# US 10,872,771 B2 · Method for depositing a material film on a substrate within a reaction chamber by a cyclical deposition process and related device structures

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- Number: US 10,872,771 B2
- Document ID: US10872771B2
- Status: Granted
- Kind: B2
- Application number: 16/242,829
- Filed: 2019-01-08
- Published: 2019-07-18
- Granted: 2020-12-22
- Earliest claimed: 2018-01-16
- Assignees: ASM IP Holding B. V.
- Applicants: ASM IP Holding B.V.
- Inventors: Petri Raisanen; Mark Olstad; Jose Alexandro Romero; Dong Li; Ward Johnson; Peijun Chen
- Web page: https://patentgrep.com/patent/US10872771B2

## CPC

- H10P 14/43: Chemical deposition, e.g. chemical vapour deposition [CVD]
- C23C 16/32: Carbides
- 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}
- 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 30/60: Insulated-gate field-effect transistors [IGFET] (H10D30/40 takes precedence)
- 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 method of depositing a material film on a substrate within a reaction chamber by a cyclical deposition process is disclosed. The method may include: contacting the substrate with a first vapor phase reactant and purging the reaction chamber with a first main purge. The method also includes: contacting the substrate with a second vapor phase reactant by two or more micro pulsing processes, wherein each micro pulsing process comprises: contacting the substrate with a micro pulse of a second vapor phase reactant; and purging the reaction chamber with a micro purge, wherein each of the micro pulses of the second vapor phase reactant provides a substantially constant concentration of the second vapor phase reactant into the reaction chamber. The method may also include; purging the reaction chamber with a second main purge. Device structures including a material film deposited by the methods of the disclosure are also disclosed.

## Claims

### Claim 1

A method of depositing a material film on a substrate within a reaction chamber by a cyclical deposition process, the method comprising;
contacting the substrate with a first vapor phase reactant;
purging the reaction chamber with a first main purge;
contacting the substrate with a second vapor phase reactant by two or more micro pulsing processes, wherein each micro pulsing process is a sub-cycle that comprises:
contacting the substrate with a micro pulse of a second vapor phase reactant, and
purging the reaction chamber with a micro purge, wherein each of the micro pulses of the second vapor phase reactant provides a constant concentration of the second vapor phase reactant into the reaction chamber; and
purging the reaction chamber with a second main purge;
wherein the material film deposited on the substrate comprises a transition metal aluminum carbide;
wherein the transition metal aluminum carbide comprises titanium aluminum carbide (TiAlC); and
wherein the titanium aluminum carbide (TiAlC) has an average titanium to aluminum content ratio (Ti:Al) of less than 0.15.

### Claim 2 (depends on 1)

The method of claim 1, wherein the cyclical deposition process comprises an atomic layer deposition process.

### Claim 3 (depends on 1)

The method of claim 1, wherein the cyclical deposition process comprises a cyclical chemical vapor deposition process.

### Claim 4 (depends on 1)

The method of claim 1, wherein the first vapor phase reactant comprises one or more metal vapor phase reactants.

### Claim 5 (depends on 4)

The method of claim 4, wherein the one or more metal vapor phase reactants comprises at least one transition metal selected from the group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), and tungsten (W).

### Claim 6 (depends on 4)

The method of claim 4, wherein the one or metal vapor phase reactants comprises at least one of a transition metal chloride, a transition metal bromide, a transition metal iodide, or a transition metal fluoride.

### Claim 7 (depends on 1)

The method of claim 1, wherein the second vapor phase reactant comprises a metalorganic precursor.

### Claim 8 (depends on 7)

The method of claim 7, wherein the metalorganic precursor comprises at least one of dimethylaluminumhydride (DMAH) or tritertbutylaluminum (TTBA).

### Claim 9 (depends on 1)

The method of claim 1, wherein each micro pulse of the second vapor phase reactant has a pulse time period of between 0.05 seconds and 10 seconds.

### Claim 10 (depends on 1)

The method of claim 1, wherein each micro purge has a purge time period of between 0.1 seconds and 10 seconds.

### Claim 11 (depends on 1)

The method of claim 1, wherein the titanium aluminum carbide (TiAlC) has an aluminum atomic-% greater than 20%.

### Claim 12 (depends on 1)

The method of claim 1, wherein the titanium aluminum carbide (TiAlC) is deposited with a thickness non-uniformity standard deviation of less than 2% one-sigma.

### Claim 13 (depends on 1)

The method of claim 1, wherein the titanium aluminum carbide (TiAlC) is deposited over a non-planar substrate with a step coverage greater than 90%.

### Claim 14 (depends on 1)

The method of claim 1, further comprising replenishing the concentration of the second vapor source at the source vessel to a constant concentration during each micro purge.

### Claim 15 (depends on 1)

A device structure including a material film deposited by the method of claim 1.

### Claim 16 (depends on 1)

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