SELECTIVE DEPOSITION USING HYDROPHOBIC PRECURSORS

• US 20170323776A1
• Filed: 04/28/2017
• Published: 11/09/2017
• Est. Priority Date: 05/05/2016
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Frm, Elina, Suemori, Hidemi, Matero, Raija, Niskanen, Antti, Haukka, Suvi P.
• Granted Patent: US 11,081,342 B2
• Time in Patent Office: Days
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/32 using masks

Abstract

Vapor deposition processes are provided in which a material is selectively deposited on a first surface of a substrate relative to a second organic surface. In some embodiments a substrate comprising a first surface, such as a metal, semi-metal or oxidized metal or semi-metal is contacted with a first vapor phase hydrophobic reactant and a second vapor phase reactant such that the material is deposited selectively on the first surface relative to the second organic surface. The second organic surface may comprise, for example, a self-assembled monolayer, a directed self-assembled layer, or a polymer, such as a polyimide, polyamide, polyuria or polystyrene. The material that is deposited may be, for example, a metal or metallic material. In some embodiments the material is a metal oxide, such as ZrO₂ or HfO₂. In some embodiments the vapor deposition process is a cyclic chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. In some embodiments the material is deposited on the first surface relative to the second surface with a selectivity of greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 90% or greater than about 95%.

Claims

1. A vapor deposition process for selectively depositing a material on a first surface of a substrate relative to a second organic surface, the method comprising:

contacting the substrate with a first vapor phase hydrophobic reactant; and

contacting substrate with a second vapor phase reactant,

wherein the material is deposited selectively on the first surface relative to the second organic surface.

2. The method of claim 1, wherein the material is a metal oxide.

3. The method of claim 1, wherein the first hydrophobic reactant comprises at least one hydrophobic hydrocarbon ligand.

4. The method of claim 1, wherein the first hydrophobic reactant comprises one or two hydrophilic ligands.

5. The method of claim 4, wherein the hydrophilic ligand comprises an alkylamine, alkoxide or halide.

6. The method of claim 1, wherein the second reactant comprises H₂O, O₃, H₂O₂, oxygen plasma, oxygen ions, oxygen radicals or excited species of oxygen.

7. The method of claim 1, wherein the first surface is a metal surface, a semi-metal surface, an oxidized metal surface or an oxidized semi-metal surface.

8. The method of claim 1, wherein the first surface is a dielectric surface.

9. The method of claim 1, wherein the second organic surface comprises a self-assembled monolayer (SAM) or a directed self-assembled layer (DSA).

10. The method of claim 1, wherein the second organic surface comprises a polymer.

11. The method of claim 10, wherein the polymer is a polyimide, polyamide, polyuria, or polystyrene.

12. The method of claim 1, wherein the vapor deposition process is a cyclic chemical vapor deposition process.

13. The method of claim 1, wherein the vapor deposition process is an atomic layer deposition process.

14. The method of claim 1, wherein the material is deposited on the first surface relative to the second surface with a selectivity of greater than about 50%.

15. A method for selectively depositing a metal oxide on a first surface of a substrate relative to a second surface, the method comprising:

contacting substrate with a first hydrophobic reactant comprising metal; and

contacting substrate with a second reactant,

wherein the first substrate surface comprises a metal or semimetal containing material and the second substrate surface comprises an organic material.

16. The method of claim 15, wherein the metal oxide is ZrO₂.

17. The method of claim 15, wherein the first hydrophobic metal reactant has the formula L_nMX_y, in which:

n is from 1 to 6;

y is from 0 to 2;

L is a hydrophobic ligand;

X is a hydrophilic ligand; and

M is a metal.

18. The method of claim 17, wherein M is selected from Hf, Zr, Ta and Nb.

19. The method of claim 17, wherein L is a Cp or C1-C4 alkyl.

20. The method of claim 15, wherein the second reactant comprises H₂O.

21. The method of claim 15, wherein the first surface is a dielectric surface.

22. The method of claim 15, wherein the second surface comprises a SAM.

23. The method of claim 15, wherein the metal oxide is selectively deposited on the first surface of the substrate relative to the second surface with a selectivity of greater than 95%.