Diblock copolymer containing fluorine group

Patent metadata

Field	Value
Publication number	US-10087270-B2
Application number	US-201715711086-A
Country	US
Kind code	B2
Filing date	Sep 21, 2017
Priority date	Sep 23, 2016
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

Abstract

Provided is a diblock copolymer comprising a first block having a repeating unit represented by the following Chemical Formula 1, and a second block having a repeating unit represented by the following Chemical Formula 2:

First claim

What is claimed is:

1. A diblock copolymer comprising: a first block having a repeating unit represented by the following Chemical Formula 1, and a second block having a repeating unit represented by the following Chemical Formula 3:

wherein
R 1 to R 4 are independently selected from the group consisting of —H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a halogen group, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms, and an alkenylcarbonyl group having 2 to 10 carbon atoms;
R 5 is selected from the group consisting of —H, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms containing any one or two or more heteroatoms selected from O, N and S, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms containing any one or two or more heteroatoms selected from O, N and S, a halogen group, a cyano group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkylthio group having 3 to 10 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms, an alkenylcarbonyl group having 2 to 10 carbon atoms, an arylcarbonyl group having 6 to 20 carbon atoms, a cycloalkylcarbonyl group having 3 to 10 carbon atoms, and a cycloalkenylcarbonyl group having 3 to 10 carbon atoms;
in the diblock copolymer, when mole fractions of repeating units A, B and C in the diblock copolymer represented by the above Chemical Formulae 1 and 3 are l, n and m, respectively, l is 0.4 to 0.6, n is 0.2 to 0.4, m is 0.1 to 0.3, and l+n+m=1, and
the diblock copolymer has a χ value at 25° C. of 0.035 to 0.1.

2. The diblock copolymer of claim 1 , wherein the first block is formed from an alkylmethacrylate-based compound.

3. The diblock copolymer of claim 1 , wherein the block copolymer satisfies the following Equation 1:
1,000≤ M n ×m ×( a/ 5)≤60,000  [Equation 1]

wherein M n is a number average molecular weight of the diblock copolymer; m is a mole fraction of the repeating unit C; and a is the number of F introduced into the repeating unit C.

4. The diblock copolymer of claim 1 , wherein the block copolymer has etching selectivity satisfying the following Equation 2:
4≤ ER 1 /ER 2   [Equation 2]

wherein ER 1 is an etching rate (nm/sec) of the first block; ER 2 is an etching rate (nm/sec) of the second block; and each of the etching rates is calculated from the following Calculation Formula 1:
Etching rate=( T 0 −T 1 )/ S   [Calculation Formula 1]

wherein T 0 is an initial thickness (nm) of the first block or the second block before etching; T 1 is a final thickness (nm) of the first block or the second block after etching; and S is etching time (sec).

5. The diblock copolymer of claim 1 , wherein the diblock copolymer forms vertically oriented lamella patterns.

6. The diblock copolymer of claim 1 , wherein the diblock copolymer forms patterns having LER of 3.3 nm or less, and LWR of 4.5 nm or less.

7. A diblock copolymer comprising: a first block having a repeating unit represented by the following Chemical Formula 1, and a second block having a repeating unit represented by the following Chemical Formula 4:

wherein
R 1 to R 4 are independently selected from the group consisting of —H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a halogen group, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms, and an alkenylcarbonyl group having 2 to 10 carbon atoms;
R 5 is selected from the group consisting of —H, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms containing any one or two or more heteroatoms selected from O, N and S, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms containing any one or two or more heteroatoms selected from O, N and S, a halogen group, a cyano group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkylthio group having 3 to 10 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms, an alkenylcarbonyl group having 2 to 10 carbon atoms, an arylcarbonyl group having 6 to 20 carbon atoms, a cycloalkylcarbonyl group having 3 to 10 carbon atoms, and a cycloalkenylcarbonyl group having 3 to 10 carbon atoms;
in the diblock copolymer, when mole fractions of repeating units A, B and C in the diblock copolymer represented by the above Chemical Formulae 1 and 4 are l, n and m, respectively, l is 0.4 to 0.6, n is 0 to 0.1, m is 0.4 to 0.6, and l+n+m=1 and
the diblock copolymer has a χ value at 25° C. of 0.035 to 0.1.

8. The diblock copolymer of claim 7 , wherein the first block is formed from an alkylmethacrylate-based compound.

9. The diblock copolymer of claim 7 , wherein the block copolymer satisfies the following Equation 1:
1,000≤ M n ×m ×( a/ 5)≤60,000  [Equation 1]

wherein M n is a number average molecular weight of the diblock copolymer; m is a mole fraction of the repeating unit C; and a is the number of F introduced into the repeating unit C.

10. The diblock copolymer of claim 7 , wherein the block copolymer has etching selectivity satisfying the following Equation 2:
4≤ ER 1 /ER 2   [Equation 2]

wherein ER 1 is an etching rate (nm/sec) of the first block; ER 2 is an etching rate (nm/sec) of the second block; and each of the etching rates is calculated from the following Calculation Formula 1:
Etching rate=( T 0 −T 1 )/ S   [Calculation Formula 1]

wherein T 0 is an initial thickness (nm) of the first block or the second block before etching; T 1 is a final thickness (nm) of the first block or the second block after etching; and S is etching time (sec).

11. The diblock copolymer of claim 7 , wherein the diblock copolymer forms vertically oriented lamella patterns.

12. The diblock copolymer of claim 7 , wherein the diblock copolymer forms patterns having LER of 3.3 nm or less, and LWR of 4.5 nm or less.

Assignees

• Korea Advanced Inst Sci & Tech
• Sk Innovation Co Ltd

Inventors

• Ham Jin Su
• Jung Yeon Sik
• Kim Sun Young
• Hur Yoon Hyung
• Lee Kwang Kuk
• Song Seung Won

Classifications

• H01J37/28

  with scanning beams {(H01J37/268, H01J37/292, H01J37/2955 take precedence)} · CPC title

• C08F220/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• C08F212/08

  Styrene · CPC title

• C08F4/04

  Azo-compounds · CPC title

• C08F220/18

  with acrylic or methacrylic acids · CPC title