# US 11,898,242 B2 · Methods for forming a polycrystalline molybdenum film over a surface of a substrate and related structures including a polycrystalline molybdenum film

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- Number: US 11,898,242 B2
- Document ID: US11898242B2
- Status: Granted
- Kind: B2
- Application number: 16/994,025
- Filed: 2020-08-14
- Published: 2021-02-25
- Granted: 2024-02-13
- Earliest claimed: 2019-08-23
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Bhushan Zope; Eric Christopher Stevens; Shankar Swaminathan; Roghayyeh Lotfi; Mustafa Muhammad; Eric Shero
- Web page: https://patentgrep.com/patent/US11898242B2

## 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 forming a polycrystalline molybdenum film over a surface of a substrate are disclosed. The methods may include: providing a substrate into a reaction chamber; depositing a nucleation film directly on an exposed surface of the substrate, wherein the nucleation film comprises one of a metal oxide nucleation film or a metal nitride nucleation film; and depositing a polycrystalline molybdenum film directly on the nucleation film; wherein the polycrystalline molybdenum film comprises a plurality of molybdenum crystallites having an average crystallite size of less than 80 Å. Structures including a polycrystalline molybdenum film disposed over a surface of a substrate with an intermediate nucleation film are also disclosed.

## Claims

### Claim 1

A method for forming a polycrystalline molybdenum film over a surface of a substrate, the method comprising:
providing a substrate into a reaction chamber;
depositing a nucleation film directly on an exposed surface of the substrate, wherein the nucleation film comprises a metal oxide nucleation film, wherein the metal oxide film comprises a metal oxide selected from the group consisting of aluminum oxide, tungsten oxide, ruthenium oxide, rhenium oxide, and iridium oxide; and
depositing a polycrystalline molybdenum film directly on the nucleation film;
wherein the polycrystalline molybdenum film comprises a plurality of molybdenum crystallites having an average crystallite size of less than 80 Angstroms.

### Claim 2 (depends on 1)

The method of claim 1, wherein depositing the nucleation film comprises performing one or more first unit deposition cycles of a first cyclical deposition process, wherein a first unit deposition cycle comprises, sequentially contacting the substrate with a metal precursor and with one of an oxygen precursor.

### Claim 3 (depends on 1)

The method of claim 1, wherein depositing the polycrystalline molybdenum metal film comprises performing one or more second unit deposition cycles of a second cyclical deposition process, wherein a second unit deposition cycle comprises, sequentially contacting the substrate with a molybdenum halide precursor and a reducing agent.

### Claim 4 (depends on 3)

The method of claim 3, wherein the molybdenum halide precursor comprises at least one of: molybdenum (V) trichloride oxide (MoOCl3), molybdenum (VI) tetrachloride oxide (MoOCl4),or molybdenum (IV) dichloride dioxide (MoO2Cl2).

### Claim 5 (depends on 1)

The method of claim 1, wherein the metal oxide nucleation film has an average film thickness of less than 50 Å.

### Claim 6 (depends on 1)

The method of claim 1, wherein depositing the polycrystalline molybdenum metal film comprises performing one or more second unit deposition cycles of a second cyclical deposition process, wherein a second unit deposition cycle comprises contacting the substrate with a metalorganic molybdenum precursor.

### Claim 7 (depends on 1)

The method of claim 1, wherein the polycrystalline molybdenum film is deposited within a plurality of non-planar features, wherein the polycrystalline molybdenum film fills the plurality of non-planar features without the formation of a seam.

### Claim 8 (depends on 1)

The method of claim 1, wherein a bilayer comprising the polycrystalline molybdenum film and the nucleation film has an electrical resistivity of less 25 μΩ-cm for an average nucleation film thickness of less than 20 Å, and an average polycrystalline molybdenum film thickness of less than 100 Å.

### Claim 9 (depends on 1)

The method of claim 1, wherein the nucleation film is a physically continuous film at an average film thickness of less than 50 Å.

### Claim 10 (depends on 1)

The method of claim 1, wherein the exposed surface of the substrate includes a plurality of vertical non-planar features and the nucleation film is deposited directly on the exposed surface, and the polycrystalline molybdenum film is deposited directly on the nucleation film, wherein the polycrystalline molybdenum film fills the plurality of vertical non-planar features without the formation of a seam.

### Claim 11 (depends on 10)

The method of claim 10, wherein the exposed surface comprises a dielectric surface.

### Claim 12 (depends on 10)

The method of claim 10, wherein the substrate further comprises a plurality of line features, wherein the percentage line bending of the plurality of line features is less than 20% post deposition of the nucleation film and the polycrystalline molybdenum film.

### Claim 13 (depends on 10)

The method of claim 10, wherein the substrate further comprises a plurality of line features, wherein the percentage line bending of the plurality of line features is less than 10% post deposition of the nucleation film and the polycrystalline molybdenum film.

