Chemi-epitaxy in directed self-assembly applications using photo-decomposable agents

Patent metadata

Field	Value
Publication number	US-8980538-B2
Application number	US-201313830859-A
Country	US
Kind code	B2
Filing date	Mar 14, 2013
Priority date	Mar 14, 2013
Publication date	Mar 17, 2015
Grant date	Mar 17, 2015

Abstract

A method of forming a layered substrate comprising a self-assembled material is provided. The method includes forming a first layer of material on a substrate, forming a layer of a radiation sensitive material on the first layer of material, imaging the layer of the radiation sensitive material with patterned light, heating the layer of the radiation sensitive material to a temperature at or above the cross-linking reaction temperature, developing the imaged layer, and forming the block copolymer pattern. The radiation sensitive material comprises at least one photo-sensitive component selected from (a) a photo-decomposable cross-linking agent, (b) a photo-base generator, or (c) a photo-decomposable base; and a cross-linkable polymer, wherein imaging by the patterned light provides a pattern defined by a first region having substantial portions of a decomposed photo-sensitive component surrounded by regions having substantial portions of intact photo-sensitive component.

First claim

What is claimed is:

1. A method of forming a layered substrate comprising a self-assembled material, comprising:
forming a first layer of material on a substrate;
forming a layer of a radiation sensitive material on the first layer of material, the radiation sensitive material comprising a photo-sensitive component comprising a photo-decomposable cross-linking agent; and a cross-linkable polymer;
imaging the layer of the radiation sensitive material with patterned light to form a pattern in the layer of the radiation sensitive material, wherein the pattern is defined by a first region having substantial portions of the photo-decomposable cross-linking agent decomposed, and a second region having substantial portions of the photo-decomposable cross-linking agent intact;
heating the layer of the radiation sensitive material to a temperature at or above the cross-linking reaction temperature to cross-link the cross-linkable polymer in one of the first or second regions to form a cross-linked region, while the other one of the first or second regions remains as a non-crosslinked region;
developing the imaged layer to remove the non-crosslinked region; and
forming a block copolymer pattern comprising the self-assembled material derived from a block copolymer.

2. The method of claim 1 , wherein at least one polymer block of the block copolymer has a chemical affinity for the first layer of material or the cross-linked region of the radiation sensitive material.

3. The method of claim 1 ,
wherein the photo-decomposable cross-linking agent comprises a plurality of a first functional group (FG′) covalently bonded to one another through a photo-decomposable functional group;
wherein the cross-linkable polymer of the radiation sensitive material comprises a plurality of a second functional group (FG″), wherein the second functional group (FG″) reacts with the first functional group (FG′) upon the heating to the temperature at or above the cross-linking reaction temperature;
and
wherein the developing is a positive-tone development.

4. The method of claim 3 , wherein the photo-decomposable cross-linking agent is defined by a general formula (I) of:
FG′-L′-Q(-L″-FG′) m ,  (I)

wherein FG′ represents the first functional group selected from primary amines, secondary amines, hydroxyls, amides, esters, epoxies, episulfides, or anhydrides; L′ and L″ represent linking groups covalently bonding the first functional groups to Q; wherein Q represents the photo-decomposable functional group; and wherein m is an integer from 1 to 3.

5. The method of claim 3 , wherein the photo-decomposable cross-linking agent is defined by a general formula (II) of:
FG′-L 1 -I + -L 2 -FG′A − ,  (II)

wherein FG′ represents the first functional group selected from primary amines, secondary amines, hydroxyls, amides, esters, epoxies, episulfides, or anhydrides; L′ and L″ represent linking groups covalently bonding the first functional groups to an iodonium group (I + ), said L 1 and L 2 comprising substituted or unsubstituted aryls; and wherein A is an anion of a complex metal halide or a strong protonic acid.

