Methods for forming vertically layered ionic liquid crystal (ILC) structures on a semiconductor substrate

Patent metadata

Field	Value
Publication number	US-12444606-B2
Application number	US-202318388240-A
Country	US
Kind code	B2
Filing date	Nov 9, 2023
Priority date	Nov 9, 2023
Publication date	Oct 14, 2025
Grant date	Oct 14, 2025

Abstract

Embodiments of improved methods and processes are provided for patterning a semiconductor substrate using direct self-assembly (DSA) of ionic liquid crystals (ILCs). In the disclosed embodiments, an ILC solution comprising ILCs is deposited on a variety of substrate surfaces. An upper surface of the ILC solution is exposed to a gas phase, non-polar solvent (such as, e.g., hexane gas). The gas phase, non-polar solvent provides an ambient environment that promotes self-assembly of the ILCs into vertically layered ILC structures.

First claim

What is claimed is:

1. A method to form a pattern on a semiconductor substrate, the method comprising:
depositing an ionic liquid crystal (ILC) solution on a surface of the semiconductor substrate, the ILC solution comprising ionic liquid crystals (ILCs) having cation head groups, alkyl tail groups and anions;
exposing an upper surface of the ILC solution to a gas phase, non-polar solvent, which promotes self-assembly of the ILCs into a vertically layered structure on the surface of the semiconductor substate, the vertically layered structure having alternating layers of head group layers and tail group layers, with the anions segregated to the head group layers; and
utilizing the vertically layered structure to form the pattern on the semiconductor substrate.

2. The method of claim 1 , wherein said depositing the ILC solution comprises depositing the ILC solution on a periodic substrate surface comprising alternating hydrophilic surface layers and hydrophobic surface layers.

3. The method of claim 2 , wherein the gas phase, non-polar solvent enables the ILCs to self-assemble into the vertically layered structure on the periodic substrate surface with the head group layers and anions vertically aligned with the hydrophilic surface layers and the tail group layers vertically aligned with the hydrophobic surface layers.

4. The method of claim 1 , wherein said depositing the ILC solution comprises depositing the ILC solution within at least one feature formed on the semiconductor substrate, the at least one feature having a neutral bottom surface and hydrophilic sidewall surfaces.

5. The method of claim 4 , wherein the gas phase, non-polar solvent enables the ILCs to self-assemble into the vertically layered structure within the at least one feature, wherein the head group layers of the vertically layered structures are oriented towards the hydrophilic sidewall surfaces of the at least one feature.

6. The method of claim 1 , wherein the cation head groups within the ILCs comprise an imidazolium, pyrazolium, pyrrolidinium, pyridinium, piperidinium, morpholinium, ammonium, phosphonium, sulphonium or cholinium based cation head group.

7. The method of claim 1 , wherein the ILCs comprise an imidazolium-based cation head group of the form: 1-R 1 -3-R 2 -imidazolium, where R 1 is an alkyl chain with a chain length ranging from 8-18 carbons, and R 2 is a hydrogen, methyl, ethyl, propyl, butyl, substituted or unsubstituted phenyl, or other hydrocarbon group.

8. The method of claim 7 , wherein the anions within the ILCs comprise tetrafluoroborate (BF 4 − ), chloride (Cl − ), acetate (CH 3 COO − ), hexafluorophosphate (PF 6 − ), trifluoromethyl acetate (C 3 H 3 F 3 O 2 − ), nitrate (NO 3 − ), dicyanamide (C 2 HN 3 − ), tetracyanoborate (B(CN) 4 − ), trifluoromethane sulfonate (CF 3 O 3 S − ) or bis((trifluoromethyl)sulfonyl)imdide ([(CF 3 SO 2 ) 2 N] − ).

9. The method of claim 7 , wherein the anions within the ILCs comprise chloroaluminate anions, chloroferrate anions, chlorostannate anions, chloroindate anions or chlorozincate anions.

10. The method of claim 1 , wherein the gas phase, non-polar solvent comprises hexane (C 6 H 14 ), cyclohexane (C 6 H 12 ), pentane (C 5 H 12 ), heptane (C 7 H 16 ) or another gas phase alkane.

