PROCESS FOR MANUFACTURING SELF-ASSEMBLED BLOCK COPOLYMER FILMS

• US 20160082472A1
• Filed: 05/09/2014
• Published: 03/24/2016
• Est. Priority Date: 05/10/2013
• Status: Active Grant

• Current Assignee: Consiglio Nazionale Delle Ricerche (Repubblica Italiana)
• Original Assignee: Consiglio Nazionale Delle Ricerche (Repubblica Italiana)
• Inventors: Perego, Michele, Seguini, Gabriele, Ferrarese Lupi, Federico
• Granted Patent: US 9,962,733 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B05D 1/005 Spin coating
• CPC Class Codes: B05D 3/007 After-treatment
• CPC Class Codes: B05D 3/06 by exposure to radiation B05D3/02 takes precedence ; plasma treatment B05D3/141
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C09D 153/00 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 Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Abstract

Self-assembled block copolymer films having two or more blocks are manufactured by distributing a solution containing at least one block copolymer onto the substrate so as to partially coat a substrate surface, obtaining an intermediate product. A block copolymer is self-assembled by heating the intermediate product. The self-assembling step includes Rapid Thermal Processing, which is performed by heating the intermediate product up to a first target temperature, ranging from a glass transition temperature to an order-disorder transition temperature of the block copolymer, through a temperature rising ramp having a rate of temperature change not lower than 5° C./second; maintaining the intermediate product at the target temperature for a time interval not longer than 60 minutes, whereby a sample is obtained on the surface of which a self-assembled film of the block copolymer has been made; and cooling the sample down to the ambient temperature through a temperature descending ramp.

Claims

1. Process for manufacturing self-assembled block copolymer films, having two or more blocks, comprising the following steps:

A. having a substrate;

B. distributing a first solution containing at least one block copolymer onto the substrate so as to at least partially coat a surface of the substrate, obtaining a first intermediate product;

C. making a step of self-assembling said at least one block copolymer by heating the first intermediate product;

where the self-assembling step C is made through a first RTP process of Rapid Thermal Processing comprising the following substeps;

C.1 heating the first intermediate product up to a first target temperature, ranging from a glass transition temperature T_g of said at least one block copolymer to an order-disorder transition temperature T_ODT of said at least one block copolymer, through a first temperature rising ramp having a first rate of temperature change not lower than 5°

C./second;

C.2 maintaining the first intermediate product at said first target temperature for a first time interval not longer than 60 minutes, whereby a sample is obtained on the surface of which a self-assembled film of said at least one block copolymer has been made;

C.3 cooling the sample down to the ambient temperature through a first temperature descending ramp.

2. Process according to claim 1, wherein said first rate of temperature change is not larger than 300°

C./s.

3. Process according to claim 1, wherein said first time interval is not longer than 30 minutes.

4. Process according to claim 1, wherein said first RTP process is made within a chamber and wherein the self-assembling step C executes, before substep C.1, the following substep at least once;

C.4 emptying said chamber and introducing inert gas.

5. Process according to claim 1, wherein said at least one block copolymer is selected from the group comprising polystyrene-polyfluorostyrene (PS-PFS), polystyrene-poly(dimethyl siloxane) (PS-PDMS), polystyrene-poly(ethylene oxide) (PS-PEO), polystyrene-poly(methylstyrene) (PS-PMS), polystyrene-poly(4-vinylpyridine) (PS-P4VP), polystyrene-poly(2-vinylpyridine) (PS-P2VP), polystyrene-polylactide (PS-PLA), polystyrene-polyimide (PS-PI), polystyrene-poly(ethylene-propylene) (PS-PEP), polyimide-poly(4-vinylpyridine) (PI-P4VP), polyimide-poly(2-vinylpyridine) (PI-P2VP), polystyrene-poly(acrylic acid) (PS-PAA), polystyrene-poly(butadiene) (PS-PBD), polystyrene-poly(vinylpyridine) (PS-PVP), poly(ethylene-propylene)-poly(ethylethylene) (PEP-PEE), poly(ethylene oxide)-polystyrene (PEO-PS), poly(meth)acrylate based copolymers, polydiene based copolymers, polyisobutylene based copolymers, polystyrene based copolymers, polyvinyl naphthalene based copolymers, polyvinylpyridine based copolymers, polypropylene oxide based copolymers, polysiloxane based copolymers, adipic anhydride based copolymers, polyolefin based copolymers, polylactide based copolymers, polyferrocenyldimethylsilane based copolymers, and polyhedral oligomeric silsesquioxane based copolymers.