6. The method of claim 3 , wherein the photo-decomposable cross-linking agent is defined by a general formula (III) of:
[FG′-L 3 -SO 2 —O—N═CR 1 ] n —Y

wherein FG′ represents the first functional group selected from primary amines, secondary amines, hydroxyls, amides, esters, epoxies, episulfides, or anhydrides; wherein L 3 is a linking group covalently bonding FG′ to a sulfonyl (SO 2 ) group; wherein R 1 comprises a substituted or unsubstituted alkyl, a haloalkyl, a cycloalkyl, a heterocycle, an aryl, a heteroaryl, or an alkaryl; n is an integer greater than 1 in order to provide a plurality of first functional groups (FG 1 ); and Y comprises a carbon-containing connecting member which covalently links the plurality of first functional groups with each other.

7. The method of claim 3 , wherein the photo-decomposable cross-linking agent is defined by a general formula (IV) of:

wherein FG′ represents the first functional group selected from primary amines, secondary amines, hydroxyls, amides, esters, epoxies, episulfides, or anhydrides; wherein L 3 is a linking group covalently bonding FG′ to a sulfonyl (SO 2 ) group; wherein R 2 and R 3 can be the same or different carbon-containing moiety, or in combination form a carbon-containing ring, provided that at least one of R 2 , R 3 , or the carbon-containing ring is substituted with at least one FG′.

8. The method of claim 3 , wherein the photo-decomposable cross-linking agent is defined by a general formula (V) of:

wherein FG′ represents the first functional group selected from primary amines, secondary amines, hydroxyls, amides, esters, epoxies, episulfides, or anhydrides; wherein W is selected from a carbonyl (C═O) group or a sulfonyl (SO 2 ) group; wherein L 4 is a linking group covalently bonding FG′ to W; and wherein R 4 , R 5 , R 6 , R 7 , and R 8 are independently selected from H; a halide; a substituted or unsubstituted alkyl, cycloalkyl, aryl, alkaryl, or ether groups; a haloalkyl; a heterocycle; a heteroaryl; an alkoxyl; or combinations thereof, provided that at least one of at least one of R 4 , R 5 , R 6 , R 7 , or R 8 comprises a functional group selected from primary amines, secondary amines, hydroxyls, amides, esters, epoxies, episulfides, and anhydrides.

9. The method of claim 3 , wherein the photo-decomposable cross-linking agent is defined by a general formula (VI) of:
FG′-L 5 -S—CR 9 ═CR 10 —S-L 6 -FG + ,  (VI)

wherein FG′ represents the first functional group selected from primary amines, secondary amines, hydroxyls, amides, esters, epoxies, episulfides, or anhydrides; wherein R 9 and R 10 are independently selected from H, or substituted or unsubstituted carbon-containing chains and rings; and wherein L 5 and L 6 are linking groups covalently bonding FG′ to sulfur.

10. The method of claim 3 , wherein forming the block copolymer pattern comprises:
forming a layer of the block copolymer, the block copolymer having a χN parameter equal to or greater than about 10.5 and comprising a first polymer block and a second polymer block;
annealing the layer of the block copolymer to form the block copolymer pattern comprising a plurality of domains; and
optionally, selectively removing a first domain of the block copolymer pattern, while leaving behind a second domain of the block copolymer pattern.

11. The method of claim 3 , wherein the forming the layer of the radiation sensitive material comprises:
casting a solution of the radiation sensitive material in a solvent on the first layer of material;
removing the solvent; and
heating the layer to the temperature at or above the cross-linking reaction temperature prior to imaging the second layer of the photosensitive material with patterned light.

12. The method of claim 1 ,
wherein the layer of the radiation sensitive material further comprises an acidic compound, and the photo-decomposable cross-linking agent comprises a plurality of a first functional group (FG′) covalently bonded to one another through a photo-decomposable functional group;
wherein the photo-sensitive component of the radiation sensitive material further comprises a photo-base generator;
wherein the cross-linkable polymer of the radiation sensitive material comprises a plurality of a second functional group (FG″), wherein the second functio

Assignees

• Tokyo Electron Ltd

Inventors

• Somervell Mark H
• Carcasi Michael A

Classifications

• G03F7/0035

  Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface · CPC title

• G03F7/0002

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

• B82Y10/00

  Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• G03F7/039

  Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) · CPC title