Fluoro-alcohol additives for orientation control of block copolymers

Patent metadata

Field	Value
Publication number	US-10040879-B2
Application number	US-201615357786-A
Country	US
Kind code	B2
Filing date	Nov 21, 2016
Priority date	Feb 16, 2015
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

A film layer comprising a high-chi (χ) block copolymer for self-assembly and a hexafluoroalcohol-containing surface active polymer (SAP) was prepared on a substrate surface that was neutral wetting to the domains of the self-assembled block copolymer. The block copolymer comprises at least one polycarbonate block and at least one other block (e.g., a substituted or unsubstituted styrene-based block). The film layer, whose top surface has contact with an atmosphere, self-assembles to form a lamellar or cylindrical domain pattern having perpendicular orientation with respect to the underlying surface. Other morphologies (e.g., islands and holes of height 1.0 Lo) were obtained with films lacking the SAP. The SAP is preferentially miscible with, and lowers the surface energy of, the domain comprising the polycarbonate block.

First claim

What is claimed is:

1. A surface active polymer (SAP) of formula (H-2):
E′-P′-E″  (H-2),

wherein
E′ is a first end group,
E″ is a second end group,
at least one of E′ and E″ comprises 1-25 fluorines, and
P′ is a polymer chain which comprises a fluoro-alcohol repeat unit (HFA repeat unit) of formula (H-1):

wherein
a′ is 1 or 2,
Q″ is a linking group covalently bound to carbon 1, has a valency of a′+1, and comprises at least one carbon, and
R″ is a monovalent radical selected from the group consisting of *—H, methyl (*—CH 3 ), ethyl (*-Et), and trifluoromethyl (*—CF 3 ).

2. The SAP of claim 1 , wherein the HFA repeat unit has a structure selected from the group consisting of

3. The SAP of claim 1 , wherein E′ and/or E″ comprises 10 to 25 fluorines.

4. The SAP of claim 1 , wherein P′ is a homopolymer of the HFA repeat unit.

5. The SAP of claim 1 , wherein E′ and/or E″ comprises a fluorinated ester group having the structure

wherein n′ is an integer of 1 to 12.

6. The SAP of claim 1 , wherein E′ comprises a fluorinated ester group having the structure

wherein n′ is an integer of 1 to 12, and E″ is bromide.

7. The SAP of claim 1 , wherein the HFA repeat unit is

8. The SAP of claim 1 , wherein the HFA repeat unit is

9. The SAP of claim 1 , wherein the HFA repeat unit is

10. The SAP of claim 1 , wherein the HFA repeat unit is

11. The SAP of claim 1 , wherein R″ is *—H.

12. The SAP of claim 1 , wherein R″ is methyl (*—CH 3 ).

13. The SAP of claim 1 , wherein R″ is ethyl (*-Et).

14. The SAP of claim 1 , wherein R″ is trifluoromethyl (*—CF 3 ).

15. The SAP of claim 1 , wherein the SAP is a random copolymer comprising the HFA repeat unit.

16. The SAP of claim 15 , wherein the random copolymer comprises at least one diluent repeat unit selected from the group consisting of

and combinations thereof, wherein each R″ is independently selected from the group consisting of *—H, *-Me, *-Et, and *—CF 3 , and each n′ is an independent integer having a value of 1 to 12.

17. The SAP of claim 16 , wherein the diluent repeat unit is

18. The SAP of claim 16 , wherein the diluent repeat unit is

19. The SAP of claim 16 , wherein the diluent repeat unit is

wherein R″ is independently selected from the group consisting of *—H, *-Me, *-Et, and *—CF 3 , and n′ is an independent integer having a value of 1 to 12.

20. The SAP of claim 16 , wherein the diluent repeat unit is

wherein R″ is independently selected from the group consisting of *—H, *-Me, *-Et, and *—CF 3 , and n′ is an independent integer having a value of 1 to 12.

21. The SAP of claim 16 , wherein the diluent repeat unit is

wherein R″ is independently selected from the group consisting of *—H, *-Me, *-Et, and *—CF 3 , and n′ is an independent integer having a value of 1 to 12.

Assignees

• IBM

Inventors

• Cheng Joy
• Chunder Anindarupa
• Vora Ankit

Classifications

• H10P76/20

  of masks comprising organic materials · CPC title

• C08F112/24

  Phenols or alcohols · CPC title

• C08F112/20

  Fluorine · CPC title

• C08F8/00 Primary

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title