# US 11,993,844 B2 · Passivation of silicon dioxide defects for atomic layer deposition

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- Number: US 11,993,844 B2
- Document ID: US11993844B2
- Status: Granted
- Kind: B2
- Application number: 16/857,335
- Filed: 2020-04-24
- Published: 2020-10-29
- Granted: 2024-05-28
- Earliest claimed: 2019-04-24
- Assignees: The Regents of the University of California
- Applicants: The Regents of the University of California
- Inventors: Steven Wolf; Michael Breeden; Ashay Anurag; Andrew Kummel
- Web page: https://patentgrep.com/patent/US11993844B2

## CPC

- 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}
- H10P 14/3434: {being oxide semiconductor materials (Group IIB-VIA semiconductor materials H10P14/3424)}
- C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence)
- C23C 16/0227: {by cleaning or etching}
- C23C 16/04: Coating on selected surface areas, e.g. using masks
- C23C 16/405: {of refractory metals or yttrium}
- C23C 16/42: Silicides
- C23C 16/45525: {Atomic layer deposition [ALD]}
- H10D 64/0112: {using conductive layers comprising silicides}
- H10P 14/24: using chemical vapour deposition [CVD]
- H10P 14/272: {using mask materials other than SiO2 or SiN}
- H10P 14/3411: {Silicon, silicon germanium or germanium}
- H10P 14/3426: {Oxides}
- H10P 14/36: {characterised by treatments done before the formation of the materials}
- H10P 14/412: {Deposition of metallic or metal-silicide materials}
- H10P 14/414: {of metal-silicide materials}
- H10P 14/6534: {by exposure to a liquid}
- H10P 14/6546: {to change the surface groups of the insulating materials}
- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- H10W 20/096: {by contacting with gases, liquids or plasmas}
- H10W 20/032: {of conductive barrier, adhesion or liner layers}
- H10W 20/038: {covering conductive structures (H10W20/037 takes precedence)}
- H10W 20/077: {on sidewalls or on top surfaces of conductors (H10W20/076 takes precedence)}
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

The present inventive concept is related to methods for passivating an oxide layer and methods of selectively depositing a metal, metal nitride, metal oxide, or metal silicide layer on a metal, metal oxide, or silicide layer over an oxide layer including exposing the oxide layer to a passivant that selectively binds to the oxide layer over the metal, metal oxide, or silicide layer, and selectively growing the metal, metal nitride, metal oxide or metal silicide layer on the metal, metal oxide or silicide layer.

## Claims

### Claim 1

A method for selectively depositing a metal, metal nitride, metal oxide, or metal silicide layer on a substrate, the substrate comprising a surface, the surface comprising: an SiO2 layer portion comprising hydroxyl groups on SiO2; and a metal or metal oxide portion, the method comprising:
a) pre-treating the SiO2 layer portion of the surface, wherein the pre-treating cleans and renders the SiO2 layer portion of the surface hydrophilic;
b) exposing the surface to a passivant for a period of time between about 2 hours and less than about 24 hours at a temperature of about 200° C. or below that renders the surface of the SiO2 layer portion of the surface hydrophobic;
c) annealing the substrate at a temperature of about 300° C. or above to selectively passivate the SiO2 layer portion of the surface over the metal or metal oxide portion of the surface, wherein the passivant binds selectively to —OH or O on the SiO2 layer portion over the metal or metal oxide portion above about 300° C., wherein the passivant is selectively bound to the SiO2 portion of the surface over the metal or metal oxide portion of the surface, and wherein the metal or metal oxide of the surface is unpassivated and/or has characteristics of an unpassivated surface after the substrate is annealed; and
d) selectively growing the metal, metal nitride, metal oxide, or metal silicide layer on the metal or metal oxide portion of the surface,
wherein the passivant enhances selective growth of the metal, metal nitride, metal oxide, or metal silicide layer on the metal or metal oxide portion of the surface over the SiO2 layer portion of the surface, and wherein the metal, metal oxide, metal nitride, or metal silicide layer is grown by atomic layer deposition (ALD), and wherein the passivant is tetramethyldisilazane (TMDS).

### Claim 2 (depends on 1)

The method of claim 1, wherein the substrate is annealed in an ultra-high vacuum (UHV) after the substrate is exposed to the passivant.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal or metal oxide portion of the surface of the substrate comprises W, Cu, or Co.

### Claim 4 (depends on 1)

The method of claim 1, wherein the metal, metal nitride, metal oxide, or metal silicide layer grown is molybdenum silicide, titanium dioxide, or hafnium dioxide.

### Claim 5 (depends on 1)

The method of claim 1, wherein exposing the oxide layer portion of the surface of the substrate to the passivant comprises exposing the oxide layer portion of the surface of the substrate to a solution comprising the passivant.

### Claim 6 (depends on 1)

The method of claim 1, wherein the surface is exposed to the passivant at a temperature between about 70° C. and about 100° C.

### Claim 7

A method for selectively depositing a molybdenum silicide TiO2 layer on a substrate, the substrate comprising a surface, the surface comprising: a SiO2 portion; and a Cu or Co portion, the method comprising:
a) pre-treating the SiO2 portion of the surface, the SiO2 portion of the surface comprising hydroxyl groups, wherein the pre-treating renders the SiO2 portion of the surface hydrophilic;
b) exposing the SiO2 portion of the surface to a passivant for a period of time of less than about 24 hours at a temperature of about 200° or below that renders the surface of the SiO2 portion of the surface hydrophobic;
c) annealing the substrate at a temperature of about 300° C. or above to selectively passivate the SiO2 portion of the surface over the Cu or Co portion of the surface, wherein the passivant is selectively bound to the SiO2 portion of the surface over the Cu or Co portion of the surface, and wherein the Cu or Co portion of the surface is unpassivated and/or has characteristics of an unpassivated surface after the substrate is annealed; and
d) selectively growing the molybdenum silicide or TiO2 layer on the Cu or Co portion of the surface,
wherein the passivant enhances selective growth of the molybdenum silicide or TiO2 layer on the Cu or Co portion of the surface over the SiO2 portion of the surface, wherein the molybdenum silicide or TiO2 layer is grown by atomic layer deposition (ALD), and wherein the passivant is tetramethyldisilazane (TMDS).

### Claim 8 (depends on 7)

The method of claim 7, wherein the substrate is annealed in an ultra-high vacuum (UHV) after the substrate is exposed to the passivant.

### Claim 9 (depends on 7)

The method of claim 7, wherein exposing the SiO2 portion of the surface to the passivant comprises exposing the SiO2 portion of the surface to a solution comprising the passivant.

### Claim 10 (depends on 7)

The method of claim 7, wherein the surface is exposed to the passivant for a period of time between about 2 hours and about 24 hours.