### Claim 14 (depends on 1)

The method of claim 1, wherein the nucleation film is a physically discontinuous film having an average film thickness of less than 50 Å.

### Claim 15 (depends on 14)

The method of claim 14, wherein the polycrystalline molybdenum film has an average crystallite size of less than 60 Å.

### Claim 16 (depends on 1)

The method of claim 1, wherein the polycrystalline molybdenum film has a percentage roughness of less than 10%.

### Claim 17 (depends on 1)

The method of claim 1, wherein the polycrystalline molybdenum film has a percentage roughness of less than 5%.

### Claim 18 (depends on 1)

The method of claim 1, wherein the nucleation film comprises an amorphous film.

### Claim 19 (depends on 1)

The method of claim 1, wherein the exposed surface of the substrate comprises a dielectric surface.

### Claim 20 (depends on 1)

A structure comprising the polycrystalline molybdenum film formed according to the method of claim 1.

### Claim 21 (depends on 1)

A reaction system configured to perform the method of claim 1.

### Claim 22

A structure comprising:
a surface of a substrate;
a nucleation film disposed directly on the surface of the substrate, wherein the nucleation film comprises a metal oxide nucleation film,
wherein the metal oxide nucleation film comprises a metal oxide selected from the group consisting of aluminum oxide, tungsten oxide, ruthenium oxide, rhenium oxide, and iridium oxide; and
a polycrystalline molybdenum film disposed directly on the nucleation film;
wherein the polycrystalline molybdenum film comprises a plurality of molybdenum crystallites having an average crystallite size of less than 80 Å.

### Claim 23 (depends on 22)

The structure of claim 22, wherein the metal oxide nucleation film has an average film thickness of less than 50 Å.

### Claim 24 (depends on 22)

The structure of claim 22, wherein the nucleation film is a physically discontinuous film having an average film thickness of less than 50 Å.

### Claim 25 (depends on 22)

The structure of claim 22, wherein the polycrystalline molybdenum film is disposed within a plurality of non-planar features, wherein the polycrystalline molybdenum film fills the plurality of non-planar features without an observable seam.

### Claim 26 (depends on 22)

The structure of claim 22, wherein a bilayer comprising the polycrystalline molybdenum film and the nucleation film has an electrical resistivity of less than 25 μΩ-cm for an average nucleation film thickness of less than 20 Å and an average polycrystalline molybdenum film thickness of less than 100 Å.

### Claim 27 (depends on 22)

The structure of claim 22, wherein the nucleation film is a physically continuous film with an average film thickness of less than 40 Å.

### Claim 28 (depends on 22)

The structure of claim 22, wherein the surface of the substrate further comprises a plurality of vertical non-planar features and the nucleation film is disposed directly on the plurality of vertical non-planar features and the polycrystalline molybdenum film is disposed directly on the nucleation film, wherein the polycrystalline molybdenum film fills the plurality of vertical non-planar features without an observable seam.

### Claim 29 (depends on 22)

The structure of claim 22, wherein the surface of the substrate comprises a dielectric surface.

### Claim 30 (depends on 28)

The structure of claim 28, wherein the substrate further comprises a plurality of line features, wherein the percentage line bending of the plurality of line features is less than 20%.

### Claim 31 (depends on 28)

The structure of claim 28, wherein the substrate further comprises a plurality of line features, wherein the percentage line bending of the plurality of line features is less than 10%.

### Claim 32 (depends on 22)

The structure of claim 22, wherein the nucleation film comprises an amorphous film.

### Claim 33 (depends on 32)

The structure of claim 32, wherein the polycrystalline molybdenum film has an average crystallite size of less than 60 Å.

### Claim 34 (depends on 22)

The structure of claim 22, wherein the polycrystalline molybdenum film has a percentage roughness of less than 10%.

### Claim 35 (depends on 22)

The structure of claim 22, wherein the substrate comprises a partially fabricated device structure including at least one of: a DRAM device structure, a 3D-NAND device structure, a 3D-integrated device structure, or an integrated logic device structure.

### Claim 36 (depends on 35)

The structure of claim 35, wherein the substrate comprises a partially fabricated DRAM device structure, wherein the substrate comprises a plurality of DRAM buried wordline trenches and a plurality of DRAM wordlines.

### Claim 37 (depends on 36)

The structure of claim 36, wherein the nucleation film is disposed directly on the plurality of DRAM buried wordline trenches and directly on the plurality of DRAM wordlines.

### Claim 38 (depends on 37)

The structure of claim 37, wherein the polycrystalline molybdenum film is disposed within and fills the plurality of DRAM buried word line trenches.

### Claim 39 (depends on 38)

The structure of claim 38, wherein the percentage line bending of the plurality of DRAM wordlines is less than 20%.

### Claim 40 (depends on 39)

The structure of claim 39, wherein the polycrystalline molybdenum film has a percentage roughness of than 1.5%.