6. Process according to claim 1, wherein said first solution comprises at least one solvent.

7. Process according to claim 1, wherein said substrate is made of a material selected from the group comprising silicon dioxide (SiO₂), silicon, zinc oxide (ZnO), permalloy, indium tin oxide (ITO), high permittivity (high-k) oxides, transition metal oxides, rare earth element oxides, and aluminium oxide (Al₂O₃).

8. Process according to claim 1, wherein it comprises, before step B, the following steps:

D. distributing a second solution containing at least one random copolymer onto the substrate so as to at least partially coat said surface of the substrate, obtaining a second intermediate product;

E. making a step of neutralisation of said surface of said substrate through a second RTP process of Rapid Thermal Processing comprising the following substeps;

E.1 heating the second intermediate product up to a second target temperature, ranging from a glass transition temperature T_g of said at least one random copolymer to an order-disorder transition temperature T_ODT of said at least one random copolymer, through a second temperature rising ramp having a second rate of temperature change not lower than 5°

C./second;

E.2 maintaining the second intermediate product at said second target temperature for a second time interval not longer than 60 minutes, whereby said at least one random copolymer is chemically bonded to said surface of said substrate so that said surface of said substrate is neutralised;

E.3 cooling said substrate with said neutralised surface down to the ambient temperature through a second temperature descending ramp.

9. Process according to claim 8, wherein the neutralisation step E further comprises, after step E.3, the following substep:

E.4 making a low-power sonication of said substrate with said neutralised surface.

10. Process according to claim 8, wherein said second RTP process is made in a chamber and wherein the neutralisation step E executes, before substep E.1, the following substep at least once:

E.5 emptying said chamber and introducing inert gas.

11. Process according to claim 8, wherein said at least one random copolymer is selected from the group comprising polystyrene-polyfluorostyrene (PS-PFS), polystyrene-poly(dimethyl siloxane) (PS-PDMS), polystyrene-poly(ethylene oxide) (PS-PEO), polystyrene-poly(methylstyrene) (PS-PMS), polystyrene-poly(4-vinylpyridine) (PS-P4VP), polystyrene-poly(2-vinylpyridine) (PS-P2VP), polystyrene-polylactide (PS-PLA), polystyrene-polyimide (PS-PI), polystyrene-poly(ethylene-propylene) (PS-PEP), polyimide-poly(4-vinylpyridine) (PI-P4VP), polyimide-poly(2-vinylpyridine) (PI-P2VP), polystyrene-poly(acrylic acid) (PS-PAA), polystyrene-poly(butadiene) (PS-PBD), polystyrene-poly(vinylpyridine) (PS-PVP), poly(ethylene-propylene)-poly(ethylethylene) (PEP-PEE), and poly(ethylene oxide)-polystyrene (PEO-PS).

12. Process according to claim 8, wherein said second solution comprises at least one solvent.

13. Process according to claim 1, wherein step A comprises the following substep:

A.1 chemically cleaning said surface of said substrate so as to remove contaminants and/or particulate possibly present onto said surface of said substrate.

15. Process according to claim 2, wherein said first rate of temperature change ranges from 10°

C./s to 50°

C./s.

16. Process according to claim 3, wherein said first time interval is not longer than 1 second.

17. Process according to claim 4, wherein substep C.4 is executed twice.

18. Process according to claim 8, wherein in substep E.1 said second temperature rising ramp has a second rate of temperature change ranging from 10°

C./s to 50°

C./s.

19. Process according to claim 8, wherein in substep E.2 said second time interval is not longer than 1 minute.

20. Process according to claim 9, wherein substep E.4 is executed by heating said substrate with said neutralised surface in an ultrasonic bath in at least one solvent.

21. Process according to claim 10, wherein substep E.5 is executed twice.

14. Self-assembled block copolymer film, having two or more blocks, manufactured through a manufacturing process comprising the following steps:

A. having a substrate;

B. distributing a first solution containing at least one block copolymer onto the substrate so as to at least partially coat a surface of the substrate, obtaining a first intermediate product;

C. making a step of self-assembling said at least one block copolymer by heating the first intermediate product;

wherein the self-assembling step C is made through a first RTP process of Rapid Thermal Processing comprising the following substeps;

C.1 heating the first intermediate product up to a first target temperature, ranging from a glass transition temperature T_g of said at least one block copolymer to an order-disorder transition temperature T_ODT of said at least one block copolymer, through a first temperature rising ramp having a first rate of temperature change not lower than 5°

C./second;

C.2 maintaining the first intermediate product at said first target temperature for a first time interval not longer than 60 minutes, whereby a sample is obtained on the surface of which a self-assembled film of said at least one block copolymer has been made;

C.3 cooling the sample down to the ambient temperature through a first temperature descending ramp.