Directed self-assembly pattern formation methods and compositions

Patent metadata

Field	Value
Publication number	US-9490117-B2
Application number	US-201414588410-A
Country	US
Kind code	B2
Filing date	Dec 31, 2014
Priority date	Dec 31, 2013
Publication date	Nov 8, 2016
Grant date	Nov 8, 2016

Abstract

A method of forming a pattern by directed self-assembly, comprising: (a) providing a semiconductor substrate comprising one or more layers to be patterned; (b) applying a crosslinkable underlayer composition over the one or more layers to be patterned to form a crosslinkable underlayer, wherein the crosslinkable underlayer composition comprises a crosslinkable polymer comprising a first unit formed from a monomer of the following general formula (I-A) or (I-B):

wherein: P is a polymerizable functional group; L is a single bond or an m+1-valent linking group; X 1 is a monovalent electron donating group; X 2 is a divalent electron donating group; Ar 1 and Ar 2 are trivalent and divalent aryl groups, respectively, and carbon atoms of the cyclobutene ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 1 or Ar 2 ; m and n are each an integer of 1 or more; and each R 1 is independently a monovalent group; (c) heating the crosslinkable underlayer to form a crosslinked underlayer; (d) forming a self-assembling layer comprising a block copolymer over the crosslinked underlayer; and (e) annealing the self-assembling layer. The methods and compositions find particular applicability in the manufacture of semiconductor devices or data storage devices for the formation of high resolution patterns.

First claim

What is claimed is:

1. A method of forming a pattern by directed self-assembly, comprising:
(a) providing a semiconductor substrate comprising one or more layers to be patterned;
(b) applying a crosslinkable underlayer composition over the one or more layers to be patterned to form a crosslinkable underlayer, wherein the crosslinkable underlayer composition comprises a crosslinkable polymer comprising a first unit formed from a monomer of the following general formula (I-A) or (I-B):

wherein: P is a polymerizable functional group; L is a single bond or an m+1-valent linking group; X 1 is a monovalent electron donating group; X 2 is a divalent electron donating group; Ar 1 and Ar 2 are trivalent and divalent aryl groups, respectively, and carbon atoms of the cyclobutene ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 1 or Ar 2 ; m and n are each an integer of 1 or more; and each R 1 is independently a monovalent group; wherein the first unit is present in the crosslinkable polymer in an amount of from 3 to 10 mol %, based on the polymer;

(c) heating the crosslinkable underlayer to form a crosslinked underlayer;
(d) patterning the crosslinked underlayer;
(e) forming a self-assembling layer comprising a block copolymer over the patterned crosslinked underlayer; and
(f) annealing the self-assembling layer.

2. The method of claim 1 , wherein the patterned crosslinked underlayer is formed by photolithography and etching, wherein recesses exposing the substrate are disposed between adjacent patterns of the crosslinked underlayer.

3. The method of claim 2 , further comprising forming a brush layer in the recesses between adjacent patterns, wherein the self-assembling layer is formed on the patterns and the brush layer.

4. The method of claim 1 , wherein the patterns are formed by chemically altering selected regions of the crosslinked underlayer.

5. The method of claim 1 , wherein the polymerizable functional group P is chosen from the following general formulae (II-A) and (II-B):

wherein R 4 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; and A is oxygen or is represented by the formula NR 5 , wherein R 5 is chosen from hydrogen and substituted and unsubstituted C 1 to C 10 linear, branched and cyclic hydrocarbons; and

wherein R 6 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl; and wherein L is chosen from optionally substituted linear or branched aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —COO—, —CONR 3 —, —CONH— and —OCONH—, wherein R 3 is chosen from hydrogen and substituted and unsubstituted C 1 to C 10 linear, branched and cyclic hydrocarbons.

6. The method of claim 1 , wherein the first unit is formed from a monomer of the general formula (I-A), wherein X 1 is chosen from C 1 -C 10 alkoxy, amine, sulfur, —OCOR 9 , wherein R 9 is chosen from substituted and unsubstituted C 1 to C 10 linear, branched and cyclic hydrocarbons, —NHCOR 10 , wherein R 10 is chosen from substituted and unsubstituted C 1 to C 10 linear, branched and cyclic hydrocarbons, and combinations thereof.

7. The method of claim 1 , wherein the first unit is formed from a monomer of the general formula (I-B), wherein X 2 is —O—, —S—, —COO—, —CONR 11 —, —CONH— and —OCONH—, wherein R 11 is chosen from hydrogen and substituted and unsubstituted C 1 to C 10 linear, branched and cyclic hydrocarbons, and combinations thereof.

8. The method of claim 1 , wherein the first unit is formed from a monomer chosen from one or more of the following monomers:

9. The method of claim 1 , wherein the polymer further comprises a second unit chosen from general formulae (III) and (IV):

wherein R 7 is chosen from hydrogen, fluorine, C 1 -C 3 alkyl and C 1 -C 3 fluoroalkyl, R 8 is chosen from optionally substituted C 1 to C 10 alkyl, and Ar 3 is an optionally substituted aryl group.

Assignees

• Rohm & Haas Elect Mat
• Dow Global Technologies Llc

Inventors

• Park Jong Keun
• Sun Jibin
• Gilmore Christopher D
• Zhang Jieqian
• Hustad Phillip D
• Trefonas Iii Peter
• O'Connell Kathleen M

Classifications

• H10P76/2041

  Photolithographic processes · CPC title

• H10P50/28

  of insulating materials · CPC title

• H10P14/6342

  Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating · CPC title

• H10P14/6322

  Formation by thermal treatments (formation by plasma treatment H10P14/6319) · CPC title

• H10P14/683

  carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC · CPC title