Method for preparing surfaces

Patent metadata

Field	Value
Publication number	US-9527108-B2
Application number	US-201214363868-A
Country	US
Kind code	B2
Filing date	Dec 5, 2012
Priority date	Dec 9, 2011
Publication date	Dec 27, 2016
Grant date	Dec 27, 2016

Abstract

The invention relates to a surface preparation method using a combination of at least two polymers, which are the same or different, which are grafted hierarchically or multiply on a surface, and also to the use of this preparation method, more particularly in applications for controlling the surface energy of a substrate. The invention may allow a block polymer to be structured with a minimum of defects.

First claim

The invention claimed is:

1. Method for preparing a surface selected from silicon, silicon having a thermal or native oxide layer, germanium, platinum, tungsten, gold, titanium nitrides, graphenes, or BARC (bottom anti-reflecting coating), utilizing n random copolymers prepared by controlled radical polymerization, which are the same or different, n being an integer greater than or equal to 2, said method comprising the following n successive steps:
(a) contacting a solution or dispersion of polymer i, wherein i is the successive Integral values from 1 to n, with the surface to be treated, then evaporating a dissolution or dispersion solvent used for contacting the polymer i with the surface to be treated, followed by a step of chemical grafting polymer i to the surface;
(b) repeating step (a) with the polymer j=i+1 on the surface treated by the polymer i in step (a) until j=n; and
followed by applying a block copolymer on the surface thus treated.

2. Method according to claim 1 , wherein the weight-average molecular mass of the polymers is less than 10 000 g/mol.

3. Method according to claim 1 , wherein the weight-average molecular mass of the polymers is greater than 10 000 g/mol.

4. Method according to claim 2 , wherein n is between 2 and 4 inclusive.

5. Method according to claim 3 , wherein n is between 3 and 7 inclusive.

6. Method according to claim 4 , wherein n is 3.

7. Method according to claim 1 , wherein the grafting is carried out hierarchically.

8. Method according to claim 1 , wherein the weight-average molecular mass of the polymer i+1 is less than that of the polymer i.

9. Method according to claim 1 , wherein the grafting is carried out multiply.

10. Method according to claim 1 , wherein adjacent grafted polymers have weight-average molecular masses exhibiting a difference of greater than or equal to 20%.

11. Method according to claim 1 , wherein the polymers are prepared by nitroxide-controlled radical polymerization.

12. Method according to claim 11 , wherein the nitroxides conform to the formula below:

wherein the radical R L has a molar mass of more than 15.0342.

13. Method according to claim 12 , wherein the nitroxides are selected from the group consisting of:
N-tert-butyl 1-phenyl-2-methylpropyl nitroxide,
N-tert-butyl 1-(2-naphthyl)-2-methylpropyl nitroxide,
N-tert-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide,
N-tert-butyl 1-dibenzylphosphono-2,2-dimethylpropyl nitroxide,
N-phenyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide,
N-phenyl 1-diethylphosphono-1-methylethyl nitroxide,
N-(1-phenyl-2-methylpropyl) 1-diethylphosphono-1-methylethyl nitroxide,
4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, and
2,4,6-tri-tert-butylphenoxy.

14. Method according to claim 13 , wherein the nitroxide is N-tert-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide.

15. Method according to claim 1 , wherein the random copolymers are composed of styrene and methyl methacrylate.

16. Method according to claim 1 , wherein the surface is silicon having a native oxide layer.

17. Method according to claim 1 , wherein the surface comprises a trench, and the height of the copolymer, h, is greater than h 0 , the height of the trench.

18. Method according to claim 1 , wherein the nanostructuring of the block copolymer, observed on the treated surface, has hexagonal cylindrical symmetry.

19. Method according to claim 1 , wherein the step of chemical grafting comprising heat treatment or photochemical treatment.

20. Method for controlling the structuring of a block copolymer on a surface selected from silicon, silicon having a thermal or native oxide layer, germanium, platinum, tungsten, gold, titanium nitrides, graphenes, or BARC (bottom anti-reflecting coating), utilizing n random copolymers prepared by controlled radical polymerization, which are the same or different, wherein n is an integer greater than or equal to 2, said method comprising the following n successive steps:
(a) contacting a solution or dispersion comprising a dissolution or dispersion solvent and polymer i, wherein i is the successive integral values from 1 to n, with the surface to be treated, then
evaporating the dissolution or dispersion solvent, followed by a step of chemically grafting polymer i the surface;
(b) repeating step (a) with the polymer j=i+1 on the surface treated by the polymer i in step (a) until j=n; and
applying the block copolymer on the surface thus treated.

Assignees

• Arkema France
• Commissariat Energie Atomique

Inventors

• Navarro Christophe
• Magnet Stéphanie
• Chevalier Xavier
• Tiron Raluca
• Couderc Christophe

Classifications

• C09D153/00

  Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers · CPC title

• B05D7/52

  Two layers · CPC title

• C09D125/14

  with unsaturated esters · CPC title

• C08F293/005 Primary

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

• C09D133/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title