Poly(thioaminal) probe based lithography

Patent metadata

Field	Value
Publication number	US-10006936-B2
Application number	US-201715601504-A
Country	US
Kind code	B2
Filing date	May 22, 2017
Priority date	Nov 30, 2015
Publication date	Jun 26, 2018
Grant date	Jun 26, 2018

Abstract

Methods and materials for patterning a substrate are disclosed herein. A poly(thioaminal) material may be utilized as a thermal resist material for patterning substrates in a thermal scanning probe lithography process. The poly(thioaminal) material may be functionalized with an electron withdrawing group and various monomers may be volatilized upon exposure to a thermal scanning probe.

First claim

What is claimed is:

1. A method of patterning a substrate, comprising:
forming a poly(thioaminal) material by either (a) ring opening of a hexahydrotriazine with a thiol, or (b) reacting a stabilized imine intermediate with a thiol;
disposing the poly(thioaminal) material on a substrate; and
patterning the poly(thioaminal) material with a thermal scanning probe.

2. The method of claim 1 , wherein the poly(thioaminal) material is disposed on the substrate by a spin coating process.

3. The method of claim 1 , wherein the thermal scanning probe contacts the poly(thioaminal) material during the patterning.

4. The method of claim 3 , wherein the thermal scanning probe is maintained at a temperature of greater than about 225° C. during the patterning.

5. The method of claim 4 , wherein monomers of the poly(thioaminal) material are volatilized upon contact with the thermal scanning probe.

6. The method of claim 5 , wherein the monomers are one or more of a dithiol, an electron deficient amine, or combinations and mixtures thereof.

7. The method of claim 1 , wherein a temperature difference between a bulk of the poly(thioaminal) material and the thermal scanning probe is greater than about 200° C.

8. The method of claim 1 , wherein the stabilized imine intermediate is synthesized from an electron deficient amine.

9. The method of claim 1 , further comprising:
etching deprotected regions of the substrate after performing the patterning.

10. A method of patterning a substrate, comprising:
forming a poly(thioaminal) material by either (a) ring opening of a hexahydrotriazine with a thiol, or (b) reacting a stabilized imine intermediate with a thiol, the poly(thioaminal) material having a CH 2 —N(R′)—CH 2 —S—R—S repeating group, wherein:
each instance of R is selected from the group consisting of alkyl, aryl, and oligomer, and
each instance of R′ is an electron withdrawing group selected from the group consisting of CnF n+1 , CnF n−1 , C 6 H 4 X, and heterocyclyl thereof, and wherein X is selected from the group consisting of Br, Cl, NO 2 CF 3 , F, CO 2 Me CO 2 H, CN, and combinations thereof;

disposing the poly(thioaminal) material on a substrate; and
patterning the poly(thioaminal) material with a thermal scanning probe.

11. The method of claim 10 , wherein each instance of R is an oligomer selected from the group consisting of ether, siloxane, styrene, carbonate, lactide, methacrylate, acrylate, polyolefin, polyester, polyamide, polyamino, and combinations thereof.

12. The method of claim 10 , wherein the thermal scanning probe is maintained at a temperature of greater than about 225° C. during the patterning.

13. The method of claim 12 , wherein a temperature difference between a bulk of the poly(thioaminal) material and the thermal scanning probe is greater than about 200° C.

14. The method of claim 10 , wherein dithiol monomers, electron deficient amines, and combinations thereof are volatilized from the poly(thioaminal) material during the patterning.

15. The method of claim 10 , further comprising:
etching deprotected regions of the substrate after performing the patterning.

16. The method of claim 10 , wherein each instance of R is selected to tune a glass transition temperature of the poly(thioaminal) material.

17. The method of claim 10 , wherein each instance of R includes aromatic substituents, hydroxyl substituents, or combinations thereof.

18. The method of claim 10 , wherein each instance of R is

wherein each W is independently hydrogen or an electron withdrawing group, and Z is selected from the group consisting of CH 2 and C(CF 3 ) 2 .

19. A method of patterning a substrate, comprising:
forming a poly(thioaminal) material by either (a) ring opening of a hexahydrotriazine with a thiol, or (b) reacting a stabilized imine intermediate with a thiol, the poly(thioaminal) material having a S—CH 2 —NH—R—NH—CH 2 repeating group, wherein each instance of R is selected from the group consisting of alkyl, aryl, and oligomer;
disposing the poly(thioaminal) material on a substrate; and
patterning the poly(thioaminal) material with a thermal scanning probe.

20. The method of claim 19 , wherein each instance of R is selected from the group consisting of siloxane, styrene, carbonate, lactide, methacrylate, acrylate, polyamide, polyamino,

and combinations thereof, wherein each W is independently hydrogen or an electron withdrawing group, and Z is selected from the group consisting of CH 2 and C(CF 3 ) 2 .

Assignees

• IBM

Inventors

• Boday Dylan J
• Garcia Jeannette M
• Hedrick James L
• Wojtecki Rudy J

Classifications

• G01Q80/00 Primary

  Applications, other than SPM, of scanning-probe techniques (manufacture or treatment of nanostructures B82B3/00; recording or reproducing information using near-field interaction G11B9/12, G11B11/24, G11B13/08) · CPC title

• C08G73/0253

  Polyamines containing sulfur in the main chain · CPC title

• G03F7/0002

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

• C08G75/00

  Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule · CPC title

• C08G16/02

  of aldehydes · CPC title