# US 11,898,240 B2 · Selective deposition of silicon oxide on dielectric surfaces relative to metal surfaces

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- Number: US 11,898,240 B2
- Document ID: US11898240B2
- Status: Granted
- Kind: B2
- Application number: 17/216,466
- Filed: 2021-03-29
- Published: 2021-09-30
- Granted: 2024-02-13
- Earliest claimed: 2020-03-30
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Andrea Illiberi; Giuseppe Alessio Verni; Shaoren Deng; Daniele Chiappe; Eva Tois; Marko Tuominen; Michael Givens
- Web page: https://patentgrep.com/patent/US11898240B2

## CPC

- C23C 16/0281: {of metallic sub-layers (C23C16/029 takes precedence)}
- C23C 16/04: Coating on selected surface areas, e.g. using masks
- B01J 21/02: Boron or aluminium; Oxides or hydroxides thereof
- B01J 37/0215: {Coating}
- C23C 16/401: {containing silicon}
- C23C 16/402: {Silicon dioxide}
- C23C 16/45523: {Pulsed gas flow or change of composition over time}
- C23C 18/1212: {Zeolites, glasses}
- C23C 18/1291: {by heating of the substrate}
- C23C 22/77: Controlling or regulating of the coating process
- C23C 22/82: After-treatment
- B05D 1/32: using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
- B05D 1/60: {Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00)}
- 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)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)

## Abstract

Methods for selective deposition of silicon oxide films on dielectric surfaces relative to metal surfaces are provided. A metal surface of a substrate may be selectively passivated relative to the dielectric surface, such as with a polyimide layer or thiol SAM. Silicon oxide is selectively deposited on the dielectric surface relative to the passivated metal surface by contacting the dielectric surface with a metal catalyst and a silicon precursor comprising a silanol.

## Claims

### Claim 1

A method of selectively depositing silicon oxide on a dielectric surface of a substrate relative to a metal surface of the substrate, the method comprising, in order:
selectively passivating the dielectric surface relative to the metal surface;
selectively forming a polymer passivation layer on the metal surface;
contacting the dielectric surface with a metal catalyst; and
contacting the dielectric surface with a silicon reactant comprising a silanol.

### Claim 2 (depends on 1)

The method of claim 1, wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.

### Claim 3 (depends on 1)

The method of claim 1, wherein the dielectric surface comprises silicon oxide.

### Claim 4 (depends on 1)

The method of claim 1, wherein selectively passivating the dielectric surface comprises contacting the dielectric surface with a silylating agent.

### Claim 5 (depends on 4)

The method of claim 4, wherein the silylating agent comprises an alkylaminosilane.

### Claim 6 (depends on 4)

The method of claim 4, wherein the silylating agent comprises allyltrimethylsilane (TMS-A), chlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA).

### Claim 7 (depends on 1)

The method of claim 1, additionally comprising treating the dielectric surface with plasma after selectively forming the polymer passivation layer on the metal surface and prior to contacting the dielectric surface with the metal catalyst.

### Claim 8 (depends on 1)

The method of claim 1, wherein the metal catalyst comprises trimethyl aluminum (TMA), dimethylaluminumchloride, aluminum trichloride (AlCl3), dimethylaluminum isopropoxide (DMAI), tri s(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA) or triethyl aluminum (TEA).

### Claim 9 (depends on 1)

The method of claim 1, wherein the metal catalyst is a metal compound comprising Zn, Mg, Mn, La, Hf, Al, Zr, Ti, Sn, or Ga.

### Claim 10 (depends on 1)

The method of claim 1, wherein the silicon reactant comprises tris(tert-butoxy)silanol (TBS), tris(isopropoxy)silanol (TIS), or tris(tert-pentoxy)silanol (TPS).

### Claim 11 (depends on 1)

The method of claim 1, wherein the polymer passivation layer formed on the metal surface comprises a self-assembled monolayer (SAM) or a polyimide layer.

### Claim 12 (depends on 1)

The method of claim 1, wherein the selectivity of deposition of silicon oxide on the catalyzed dielectric surface relative to the metal surface on which the polymer passivation layer has been formed is greater than about 50%.

### Claim 13

A method of selectively depositing silicon oxide on a dielectric surface of a substrate relative to a metal surface of the substrate comprising:
selectively forming a polymer passivation layer on the metal surface, and
conducting one or more silicon oxide deposition cycles comprising alternately and sequentially contacting the substrate with a metal catalyst and a silanol.

### Claim 14 (depends on 13)

The method of claim 13, additionally comprising contacting the dielectric surface with a silylating agent prior to selectively forming the polymer passivation layer on the metal surface.

### Claim 15 (depends on 14)

The method of claim 14, wherein the silylating agent comprises alyltrimethylsilane (TMS-A), chlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA).

### Claim 16 (depends on 13)

The method of claim 13, wherein the metal catalyst comprises trimethyl aluminum (TMA), dimethylaluminumchloride, aluminum trichloride (AlCl3), dimethylaluminum isopropoxide (DMAI), tris(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA) or triethyl aluminum (TEA).

### Claim 17 (depends on 13)

The method of claim 13, wherein the silanol is tris(tert-pentoxy)silanol (TPS).

### Claim 18 (depends on 13)

The method of claim 13, wherein the silicon oxide deposition cycle is repeated two or more times in a row.

### Claim 19 (depends on 13)

The method of claim 13, wherein the substrate is contacted with the silanol two or more times in at least one silicon oxide deposition cycle.

### Claim 20 (depends on 13)

The method of claim 13, wherein the polymer passivation layer comprises a polyimide layer or a thiol SAM.