Additives for orientation control of block copolymers

Patent metadata

Field	Value
Publication number	US-10066040-B2
Application number	US-201615250139-A
Country	US
Kind code	B2
Filing date	Aug 29, 2016
Priority date	Apr 15, 2015
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

A film layer comprising a high-chi (χ) block copolymer for self-assembly and a 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 styrene-based block). The SAP comprises a hydrophobic fluorinated first repeat unit and a non-fluorinated second repeat unit bearing at least one pendent OH group present as an alcohol or acid (e.g., carboxylic acid). 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 1.0Lo) 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-5):
E′-P′-E″  (H-5),

wherein
E′ is a first end group,
E″ is a second end group,
at least one of E′ and E″ comprises 1 to 25 fluorine atoms, and
P′ is a polymer chain consisting essentially of:
 i) first repeat units selected from the group consisting of:

and combinations thereof, wherein each R′ is independently selected from the group consisting of hydrogen (*—H), methyl (*-Me), ethyl (*-Et), and trifluormethyl (*—CF 3 ), and each n′ is an independent integer having a value of 1 to 12, and
 ii) second repeat units selected from the group consisting of

and combinations thereof, wherein each R″ is independently selected from the group consisting of *—H, *-Me, *-Et.

2. The SAP of claim 1 , wherein P′ is a random copolymer chain.

3. The SAP of claim 1 , wherein P′ contains 40-90 mol % of the first repeat unit and 60-10 mol % of the second repeat unit, wherein mol % of the first repeat unit plus mol % of the second repeat unit equals 100 mol %.

4. The SAP of claim 1 , wherein P′ contains 55-80 mol % of the first repeat unit and 45-20 mol % of the second repeat unit, wherein mol % of the first repeat unit plus mol % of the second repeat unit equals 100 mol %.

5. The SAP of claim 1 , wherein the first repeat unit is

6. The SAP of claim 1 , wherein the first repeat unit is

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

wherein n′ is an independent integer having a value of 1 to 12.

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

wherein n′ is an independent integer having a value of 1 to 12.

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

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

11. The SAP of claim 1 , wherein E′ is

and E″ is bromide.

12. The SAP of claim 1 , wherein the first repeat unit is

and the second repeat unit is

13. The SAP of claim 1 , wherein the first repeat unit is

and the second repeat unit is

14. The SAP of claim 1 , wherein the first repeat unit is

and the second repeat unit is

15. The SAP of claim 1 , wherein E′ comprises a fluorinated ester group and E′ is bromide.

16. The SAP of claim 15 , wherein the fluorinated ester group is

wherein n′ is an integer of 1 to 12.

17. The SAP of claim 1 , wherein the SAP is suitable for effecting a desirable orientation of polymer domains formed during self-assembly of a layer comprising the SAP and a self-assembling block copolymer, the SAP and block copolymer in non-covalent association, the block copolymer comprising a polycarbonate block.

18. The SAP of claim 17 , wherein the block copolymer comprises a poly(styrene) block linked to the polycarbonate block.

19. The SAP of claim 17 , wherein the layer containing the SAP has a top surface in contact with an atmosphere during self-assembly.

20. The SAP of claim 17 , wherein the SAP is preferentially soluble in a self-assembled polymer domain comprising the polycarbonate block.

Assignees

• IBM

Inventors

• Cheng Joy
• Chunder Anindarupa
• Sanders Daniel P
• Vora Ankit

Classifications

• C08F212/22 Primary

  Oxygen · CPC title

• C08F212/20

  Fluorine · CPC title

• H10P76/20

  of masks comprising organic materials · CPC title

• G03F7/0002

  Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping · CPC title

• B81C2201/0149

  Forming nanoscale microstructures using auto-arranging or self-assembling material · CPC title