11. The method of claim 1 , wherein the gas phase, non-polar solvent comprises benzene (C 6 H 6 ), toluene (C 6 H 5 CH 3 ), xylene (C 8 H 10 ) or another gas phase aromatic hydrocarbon.

12. A method to form a pattern on a semiconductor substrate, the method comprising:
depositing an ionic liquid crystal (ILC) solution on a periodic surface of the semiconductor substrate, the ILC solution comprising ionic liquid crystals (ILCs) having cation head groups, alkyl tail groups and anions, the periodic surface comprising alternating hydrophilic surface layers and hydrophobic surface layers;
exposing an upper surface of the ILC solution to a gas phase, non-polar solvent, wherein the gas phase, non-polar solvent promotes self-assembly of the ILCs into a vertically layered structure having alternating layers of head group layers and tail group layers, with the anions segregated to the head group layers, by providing an ambient environment that enables: (a) the head group layers to vertically align with the hydrophilic surface layers of the periodic surface, and (b) the tail group layers to vertically align with the hydrophobic surface layers of the periodic surface; and
utilizing the vertically layered structure to form the pattern on the semiconductor substrate.

13. The method of claim 12 , wherein the cation head groups within the ILCs comprise an imidazolium, pyrazolium, pyrrolidinium, pyridinium, piperidinium, morpholinium, ammonium, phosphonium, sulphonium or cholinium based cation head group.

14. The method of claim 12 , wherein the ILCs comprise an imidazolium-based cation head group of the form: 1-R 1 -3-R 2 -imidazolium, where R 1 is an alkyl chain with a chain length ranging from 8-18 carbons, and R 2 is a hydrogen, methyl, ethyl, propyl, butyl, substituted or unsubstituted phenyl, or other hydrocarbon group.

15. The method of claim 14 , wherein the anions within the ILCs comprise tetrafluoroborate (BF 4 − ), chloride (Cl − ), acetate (CH 3 COO − ), hexafluorophosphate (PF 6 − ), trifluoromethyl acetate (C 3 H 3 F 3 O 2 − ), nitrate (NO 3 − ), dicyanamide (C 2 HN 3 − ), tetracyanoborate (B(CN) 4 − ), trifluoromethane sulfonate (CF 3 O 3 S − ) or bis((trifluoromethyl)sulfonyl)imdide ([(CF 3 SO 2 ) 2 N] − ).

16. The method of claim 14 , wherein the anions within the ILCs comprise chloroaluminate anions, chloroferrate anions, chlorostannate anions, chloroindate anions or chlorozincate anions.

17. The method of claim 16 , wherein said utilizing the vertically layered structure to form the pattern on the semiconductor substrate comprises exposing the semiconductor substrate to an oxidization process to remove the tail group layers from the vertically layered structure and convert the head group layers of the vertically layered structure into a metal oxide pattern.

18. The method of claim 17 , wherein said exposing the semiconductor substrate to the oxidization process comprises exposing the semiconductor substrate to an oxygen plasma ashing process, an ultra-violet (UV) ozone process, a gas phase oxidation process or a solution phase oxidation process.

19. The method of claim 12 , wherein the gas phase, non-polar solvent comprises hexane (C 6 H 14 ), cyclohexane (C 6 H 12 ), pentane (C 5 H 12 ), heptane (C 7 H 16 ) or another gas phase alkane.

20. The method of claim 12 , wherein the gas phase, non-polar solvent comprises benzene (C 6 H 6 ), toluene (C 6 H 5 CH 3 ), xylene (C 8 H 10 ) or another gas phase aromatic hydrocarbon.

Assignees

• Tokyo Electron Ltd

Inventors

• Aryal Dipak
• Pacheco Rotondaro Antonio Luis
• Nakano Takeo
• Iwashita Mitsuaki
• Asako Ryuichi
• Morimoto Tamotsu
• Abel Paul

Classifications

• H10P76/4083

  characterised by their behaviours during the lithography processes, e.g. soluble masks or redeposited masks · CPC title

• H10P76/405 Primary

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

• H10P76/4085 Primary

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

• C09K19/04

  characterised by the chemical structure of the liquid crystal components {, e.g. by a specific unit} · CPC title

• H01L21/0335

  Electricity · mapped topic