# US 10,319,624 B2 · Oxidative volumetric expansion of metals and metal containing compounds

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- Number: US 10,319,624 B2
- Document ID: US10319624B2
- Status: Granted
- Kind: B2
- Application number: 15/621,120
- Filed: 2017-06-13
- Published: 2017-12-14
- Granted: 2019-06-11
- Earliest claimed: 2016-06-14
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Susmit Singha Roy; Yihong Chen; Kelvin Chan; Abhijit Basu Mallick; Srinivas Gandikota; Pramit Manna
- Web page: https://patentgrep.com/patent/US10319624B2

## CPC

- H10W 10/17: formed using trench refilling with dielectric materials, e.g. shallow trench isolations
- H10D 64/01344: {in a nitrogen-containing ambient, e.g. N2O oxidation}
- H10D 64/60: Electrodes characterised by their materials
- H10D 84/0151: {Manufacturing their isolation regions}
- H10D 84/038: {using silicon technology, e.g. SiGe}
- H10P 14/61: using masks
- H10W 10/014: {using trench refilling with dielectric materials, e.g. shallow trench isolations}
- H10W 10/0143: {comprising concurrently refilling multiple trenches having different shapes or dimensions}
- H10W 10/0145: {of trenches having shapes other than rectangular or V-shape (H10W10/0143 takes precedence)}
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Methods comprising forming a film on at least one feature of a substrate surface are described. The film is expanded to fill the at least one feature and cause growth of the film from the at least one feature. Methods of forming self-aligned vias are also described.

## Claims

### Claim 1

A processing method comprising:
providing a substrate surface having at least one feature therein, the at least one feature extending a depth from the substrate surface to a bottom surface, the at least one feature having a width defined by a first sidewall and a second sidewall;
forming a film on the substrate surface and the first sidewall second sidewall and bottom surface of the at least one feature; and
expanding the film to fill the at least one feature and cause the film to expand straight up from the at least one feature and form a gap between the substrate surface and the film.

### Claim 2 (depends on 1)

The method of claim 1, wherein the film comprises one or more of Co, Mo, W, Ta, Ti, Ru, Rh, Cu, Fe, Mn, V, Nb, Hf, Zr, Y, Al, Sn, Cr or La.

### Claim 3 (depends on 2)

The method of claim 2, wherein expanding the film comprises exposing the film to an oxidizing agent comprising one or more of O2, O3, N2O, H2O, H2O2, CO, CO2, NH3, N2/Ar, N2/He or N2/Ar/He, a nitridation agent comprising one or more of ammonia, hydrazine, NO2 or nitrogen plasma, a siliciding agent comprising one or more of trimethylsilane, silane, disilane, and/or a compound comprising germanium.

### Claim 4 (depends on 1)

The method of claim 1, wherein expanding the film occurs at a temperature greater than or equal to about 300° C.

### Claim 5 (depends on 1)

The method of claim 1, wherein the deposited film is conformal.

### Claim 6 (depends on 1)

The method of claim 1, wherein the feature has an aspect ratio greater than or equal to 10:1.

### Claim 7 (depends on 1)

The method of claim 1, further comprising doping the film with a dopant.

### Claim 8 (depends on 6)

The method of claim 6, wherein doping the film occurs with the formation of the film.

### Claim 9 (depends on 6)

The method of claim 6, wherein doping the film is performed sequentially with formation of the film.

### Claim 10 (depends on 1)

The method of claim 1, further comprising treating the film.

### Claim 11 (depends on 10)

The method of claim 10, wherein treating the film comprises annealing the film.

### Claim 12 (depends on 1)

The method of claim 1, wherein forming the film does not form a seam in the at least one feature.

### Claim 13

A processing method comprising:
providing a substrate surface having at least one feature thereon, the at least one feature extending a depth from the substrate surface to a bottom surface, the at least one feature having a width defined by a first sidewall and a second sidewall;
forming a metal film on the substrate surface and the first sidewall, second sidewall and bottom surface of the at least one feature; and
expanding the metal film to fill the at least one feature so that a top portion of the film comprises a metal oxide, metal nitride, metal silicide and/or metal-germanium species and the bottom portion of the film comprises the metal film.

### Claim 14 (depends on 13)

The method of claim 13, further comprising exposing the substrate to an etchant to remove the metal oxide film leaving the metal film in the bottom portion of the at least one feature.

### Claim 15 (depends on 13)

The method of claim 13, wherein expanding the metal film occurs at a temperature less than about 400° C.

### Claim 16 (depends on 13)

The method of claim 13, wherein the substrate comprises silicon nitride, the metal film comprises tungsten and the metal oxide film comprises tungsten oxide.

### Claim 17 (depends on 13)

The method of claim 13, wherein expanding the film occurs at a temperature less than about 350° C.

### Claim 18

A processing method comprising:
providing a substrate surface having at least one feature thereon, the at least one feature extending a depth from the substrate surface to a bottom surface, the at least one feature having a width defined by a first sidewall and a second sidewall, the substrate surface including a film filling the at least one feature and extending above the substrate surface;
removing the film above the substrate surface to leave the substrate surface and film in the features exposed;
expanding the film in the features to cause straight up growth of the film to form pillars of the film extending from the at least one feature;
forming a material layer on the substrate surface; and
removing the pillars of the film to leave the at least one feature with the material layer thereon.