Spin-on layer for directed self assembly with tunable neutrality

Patent metadata

Field	Value
Publication number	US-9733566-B2
Application number	US-201615068833-A
Country	US
Kind code	B2
Filing date	Mar 14, 2016
Priority date	Mar 17, 2015
Publication date	Aug 15, 2017
Grant date	Aug 15, 2017

Abstract

Techniques disclosed herein include methods for creating a directed self-assembly tunable neutral layer that works with multiple different block copolymer materials. Techniques herein can include depositing a neutral layer and then post-processing this neutral layer to tune its characteristics so that the neutral layer is compatible with a particular block copolymer scheme or schemes. Post-processing herein of such a neutral layer can modify a ratio of pi and sigma bonds in a given carbon film or other film to approximate a given self-assembly film that will be deposited on this neutral layer. Accordingly, a generic or single material can be used for a neutral layer and modified to match a given block copolymer to be deposited.

First claim

The invention claimed is:

1. A method for patterning a substrate, the method comprising:
depositing a tunable layer on a substrate, the tunable layer being an organic material having a first ratio of sigma bonds to pi bonds;
identifying a mixture ratio of a first block copolymer to a second block copolymer that corresponds to a block copolymer mixture specified for deposition on the substrate;
modifying the tunable layer, to result in a neutral layer, by increasing the first ratio of sigma bonds to pi bonds to a second ratio of sigma bonds to pi bonds, the second ratio of sigma bonds to pi bonds having a value that is equivalent to the mixture ratio of the first block copolymer to the second block copolymer, the neutral layer being neutral to both the first block copolymer and the second block copolymer;
depositing the block copolymer mixture on the substrate;
causing phase-separation of the block copolymer mixture such that self-assembly of the block copolymer mixture occurs: and
forming a relief pattern from the tunable layer subsequent to modifying the tunable layer and prior to depositing the block copolymer mixture on the substrate.

2. The method of claim 1 , wherein modifying the tunable layer includes increasing a number of pi bonds in the tunable layer.

3. The method of claim 1 , wherein modifying the tunable layer includes increasing cross-linking of the tunable layer by exposure to a flux of ballistic electrons or exposure to a patterned electron beam.

4. The method of claim 1 , wherein modifying the tunable layer includes exposing the tunable layer to actinic radiation.

5. The method of claim 4 , wherein exposing the tunable layer to actinic radiation includes exposing the tunable layer to light having a wavelength of 172 nanometers or 248 nanometers.

6. The method of claim 1 , wherein the tunable layer includes thermal acid generators and wherein modifying the tunable layer includes executing a bake process that heats the tunable layer sufficient to generate acid from the thermal acid generators.

7. The method of claim 1 , wherein the tunable layer comprises a polymethyl methacrylate film.

8. A method for patterning a substrate, the method comprising:
depositing a tunable layer on a reief pattern on a substrate, the tunable layer being a material having a surface energy with a modification potential;
identifying a block copolymer mixture specified for deposition on the substrate;
modifying the tunable layer by changing an initial surface energy value of the tunable layer to a modified surface energy value, modifying the tunable layer resulting in a neutral layer, the neutral layer having the modified surface energy value, the neutral layer enabling vertically-oriented structures to self-assemble from the block copolymer mixture specified for deposition on the substrate, the neutral layer being neutral to both a first block copolymer and a second block copolymer of the block copolymer mixture;
depositing the block copolymer mixture on the substrate; and
causing phase-separation of the block copolymer mixture such that self-assembly of the block copolymer mixture occurs on the neutral layer forming vertically-oriented structures.

9. The method of claim 8 , wherein modifying the tunable layer includes increasing a number of pi bonds in the tunable layer.

10. The method of claim 8 , wherein modifying the tunable layer includes increasing cross-linking of the tunable layer by exposure to a flux of ballistic electrons or exposure to a patterned electron beam.

11. The method of claim 8 , wherein modifying the tunable layer includes exposing the tunable layer to actinic radiation.

12. The method of claim 11 , wherein exposing the tunable layer to actinic radiation includes exposing the tunable layer to light having a wavelength of 172 nanometers or 248 nanometers.

13. The method of claim 8 , wherein the tunable layer includes thermal acid generators and wherein modifying the tunable layer includes executing a bake process that heats the tunable layer sufficient to generate acid from the thermal acid generators.

14. The method of claim 8 , wherein the tunable layer comprises a polymethyl methacrylate film.

15. A method for patterning a substrate, the method comprising:
receiving a substrate having a tunable layer positioned on one or more underlying layers, the tunable layer having an initial surface energy value, wherein the tunable layer has been deposited by spin-on deposition or vapor deposition; and
executing a bond-changing surface treatment of the tunable layer such that an initial ratio of carbon sigma to pi bonds is modified to result in a neutral layer having a predetermined ratio of carbon sigma to pi bonds, the bond-changing surface treatment resulting in a modified surface energy value of the tunable layer that is different from the initial surface energy value, the modified surface energy value corresponding to a specified surface energy value that enables directed self-assembly of vertical structures from a specific block copolymer mixture, wherein the neutral layer is neutral to the specific block copolymer mixture.

16. The method of claim 15 , wherein the bond-changing surface treatment is selected from the group consisting of exposure to electromagnetic radiation, thermal exposure, exposure to plasma products, acid deposition, and exposure to a flux of ballistic electrons.

17. The method of claim 15 , wherein executing the bond-changing surface treatment generates acid within the neutral layer.

18. The method of claim 15 , further comprising: subsequent to executing the bond-changing surface treatment, executing a patterning treatment that results in either a grapho-epitaxial or chemo-epitaxy pattern of the neutral layer.

Assignees

• Tokyo Electron Ltd

Inventors

• Smith Jeffrey

Classifications

• H10P95/08

  Planarisation of organic insulating materials · CPC title

• H10P76/4085

  characterised by the processes involved to create the masks · CPC title

• H10P76/20 Primary

  of masks comprising organic materials · CPC title

• H10P50/695

  characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask · CPC title

• H10P50/692

  characterised by their composition, e.g. multilayer masks or materials · CPC title