# US 12,215,416 B2 · Methods for depositing a molybdenum nitride film on a surface of a substrate by a cyclical deposition process and related semiconductor device structures including a molybdenum nitride film

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- Number: US 12,215,416 B2
- Document ID: US12215416B2
- Status: Granted
- Kind: B2
- Application number: 18/387,914
- Filed: 2023-11-08
- Published: 2024-02-29
- Granted: 2025-02-04
- Earliest claimed: 2019-08-23
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Eric Christopher Stevens; Bhushan Zope; Shankar Swaminathan; Charles Dezelah; Qi Xie; Giuseppe Alessio Verni
- Web page: https://patentgrep.com/patent/US12215416B2

## CPC

- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- H10W 20/033: {in openings in dielectrics}
- C23C 16/0272: {Deposition of sub-layers, e.g. to promote the adhesion of the main coating}
- C23C 16/08: from metal halides
- C23C 16/45523: {Pulsed gas flow or change of composition over time}
- 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 16/45553: {characterized by the use of precursors specially adapted for ALD}
- G11C 5/063: {Voltage and signal distribution in integrated semi-conductor memory access lines, e.g. word-line, bit-line, cross-over resistance, propagation delay}
- H10B 12/053: {the transistor being at least partially in a trench in the substrate (vertical transistor in combination with a capacitor formed in a substrate trench H10B12/0383)}
- H10B 12/34: {the transistor being at least partially in a trench in the substrate}
- H10B 12/488: {Word lines}
- H10D 30/6211: {having fin-shaped semiconductor bodies integral with the bulk semiconductor substrates}
- H10D 30/6735: {having gates fully surrounding the channels, e.g. gate-all-around}
- H10D 30/6739: {Conductor-insulator-semiconductor electrodes}
- H10D 30/6757: {characterised by the structure of the channel, e.g. transverse or longitudinal shape or doping profile (TFTs having channel structures for preventing kink or snapback effects H10D30/6708; TFTs having lightly-doped source or drain extensions H10D30/6715)}
- H10D 62/121: {oriented parallel to substrates}
- H10D 64/01318: {the conductor comprising a layer of alloy material, compound material or organic material contacting the insulator, e.g. TiN (comprising a layer of alloys of Si, Ge or C H10D64/01314)}
- H10D 64/667: {the conductor comprising a layer of alloy material, compound material or organic material contacting the insulator, e.g. TiN workfunction layers (having lateral variation H10D64/671)}
- H10D 30/024: {of fin field-effect transistors [FinFET]}
- 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)
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- G11C: STATIC STORES (semiconductor memory devices H10B)
- H10B: ELECTRONIC MEMORY DEVICES
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

Methods for depositing a molybdenum nitride film on a surface of a substrate are disclosed. The methods may include: providing a substrate into a reaction chamber; and depositing a molybdenum nitride film directly on the surface of the substrate by performing one or more unit deposition cycles of cyclical deposition process, wherein a unit deposition cycle may include, contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor, and contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor. Semiconductor device structures including a molybdenum nitride film are also disclosed.

## Claims

### Claim 1

A method for depositing a molybdenum nitride film on a surface of a substrate, the method comprising:
performing one or more unit deposition cycles of a cyclical deposition process, wherein a unit deposition cycle comprises:
contacting the substrate with a first vapor phase reactant comprising a molybdenum precursor; and
contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor,
wherein the molybdenum nitride film has a percentage roughness of less than 1.5%.

### Claim 2 (depends on 1)

The method of claim 1, wherein the nitrogen precursor comprises at least one of: molecular nitrogen (N2), ammonia (NH3), hydrazine (N2H4), a hydrazine derivative, or a nitrogen-based plasma.

### Claim 3 (depends on 1)

The method of claim 1, wherein the molybdenum precursor comprises a molybdenum oxyhalide precursor.

### Claim 4 (depends on 1)

The method of claim 1, wherein the molybdenum precursor comprises at least one of: molybdenum pentachloride (MoCl5), molybdenum hexachloride (MoCl6), Mo(NMe2)4, Mo(NEt2)4, Mo2(NMe2)6, Mo(tBuN)2(NMe2)2, Mo(tBuN)2(NEt2)2, Mo(NEtMe)4, Mo(NtBu)2(StBu)2, Mo(NtBu)2(iPr2AMD)2 Mo(thd)3, MoO2(acac), MoO2(thd)2, MoO2(iPr2AMD)2 Mo(CO)6, Mo(Cp)2H2, Mo(iPrCp)2H2, Mo(η6-ethylbenzene)2, MoCp(CO)2(η3-allyl), and MoCp(CO)2(NO).

### Claim 5 (depends on 1)

The method of claim 1, wherein the molybdenum nitride film has an electrical resistivity of less than 750 μΩ-cm at an average molybdenum nitride film thickness of less than 100 Å.

