# US 10,483,100 B2 · Method for forming TiON film

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- Number: US 10,483,100 B2
- Document ID: US10483100B2
- Status: Granted
- Kind: B2
- Application number: 15/273,383
- Filed: 2016-09-22
- Published: 2017-03-30
- Granted: 2019-11-19
- Earliest claimed: 2015-09-25
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Tadahiro Ishizaka; Masaki Koizumi; Masaki Sano; Seokhyoung Hong
- Web page: https://patentgrep.com/patent/US10483100B2

## CPC

- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- C23C 16/308: {Oxynitrides}
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- H10B 43/27: the channels comprising vertical portions, e.g. U-shaped channels
- H10D 1/00: Resistors, capacitors or inductors
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6522: {introduced into a nitride material, e.g. changing SiN to SiON}
- H10P 14/6532: {by exposure to a plasma}
- H10P 72/0402: {Apparatus for fluid treatment (H10P72/0441, H10P72/0448 take precedence)}
- H10P 72/0471: {comprising at least one ion or electron beam chamber}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- 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)
- H10B: ELECTRONIC MEMORY DEVICES
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

A TiON film forming method is provided. A cycle of forming a unit TiN film at a predetermined processing temperature by alternately supplying a Ti-containing gas and a nitriding gas into the processing chamber accommodating a target substrate and oxidizing the unit TiN film by supplying an oxidizing agent into the processing chamber is repeated multiple times. In an initial stage of the film formation, a cycle of repeating the alternate supply of the Ti-containing gas and the nitriding gas X1 times and supplying the oxidizing agent is repeated Y1 times. In a later stage of the film formation, a cycle of repeating the alternate supply of the Ti-containing gas and the nitriding gas X2 times and supplying the oxidizing agent is repeated Y2 times until a desired film thickness is obtained. The number of repetition X1 is set to be greater than the number of repetition X2.

## Claims

### Claim 1

A TiON film forming method comprising:
accommodating a target substrate in a processing chamber;
maintaining an inside of the processing chamber in a depressurized state; and
repeating multiple times a cycle of forming a unit TiN film at a predetermined processing temperature by alternately supplying a Ti-containing gas and a nitriding gas into the processing chamber and oxidizing the unit TiN film by supplying an oxidizing agent into the processing chamber,
wherein in an initial stage of the film formation, a cycle of supplying the oxidizing agent after repeating the alternate supply of the Ti-containing gas and the nitriding gas X1 times is repeated Y1 times,
wherein in a later stage of the film formation; a cycle of supplying the oxidizing agent after repeating the alternate supply of the Ti-containing gas and the nitriding gas X2 times is repeated Y2 times until a desired film thickness is obtained,
wherein the number of repetition X1 in the initial stage of the film formation is set to be greater than the number of repetition X2 in the later stage of the film formation, and
wherein the Y1 is within a range of wherein a relation between X1 and X2 is selected based on a desired film surface smoothness.

### Claim 2 (depends on 1)

The TiON film forming method of claim 1, wherein the X1 is within a range of 10≤X≤160 and the X2 is within a range of 1≤X2≤25.

### Claim 3 (depends on 1)

The TiON film forming method of claim 1, wherein the X1 is at least three times greater than the X2.

### Claim 4 (depends on 1)

The TiON film forming method of claim 1, further comprising:
after the forming of the unit TiN film and before the oxidizing of the unit TiN film, performing a post flow process of supplying the nitriding gas into the processing chamber.

### Claim 5 (depends on 4)

The TiON film forming method of claim 4, wherein the post flow process is performed by repeating supply of the nitriding gas and supply of a purge gas multiple times.

### Claim 6 (depends on 4)

The TiON film forming method of claim 4, wherein the oxidizing agent is supplied intermittently multiple times.

### Claim 7 (depends on 1)

The TiON film forming method of claim 1, further comprising:
after the film formation, performing Ar ion treatment on the surface of the film.

### Claim 8 (depends on 7)

The TiON film forming method of claim 7, wherein the Ar ion treatment is performed by generating an Ar plasma and attracting Ar ions in the Ar plasma to the target substrate.

### Claim 9 (depends on 7)

The TiON film forming method of claim 7, wherein the Ar ion treatment is performed on the surface of the film by bombardment effect of the Ar ions.

### Claim 10 (depends on 7)

The TiON film forming method of claim 7, wherein the film formation and the Ar ion treatment are performed by separate apparatuses.

### Claim 11 (depends on 10)

The TiON film forming method of claim 10, wherein the apparatus for performing the film formation and the apparatus for performing the Ar ion treatment are installed in a processing system including a transfer system for transferring the target substrate in a vacuum state and consecutively perform the film formation and the Ar ion treatment while maintaining a vacuum state.

### Claim 12 (depends on 7)

The TiON film forming method of claim 7, wherein the film formation and the Ar ion treatment are performed in a same processing chamber.

### Claim 13 (depends on 1)

The TiON film forming method of claim 1, wherein
the oxidizing of the unit Ti N film is performed by intermittently supplying the oxidizing agent into the processing chamber.

### Claim 14 (depends on 1)

The TiON film forming method of claim 1, wherein the Ti-containing gas is TiCl4 gas and the nitriding gas is NH3 gas.

### Claim 15 (depends on 1)

The TiON film forming method of claim 1, wherein the oxidizing agent is an oxygen-containing gas selected from a group consisting of O2 gas, O3 gas, H2O and NO2 or a plasma of the oxygen-containing gas.

### Claim 16 (depends on 1)

The TiON film forming method of claim 1, wherein the processing temperature ranges from 300° C. to 500° C.

### Claim 17 (depends on 13)

The TiON film forming method of claim 13, wherein the oxidizing agent is supplied in a pulsed manner.

### Claim 18 (depends on 13)

The TiON film forming method of claim 13, wherein the oxidizing of the unit TiN film is performed by repeating multiple times a cycle of supplying the oxidizing agent into the processing chamber and purging the processing chamber.