Deposition of organic films

• US 10,453,701 B2
• Filed: 04/12/2017
• Issued: 10/22/2019
• Est. Priority Date: 06/01/2016
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Tois, Eva E., Suemori, Hidemi, Pore, Viljami J., Haukka, Suvi P., Sharma, Varun, Maes, Jan Willem, Longrie, Delphine, Kachel, Krzysztof
• Primary Examiner(s): Nikmanesh, Seahvosh
• Application Number:
  US15/486,124
• Publication Number:
  US 20170352550A1
• Time in Patent Office: 923 Days
• CPC Class Codes: C23C 16/04 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01L 21/02118 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC polymers per se C08G, photoresist per se G03F
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02186 the material containing titanium, e.g. TiO2
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/0337 characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
• CPC Class Codes: H01L 21/31138 by dry-etching
• CPC Class Codes: H01L 21/31144 using masks
• CPC Class Codes: H01L 21/32 using masks
• CPC Class Codes: H01L 21/32139 using masks
• CPC Class Codes: H01L 21/76834 formation of thin insulating films on the sidewalls or on top of conductors H01L21/76831 takes precedence

Abstract

Processes are provided herein for deposition of organic films. Organic films can be deposited, including selective deposition on one surface of a substrate relative to a second surface of the substrate. For example, polymer films may be selectively deposited on a first metallic surface relative to a second dielectric surface. Selectivity, as measured by relative thicknesses on the different layers, of above about 50% or even about 90% is achieved. The selectively deposited organic film may be subjected to an etch process to render the process completely selective. Processes are also provided for particular organic film materials, independent of selectivity. Masking applications employing selective organic films are provided. Post-deposition modification of the organic films, such as metallic infiltration and/or carbon removal, is also disclosed.

Claims

1. A process for forming an etch mask on a first surface of a substrate comprising the first surface and a second surface, the process comprising:

contacting the substrate with a first vapor phase precursor; and

contacting the substrate with a second vapor phase precursor;

wherein contacting the substrate with the first and second vapor phase precursors forms an organic film selectively on the first surface relative to the second surface,

wherein the etch mask comprises the organic film formed on the first surface of the substrate.

2. The process of claim 1, wherein the contacting steps comprise a deposition cycle, the process comprising one or more deposition cycles.

3. The process of claim 2, further comprising repeating the contacting steps until an etch mask of a desired thickness has been formed.

4. The process of claim 2, wherein the first surface is a metallic surface.

5. The process of claim 2, wherein the second surface is a dielectric surface.

6. The process of claim 2, wherein the organic film comprises a polyimide film.

7. The process of claim 6 wherein the first vapor phase precursor comprises 1,6-diaminohexane (DAH).

8. The process of claim 6, wherein the second vapor phase precursor comprises pyromellitic dianhydride (PMDA).

9. The process of claim 2, further comprising subjecting the substrate to an etch process, wherein the etch process removes substantially all of any formed organic film from the second surface of the substrate and does not remove all of the formed organic film from the first surface of the substrate.

10. The process of claim 2, wherein the etch mask is used in a tone reversal process.

11. The process of claim 2, wherein the etch mask comprises a block mask for use in a block mask process.

12. The process of claim 2, wherein the etch mask comprises a protection layer in a selective deposition process comprising selectively depositing a material on the second surface of the substrate relative to the etch mask.

13. A process for forming an infiltrated film as a hard mask on a first surface of a substrate comprising the first surface and a second surface, the process comprising:

performing a selective deposition process comprising;

contacting the substrate with a first vapor phase precursor;

contacting the substrate with a second vapor phase precursor;

wherein contacting the substrate with the first and second vapor phase precursors forms an organic thin film selectively on the first surface relative to the second surface; and

subjecting the selectively formed organic film to an infiltration process to incorporate a metal into the selectively formed organic film and thereby form the infiltrated film as the hard mask.

14. The process of claim 13, wherein the contacting steps of the selective deposition process comprise a deposition cycle, the selective deposition process comprising one or more deposition cycles.

15. The process of claim 14, wherein incorporating the metal comprises incorporating an elemental metal, multiple metals, metal alloy, metal oxide, metal nitride, metal carbide and/or combinations thereof.

16. The process of claim 15, wherein the infiltration process comprises alternately and sequentially exposing the selectively formed organic film to a first reactant comprising the metal and a second reactant.

17. The process of claim 15, wherein aluminum oxide (Al₂O₃) and/or or titanium dioxide (TiO₂) is incorporated into the selectively formed organic film.

18. The process of claim 14, further comprising subjecting the selectively formed organic film to an ashing process removing carbon from the selectively formed organic film.

19. The process of claim 18, wherein the ashing process comprises exposing the selectively formed organic film to oxygen atoms, oxygen radicals, oxygen plasma, or combinations thereof.

20. The process of claim 19, wherein the infiltrated organic film has an increased resistance to an HF etch relative to the same organic film that has not been subjected to an infiltration process.