# US 12,180,583 B2 · Methods of forming low resistivity titanium nitride thin film in horizontal vias and related devices

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,180,583 B2
- Document ID: US12180583B2
- Status: Granted
- Kind: B2
- Application number: 18/062,274
- Filed: 2022-12-06
- Published: 2023-06-08
- Granted: 2024-12-31
- Earliest claimed: 2021-12-06
- Assignees: The Regents of the University of California; Merck Patent GmbH
- Applicants: The Regents of the University of California; Merck Patent GmbH
- Inventors: Andrew Kummel; Cheng-Hsuan Kuo; SeongUk Yun; Ravindra Kanjolia; Mansour Moinpour; Daniel Moser
- Web page: https://patentgrep.com/patent/US12180583B2

## CPC

- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/0227: {by cleaning or etching}
- C23C 16/0272: {Deposition of sub-layers, e.g. to promote the adhesion of the main coating}
- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- C23C 16/54: Apparatus specially adapted for continuous coating
- C23C 16/56: After-treatment
- C23C 28/04: only coatings of inorganic non-metallic material
- H10P 14/432: {using selective deposition}
- H10W 20/033: {in openings in dielectrics}
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

A method of forming a conformal layer including TiN in a via includes introducing a precursor into a reaction chamber according to a first exposure schedule. The precursor includes non-halogenated metal-organic titanium. The first exposure schedule indicates precursor exposure periods. Each precursor exposure period is associated with a particular duration of time and a particular duty cycle over which to introduce the precursor during the particular duration of time. The method includes introducing a co-reactant into the reaction chamber according to a second exposure schedule. The co-reactant includes nitrogen. The second exposure schedule indicates co-reactant exposure periods. Each co-reactant exposure period is associated with a particular duration of time and a particular duty cycle over which to introduce the co-reactant during the particular duration of time. The method includes providing the conformal layer including TiN in the via based on said introducing the precursor and the co-reactant.

## Claims

### Claim 1

A method of forming a conformal layer including titanium nitride (TiN) in a horizontal via on a substrate in a reaction chamber comprising:
introducing a precursor into the reaction chamber according to a first exposure schedule, wherein the precursor includes non-halogenated metal-organic titanium, wherein the first exposure schedule indicates a plurality of precursor exposure periods, wherein each precursor exposure period of the plurality of precursor exposure periods is associated with a particular duration of time and a particular duty cycle over which to introduce the precursor into the reaction chamber during the particular duration of time;
introducing a co-reactant into the reaction chamber according to a second exposure schedule, wherein the co-reactant includes nitrogen, wherein the second exposure schedule indicates a plurality of co-reactant exposure periods, wherein each co-reactant exposure period of the plurality of co-reactant exposure periods is associated with a particular duration of time and a particular duty cycle over which to introduce the co-reactant into the reaction chamber during the particular duration of time; and
providing the conformal layer including TiN in the horizontal via based on said introducing a precursor into the reaction chamber said introducing the co-reactant into the reaction chamber.

### Claim 2 (depends on 1)

The method of claim 1, wherein the first exposure schedule indicates that the particular duration of time is between about 100 ms and about 250 ms.

### Claim 3 (depends on 1)

The method of claim 1, wherein the second exposure schedule indicates that the particular duration of time is between about 3600 ms and about 8000 ms.

### Claim 4 (depends on 1)

The method of claim 1, wherein the second exposure schedule indicates that the particular duration of time is about 6000 ms.

### Claim 5 (depends on 1)

The method of claim 1, wherein each of the precursor exposure periods has a lower duty cycle than each of the co-reactant exposure periods.

### Claim 6 (depends on 1)

The method of claim 1, wherein the duty cycle of a first precursor exposure period of the plurality of precursor exposure periods is about 50%.

### Claim 7 (depends on 1)

The method of claim 1, wherein the duty cycle of a first co-reactant exposure period of the plurality of co-reactant exposure periods is about 75%.

### Claim 8 (depends on 1)

The method of claim 1, wherein at least one precursor exposure period at least partially overlaps with at least one co-reactant exposure period.

### Claim 9 (depends on 1)

The method of claim 1, wherein a thickness of the conformal layer is about 15 nm.

### Claim 10 (depends on 1)

The method of claim 1, wherein the wherein a temperature of the reaction chamber is between about 350° C. and about 525° C.

### Claim 11 (depends on 1)

The method of claim 1, wherein the wherein a temperature of the reaction chamber is between about 400° C. and about 450° C.

### Claim 12 (depends on 1)

The method of claim 1, wherein a resistivity of the conformal layer is between about 100 uΩ-cm and about 500 uΩ-cm.

### Claim 13 (depends on 1)

The method of claim 1, wherein a resistivity of the conformal layer is less than or equal to about 400 uΩ-cm.

### Claim 14 (depends on 1)

The method of claim 1, wherein the co-reactant comprises anhydrous hydrazine (N2H4).

### Claim 15 (depends on 1)

The method of claim 1, wherein via is a horizontal via having an aspect ratio of about 5:1.

### Claim 16 (depends on 1)

The method of claim 1, wherein the horizontal via has dimensions of about 20 nm by about 100 nm.

### Claim 17

A method of forming a conformal layer comprising titanium nitride (TiN) on a substrate with a horizontal via within a reaction chamber, the method comprising:
introducing a precursor comprising titanium into the reaction chamber according to a precursor exposure schedule, wherein the precursor exposure schedule specifies a first duration and a first duty cycle for introduction of the precursor into the reaction chamber; and
introducing a co-reactant comprising nitrogen into the reaction chamber according to a co-reactant exposure schedule, wherein the co-reactant exposure schedule specifies a second duration and a second duty cycle for introduction of the co-reactant into the reaction chamber, wherein the second duty cycle is greater than the first duty cycle,
wherein the conformal layer is formed in the horizontal via.

### Claim 18 (depends on 17)

The method of claim 17, wherein the reaction chamber is maintained at a temperature between about 350° C. and about 525° C. during formation of the conformal layer, and the conformal layer has a resistivity of less than or equal to about 400 uΩ-cm.

### Claim 19 (depends on 17)

The method of claim 17, wherein the precursor comprises a non-halogenated metal-organic titanium compound, and the co-reactant comprises anhydrous hydrazine (N2H4).

### Claim 20 (depends on 17)

The method of claim 17, wherein the horizontal via runs generally parallel to a major surface of the substrate, and wherein the horizontal via has an aspect ratio of about 5:1.