotropic transition peak in a range of −80° C. to 200° C. in a DSC analysis:
condition 2: the polymer segment A exhibits a peak having a half-value width in a range of 0.2 nm −1 to 0.9 nm −1 within a scattering vector (q) range of 0.5 nm −1 to 10 nm −1 in an XRD analysis:
condition 3: the polymer segment A comprises a side chain, wherein a number (n) of chain-forming atoms in the side chain satisfies Equation 1 below with the scattering vector (q) in the XRD analysis:
3 nm −1 ≤nq /(2×π)≤5 nm −1 [Equation 1]
wherein, n is the number of the chain-forming atoms and q is the smallest scattering vector (q) in which the peak is observed in the XRD analysis for the block copolymer or the scattering vector (q) in which the peak of the largest peak area is observed.
3. The polymer composition according to claim 1 , wherein the polymer segment A in the block copolymer has a volume fraction of 0.3 to 0.7, and a sum of volume fractions of the polymer segment A and the polymer segment B is 1.
4. The polymer composition according to claim 1 , wherein the block copolymer has a number average molecular weight in a range of 5,000 to 100,000.
5. The polymer composition according to claim 1 , wherein the block copolymer has polydispersity in a range of 1.01 to 1.60.
6. The polymer composition according to claim 1 , wherein the random copolymer has a number average molecular weight in a range of 5,000 to 100,000.
7. The polymer composition according to claim 1 , wherein the random copolymer has polydispersity in a range of 1.01 to 1.80.
8. A laminate comprising:
a substrate;
a polymer membrane formed on a surface of the substrate, wherein the polymer membrane comprises a block copolymer which comprises a polymer segment A containing a first monomer unit and a polymer segment B having an absolute value of a surface energy difference with the polymer segment A of 10 mN/m or less and the polymer segment B containing a second monomer unit; and
a random copolymer containing the first monomer unit and the second monomer unit, and the second monomer unit in the random copolymer has a volume fraction of 0.3 to 0.7 , and a sum of volume fractions of the first monomer unit and the second monomer unit in the random copolymer is 1,
wherein the random copolymer is contained in a ratio of 1 vol % to 50 vol % based on a total volume of the block copolymer and the random copolymer, and
wherein the first monomer unit is a unit represented by formula 1 below:
wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, a sulfur atom, —S(═O) 2 —, a carbonyl group, an alkylene group, an alkenylene group, —C(═O)—X 1 —or —X 1 —C(═O)—, where X 1 is an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group, and Y is a monovalent substituent comprising a ring structure to which a side chain having 8 or more chain-forming atoms is linked,
wherein the second monomer unit is a unit represented by formula 2 below:
wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X 2 is a single bond, an oxygen atom, a sulfur atom, —S(═O) 2 —, an alkylene group, an alkenylene group, —C(═O)—X 1 — or —X 1 —C(═O)—, where X 1 is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group, and W is an aryl group containing at least one halogen atom.
9. The laminate according to claim 8 , wherein the block copolymer forms a lamellar structure.
10. The laminate according to claim 9 , wherein the polymer membrane has a thickness of 1 L to 10 L, where L is a pitch of the lamellar structure.
11. A method for producing a patterned substrate, comprising:
coating the polymer composition of claim 1 on a substrate; and
annealing the polymer composition to form a self-assembled structure of the block copolymer.
12. The method according to claim 11 , wherein a neutral layer is not present on the surface of the substrate on which the polymer composition is coated.
13. The method according to claim 12 , further comprising:
selectively removing one of the polymer segments of the block copolymer forming the self-assembled structure.
14. The method according to claim 13 , further comprising:
etching the substrate using the block copolymer from which one of the polymer segments has been removed as a mask.