# US 10,373,820 B2 · Deposition of organic films

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- Number: US 10,373,820 B2
- Document ID: US10373820B2
- Status: Granted
- Kind: B2
- Application number: 15/170,769
- Filed: 2016-06-01
- Published: 2017-12-07
- Granted: 2019-08-06
- Earliest claimed: 2016-06-01
- Assignees: ASM IP Holding B.V.
- Applicants: Asm IP Holding B.V.
- Inventors: Eva E. Tois; Hidemi Suemori; Viljami J. Pore; Suvi P. Haukka; Varun Sharma
- Web page: https://patentgrep.com/patent/US10373820B2

## CPC

- H10P 14/432: {using selective deposition}
- B05D 1/60: {Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00)}
- C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence)
- C23C 16/04: Coating on selected surface areas, e.g. using masks
- C23C 16/45525: {Atomic layer deposition [ALD]}
- C23C 16/45527: {characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/56: After-treatment
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/683: {carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC}
- H10P 50/242: {of Group IV materials}
- H10P 50/287: {by chemical means}
- H10W 20/077: {on sidewalls or on top surfaces of conductors (H10W20/076 takes precedence)}
- H10W 20/096: {by contacting with gases, liquids or plasmas}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## 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.

## Claims

### Claim 1

A process for selectively depositing an organic film on a substrate comprising a first surface and a second surface, the process comprising:
multiple consecutive deposition cycles each 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 the organic thin film selectively on the first surface relative to the second surface; and
subjecting the substrate to an etch process subsequent to the multiple consecutive deposition cycles, wherein the etch process has a chemistry for removal of organic material and removes substantially all of any deposited organic film from the second surface of the substrate and does not remove substantially all of the deposited organic film from the first surface of the substrate.

### Claim 2 (depends on 1)

The process of claim 1, wherein the multiple consecutive deposition cycles are repeated until an organic thin film of a desired thickness is formed.

### Claim 3 (depends on 2)

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

### Claim 4 (depends on 3)

The process of claim 3, wherein the first vapor phase precursor comprises a diamine.

### Claim 5 (depends on 4)

The process of claim 4, wherein the substrate is contacted with the first vapor phase precursor comprising a diamine before it is contacted with another, different precursor.

### Claim 6 (depends on 3)

The process of claim 3, wherein the second vapor phase precursor comprises a dianyhydride.

### Claim 7 (depends on 3)

The process of claim 3, wherein the substrate is held at a temperature of greater than about 170° C. during the multiple consecutive deposition cycles.

### Claim 8 (depends on 2)

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

### Claim 9 (depends on 8)

The process of claim 8, wherein the first vapor phase precursor comprises a halogen.

### Claim 10 (depends on 8)

The process of claim 8, wherein the substrate is held at a temperature of greater than about 80° C. during the multiple consecutive deposition cycles.

### Claim 11 (depends on 1)

The process of claim 1, wherein the second surface comprises an inorganic dielectric surface.

### Claim 12 (depends on 11)

The process of claim 11, wherein the second surface is an inorganic dielectric surface.

### Claim 13 (depends on 1)

The process of claim 1, wherein the substrate is contacted with the second vapor phase precursor before the substrate is contacted with the first vapor phase precursor.

### Claim 14 (depends on 1)

The process of claim 1, wherein the thin organic film is deposited on the first surface relative to the second surface with a selectivity of above about 50%.

### Claim 15 (depends on 1)

The process of claim 1, wherein the first surface comprises a metal oxide, elemental metal, or metallic surface.

### Claim 16 (depends on 1)

The process of claim 1, wherein the first surface comprises tungsten.

### Claim 17 (depends on 1)

The process of claim 1, wherein the second surface comprises silicon.

### Claim 18 (depends on 17)

The process of claim 17, wherein the second surface comprises SiO2.

### Claim 19 (depends on 1)

The process of claim 1, wherein the etch process comprises exposing the substrate to hydrogen atoms, hydrogen radicals, hydrogen plasma, or combinations thereof.

### Claim 20 (depends on 1)

The process of claim 1, wherein the etch process comprises exposing the substrate to oxygen atoms, oxygen radicals, oxygen plasma, or combinations thereof.

### Claim 21 (depends on 1)

The process of claim 1, wherein each deposition cycle further comprises removing excess of the first vapor phase precursor and reaction by-products prior to contacting the substrate with the second vapor phase precursor.

### Claim 22 (depends on 21)

The process of claim 21, wherein each deposition cycle further comprises removing excess of the second vapor phase precursor after contacting the substrate with the second vapor phase precursor and prior to a next deposition cycle.

### Claim 23

A process for selectively depositing an organic film on a substrate comprising a first surface and a second surface, the process comprising:
multiple consecutive deposition cycles each comprising:
contacting the first surface and the second surface of the substrate with a first vapor phase precursor;
contacting the first surface and the second surface of the substrate with a second vapor phase precursor,
wherein contacting the first surface and the second surface of the substrate with the first and second vapor phase precursors forms the organic thin film selectively on the first surface relative to the second surface,
wherein the second surface comprises an inorganic dielectric surface; and
repeating the contacting steps until an organic thin film of a desired thickness is formed; and
subjecting the substrate to an etch process subsequent to the multiple consecutive deposition cycles, wherein the etch process has a chemistry for removal or organic material and removes substantially all of any deposited organic film from the second surface of the substrate and does not remove substantially all of the deposited organic film from the first surface of the substrate.

### Claim 24 (depends on 23)

The process of claim 23, wherein the etch process comprises exposing the substrate to hydrogen atoms, hydrogen radicals, hydrogen plasma, or combinations thereof.

### Claim 25 (depends on 23)

The process of claim 23, wherein the etch process comprises exposing the substrate to oxygen atoms, oxygen radicals, oxygen plasma, or combinations thereof.