### Claim 6 (depends on 1)

The method of claim 1, wherein the molybdenum nitride film is physically continuous at an average film thickness of less than 40 Å.

### Claim 7 (depends on 1)

The method of claim 1, wherein the molybdenum nitride film comprises a portion of a gate stack disposed over a semiconductor channel region, wherein the gate stack has an effective work function of greater than 4.6 eV at an average molybdenum nitride film thickness of less than 50 Å.

### Claim 8

A method for depositing a molybdenum nitride film on a surface of a substrate, the method comprising:
performing one or more unit deposition cycles of a cyclical deposition process, wherein a unit deposition cycle comprises:
contacting the substrate with a first vapor phase reactant comprising a molybdenum precursor; and
contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor,
wherein the molybdenum nitride film has an electrical resistivity of less than 750 μΩ-cm at an average molybdenum nitride film thickness of less than 100 Å.

### Claim 9 (depends on 8)

The method of claim 8, wherein the molybdenum nitride film has a percentage roughness of less than 1.5%.

### Claim 10 (depends on 8)

The method of claim 8, wherein the nitrogen precursor comprises at least one of: molecular nitrogen (N2), ammonia (NH3), hydrazine (N2H4), a hydrazine derivative, or a nitrogen-based plasma.

### Claim 11 (depends on 8)

The method of claim 8, wherein the molybdenum precursor comprises a molybdenum oxyhalide precursor.

### Claim 12 (depends on 8)

The method of claim 8, wherein the molybdenum precursor comprises at least one of: molybdenum pentachloride (MoCl5), molybdenum hexachloride (MoCl6), Mo(NMe2)4, Mo(NEt2)4, Mo2(NMe2)6, Mo(tBuN)2(NMe2)2, Mo(tBuN)2(NEt2)2, Mo(NEtMe)4, Mo(NtBu)2(StBu)2, Mo(NtBu)2(iPr2AMD)2 Mo(thd)3, MoO2(acac), MoO2(thd)2, MoO2(iPr2AMD)2 Mo(CO)6, Mo(Cp)2H2, Mo(iPrCp)2H2, Mo(η6-ethylbenzene)2, MoCp(CO)2(η3-allyl), and MoCp(CO)2(NO).

### Claim 13 (depends on 8)

The method of claim 8, wherein the molybdenum nitride film is physically continuous at an average film thickness of less than 40 Å.

### Claim 14 (depends on 8)

The method of claim 8, wherein the molybdenum nitride film comprises a portion of a gate stack disposed over a semiconductor channel region, wherein the gate stack has an effective work function of greater than 4.6 eV at an average molybdenum nitride film thickness of less than 50 Å.

### Claim 15

A method for depositing a molybdenum nitride film on a surface of a substrate, the method comprising:
performing one or more unit deposition cycles of a cyclical deposition process, wherein a unit deposition cycle comprises:
contacting the substrate with a first vapor phase reactant comprising a molybdenum precursor; and
contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor,
wherein the molybdenum nitride film comprises a portion of a gate stack disposed over a semiconductor channel region, wherein the gate stack has an effective work function greater than 4.6 eV at an average molybdenum nitride film thickness of less than 50 Å.

### Claim 16 (depends on 15)

The method of claim 15, wherein the molybdenum nitride film has a percentage roughness of less than 1.5%.

### Claim 17 (depends on 15)

The method of claim 15, wherein the nitrogen precursor comprises at least one of: molecular nitrogen (N2), ammonia (NH3), hydrazine (N2H4), a hydrazine derivative, or a nitrogen-based plasma.

### Claim 18 (depends on 15)

The method of claim 15, wherein the molybdenum precursor comprises a molybdenum oxyhalide precursor.

### Claim 19 (depends on 15)

The method of claim 15, wherein the molybdenum precursor comprises at least one of: molybdenum pentachloride (MoCl5), molybdenum hexachloride (MoCl6), Mo(NMe2)4, Mo(NEt2)4, Mo2(NMe2)6, Mo(tBuN)2(NMe2)2, Mo(tBuN)2(NEt2)2, Mo(NEtMe)4, Mo(NtBu)2(StBu)2, Mo(NtBu)2(iPr2AMD)2 Mo(thd)3, MoO2(acac), MoO2(thd)2, MoO2(iPr2AMD)2 Mo(CO)6, Mo(Cp)2H2, Mo(iPrCp)2H2, Mo(η6-ethylbenzene)2, MoCp(CO)2(η3-allyl), and MoCp(CO)2(NO).

### Claim 20 (depends on 15)

The method of claim 15, wherein the molybdenum nitride film is physically continuous at an average film thickness of less than 40 Å.