Self-assembled structures, method of manufacture thereof and articles comprising the same

Patent metadata

Field	Value
Publication number	US-10078261-B2
Application number	US-201314020343-A
Country	US
Kind code	B2
Filing date	Sep 6, 2013
Priority date	Sep 6, 2013
Publication date	Sep 18, 2018
Grant date	Sep 18, 2018

Abstract

Disclosed herein is a graft block copolymer comprising a first block polymer; the first block polymer comprising a backbone polymer and a first graft polymer; where the first graft polymer comprises a surface energy reducing moiety that comprises a halocarbon moiety, a silicon containing moiety, or a combination of a halocarbon moiety and a silicon containing moiety; a second block polymer; the second block polymer being covalently bonded to the first block; wherein the second block comprises the backbone polymer and a second graft polymer; where the second graft polymer comprises a functional group that is operative to undergo acid-catalyzed deprotection causing a change of solubility of the graft block copolymer in a developer solvent.

First claim

What is claimed is:

1. A graft block copolymer comprising:
a first block polymer; the first block polymer comprising a backbone polymer and a first graft polymer; where the first graft polymer comprises a repeat unit comprising a surface energy reducing moiety chosen from a halocarbon containing moiety, a silicon containing moiety, or a combination of a halocarbon moiety and a silicon containing moiety; and
a second block polymer; the second block polymer being covalently bonded to the first block; wherein the second block comprises the backbone polymer and a second graft polymer; where the second graft polymer comprises a functional group that is operative to undergo acid-catalyzed deprotection causing a change of solubility of the graft block copolymer in a developer solvent; where the second graft polymer comprises poly(1-ethylcyclopentyl methacrylate).

2. The copolymer of claim 1 , where the backbone polymer is a polynorbornene.

3. The copolymer of claim 1 , where the first graft polymer is a polymer derived from the polymerization of a fluorinated (meth)acrylate or a fluorinated (meth)acrylic.

4. The copolymer of claim 1 , where the first graft polymer comprises poly(5,5,5-trifluoro-4-hydroxy-2-methyl-4-(trifluoromethyl)pentyl methacrylate).

5. The copolymer of claim 1 , where the second graft polymer comprises a poly(1-tri(alkyl)methyl methacrylate).

6. The copolymer of claim 1 , where the second graft polymer is a copolymer derived from the polymerization of at least two of 1-ethylcyclopentyl methacrylate, γ-butyrolactone-2-yl methacrylate, tertiary butoxycarbonyl protected hydroxystyrene, N-phenyl maleimide and triphenylsulfonium 1,1-difluoro-2-(methacryloxy)ethanesulfonate.

7. The copolymer of claim 1 , where the second graft polymer comprises a first block copolymer and a second block copolymer; where the first block copolymer comprises poly(1-ethylcyclopentyl methacrylate) and poly(triphenylsulfonium 1,1-difluoro-2-(methacryloxy)ethanesulfonate) and where the second block copolymer comprises poly(1-ethylcyclopentyl methacrylate and poly(γ-butyrolactone-2-yl methacrylate).

8. The copolymer of claim 1 , where the first graft polymer and/or the second graft polymer each comprise a functional group that undergoes acid-catalyzed deprotection causing a change of solubility of the graft block copolymer in a developer solvent and where the graft block copolymer further comprises a photoacid generator.

9. A method of manufacturing a graft block copolymer comprising:
reacting a precursor to a backbone polymer with a first chain transfer agent to form a first backbone polymer precursor-chain transfer agent moiety;
reacting the first backbone polymer precursor-chain transfer agent moiety with a precursor to a first graft polymer;
polymerizing the precursor to the first graft polymer to form a first graft polymer; where the first graft polymer comprises a repeat unit comprising a surface energy reducing moiety chosen from a halocarbon containing moiety, a silicon containing moiety, or a combination of a halocarbon moiety and a silicon containing moiety;
polymerizing the backbone polymer precursor of the first graft polymer to form the first block polymer;
reacting a precursor to a backbone polymer with a second chain transfer agent to form a second backbone polymer precursor-chain transfer agent moiety;
reacting the second backbone polymer precursor-chain transfer agent moiety with a precursor or precursors to a second graft copolymer;
polymerizing the precursor or precursors to the second graft polymer to form the second graft polymer; where the second graft polymer comprises a functional group that is operative to undergo acid-catalyzed deprotection causing a change of solubility of the graft block copolymer in a developer solvent; and
polymerizing the backbone polymer precursor of the second graft polymer to form the second block polymer; and
reacting the first block polymer with the second block polymer to form the graft block copolymer.

Assignees

• Texas A & M Univ Sys
• Rohm & Haas Elect Mat

Inventors

• Cho Sangho
• Sun Guorong
• Wooley Karen L
• Thackeray James W
• Trefonas Iii Peter

Classifications

• G03F7/0397

  the macromolecular compound having an alicyclic moiety in a side chain · CPC title

• C08F293/005 Primary

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08G81/02 Primary

  at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds · CPC title

• G03F7/0395

  the macromolecular compound having a backbone with alicyclic moieties · CPC title

• C08G2261/90

  Applications · CPC title