# US 2019/0172705 A1 · Process for deposition of titanium oxynitride for use in integrated circuit fabrication

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- Number: US 2019/0172705 A1
- Document ID: US20190172705A1
- Status: Published application
- Kind: A1
- Application number: 16/268,260
- Filed: 2019-02-05
- Published: 2019-06-06
- Earliest claimed: 2015-08-25
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Viljami J. Pore; Seiji Okura; Hidemi Suemori
- Web page: https://patentgrep.com/patent/US20190172705A1

## CPC

- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- C23C 16/308: {Oxynitrides}
- 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 16/45531: {specially adapted for making ternary or higher compositions}
- C23C 16/45534: {Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers}
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/4554: {Plasma being used non-continuously in between ALD reactions (C23C16/56 takes precedence)}
- C23C 16/45542: {Plasma being used non-continuously during the ALD reactions}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10D 64/01344: {in a nitrogen-containing ambient, e.g. N2O oxidation}
- H10P 14/6318: {Formation by simultaneous oxidation and nitridation}
- H10P 14/6334: {using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329)}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- 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 50/283: {by chemical means}
- H10P 50/285: {of materials not containing Si, e.g. PZT or Al2O3}
- H10P 50/73: {using masks for insulating materials}
- H10P 76/4085: {characterised by the processes involved to create the masks}
- 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)
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

A process is provided for depositing a substantially amorphous titanium oxynitride thin film that can be used, for example, in integrated circuit fabrication, such as in forming spacers in a pitch multiplication process. The process comprises contacting the substrate with a titanium reactant and removing excess titanium reactant and reaction byproducts, if any. The substrate is then contacted with a second reactant which comprises reactive species generated by plasma, wherein one of the reactive species comprises nitrogen. The second reactant and reaction byproducts, if any, are removed. The contacting and removing steps are repeated until a titanium oxynitride thin film of desired thickness has been formed.

## Claims

### Claim 1

A process for depositing a titanium oxynitride thin film comprising:
contacting a substrate with an organometallic titanium reactant;
subsequently contacting the substrate with a plurality of reactive species generated by plasma from a gas; and
repeating the contacting steps until an amorphous titanium oxynitride thin film comprising from 0.05 at-% to 30 at-% of nitrogen has been formed on the substrate, wherein the titanium oxynitride thin film is deposited at a temperature from 50° C. to 300° C.

### Claim 2 (depends on 1)

The process of claim 1, wherein the gas comprises oxygen but not nitrogen.

### Claim 3 (depends on 1)

The process of claim 1, wherein the gas is O2 gas.

### Claim 4 (depends on 1)

The process of claim 1, wherein the gas does not comprise a noble gas.

### Claim 5 (depends on 1)

The process of claim 1, wherein the plurality of reactive species comprises reactive nitrogen and oxygen species.

### Claim 6 (depends on 5)

The process of claim 5, wherein the ratio of reactive nitrogen species to reactive oxygen species is from 1:2 to 250:1.

### Claim 7 (depends on 1)

The process of claim 1, wherein the reactive species comprise nitrogen atoms, nitrogen ions, nitrogen radicals, or nitrogen plasma and oxygen atoms, oxygen radicals, or oxygen plasma.

### Claim 8 (depends on 1)

The process of claim 1, wherein the gas comprises N2, NH3, or N2H2.

### Claim 9 (depends on 1)

The process of claim 1, wherein the gas comprises a noble gas.

### Claim 10 (depends on 9)

The process of claim 9, wherein the gas comprises Ar.

### Claim 11 (depends on 1)

The process of claim 1, wherein the plasma is generated by applying RF power of 200 W to 500 W to the gas.

### Claim 12 (depends on 1)

The process of claim 1, further comprising exposing the substrate to a purge gas and/or vacuum to remove excess titanium reactant and reaction byproducts, if any, after contacting the substrate with the titanium reactant and prior to contacting the substrate with the reactive species.

### Claim 13 (depends on 1)

The process of claim 1, further comprising after contacting the substrate with the titanium reactant moving the substrate such that it is subsequently contacted with the reactive species.

### Claim 14 (depends on 13)

The process of claim 13, wherein the substrate is moved within a single reaction space.

### Claim 15 (depends on 13)

The process of claim 13, wherein the substrate is moved from a first reaction space where it is contacted with the titanium reactant to a second, different reaction space where it is contacted with the reactive species.

### Claim 16 (depends on 1)

The process of claim 1, wherein the process is used to form spacers for use in a spacer patterning process.

### Claim 17 (depends on 1)

The process of claim 1, wherein the titanium oxynitride film is a sacrificial film in an integrated circuit patterning process.

### Claim 18 (depends on 1)

The process of claim 1, wherein the titanium oxynitride thin film has an RMS surface roughness of less than about 0.5 nm.

### Claim 19 (depends on 1)

The process of claim 1, wherein the titanium oxynitride thin film has a wet etch rate of 0.01 nm/min to 50 nm/min in 1% dHF.

### Claim 20 (depends on 1)

The process of claim 1, wherein the titanium reactant comprises a titanium alkylamide.

### Claim 21 (depends on 1)

The process of claim 1, wherein the titanium reactant comprises an alkylamine ligand.

### Claim 22 (depends on 1)

The process of claim 1, wherein the titanium reactant comprises Ti(NRIRII)4, wherein RI and RII can be independently selected to be alkyl groups.

### Claim 23 (depends on 1)

The process of claim 1, wherein the process is a plasma enhanced atomic layer deposition process.

### Claim 24

A method for depositing an insulator thin film for spacer patterning comprising:
a deposition cycle comprising alternately and sequentially contacting a substrate with a titanium alkylamide reactant and a second reactant,
wherein the second reactant comprises a plurality of reactive species from a plasma generated in a gas comprising oxygen but not nitrogen by applying RF power of 200 W to 500 W, and
wherein the deposition cycle is repeated two or more times to form an amorphous thin film comprising from about 0.05 at-% to about 30 at-% of nitrogen on the substrate, wherein the thin film is deposited at a temperature from 50° C. to 300° C. and has a wet etch rate of 0.01 nm/min to 50 nm/min 1% dHF.

### Claim 25 (depends on 24)

The method of claim 24, wherein the plurality of reactive species are from a plasma generated in O2 gas.

### Claim 26 (depends on 25)

The method of claim 25, wherein the plasma is generated in a gas consisting of O2 gas.

### Claim 27 (depends on 24)

The method of claim 24, where the reactive species comprise oxygen atoms or oxygen radicals.

### Claim 28 (depends on 24)

The method of claim 24, wherein the second reactant additionally comprises reactive species from a plasma generated in a gas comprising Ar.

### Claim 29 (depends on 24)

The method of claim 24, wherein the plasma is generated in a gas that does not comprise a noble gas.

### Claim 30 (depends on 24)

The method of claim 24, further comprising exposing the substrate to a purge gas and/or vacuum after contacting the substrate with the titanium alkylamide reactant and prior to contacting the substrate with the second reactant.