# US 10,501,846 B2 · Electrochemical doping of thin metal layers employing underpotential deposition and thermal treatment

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- Number: US 10,501,846 B2
- Document ID: US10501846B2
- Status: Granted
- Kind: B2
- Application number: 15/701,265
- Filed: 2017-09-11
- Published: 2019-03-14
- Granted: 2019-12-10
- Earliest claimed: 2017-09-11
- Assignees: Lam Research Corporation
- Applicants: Lam Research Corporation
- Inventors: Kailash Venkatraman; Yezdi Dordi; Aniruddha Joi
- Web page: https://patentgrep.com/patent/US10501846B2

## CPC

- C23C 16/406: {of iron group metals}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/06: characterised by the deposition of metallic material
- C23C 16/407: {of zinc, germanium, cadmium, indium, tin, thallium or bismuth}
- C23C 18/1692: {Heat-treatment}
- C23C 18/54: Contact plating, i.e. electroless electrochemical plating
- 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)}
- H10W 20/031: {of conductive parts of the interconnections}
- H10W 20/033: {in openings in dielectrics}
- H10W 20/036: {the barrier, adhesion or liner layers being within a main fill metal}
- H10W 20/047: {by introducing additional elements therein}
- H10W 20/049: {by diffusing alloying elements}
- H10W 20/0552: {by diffusing metallic dopants to react with dielectrics}
- H10W 20/056: {by filling conductive material into holes, grooves or trenches}
- H10W 20/076: {in via holes or trenches}
- H10W 20/425: {Barrier, adhesion or liner layers}
- H10W 20/4403: {based on metals, e.g. alloys, metal silicides (H10W20/4484 takes precedence)}
- H10W 20/4437: {the principal metal being a transition metal}
- C23C 16/408: {of copper or solid solutions thereof}
- C23C 18/1653: {Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating}
- C23C 18/38: Coating with copper
- H10P 14/47: Electrolytic deposition, i.e. electroplating; Electroless plating
- H10P 14/6329: {using physical ablation of a target, e.g. physical vapour deposition or pulsed laser deposition}
- H10W 20/042: {the barrier, adhesion or liner layers being seed or nucleation layers}
- 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 is provided, including the following operations: depositing a ruthenium liner in a feature of a substrate; depositing a monolayer of zinc over the ruthenium liner; after depositing the monolayer of zinc, performing a thermal treatment on the substrate, wherein the thermal treatment is configured to cause migration of the zinc to an interface of the ruthenium liner and an oxide layer of the substrate, the migration of the zinc producing an adhesive barrier at the interface that improves adhesion between the ruthenium liner and the oxide layer of the substrate; repeating the operations of depositing the monolayer of zinc and performing the thermal treatment until a predefined number of cycles is reached.

## Claims

### Claim 1

A method, comprising:
depositing a ruthenium liner in a feature of a substrate;
depositing a monolayer of zinc over the ruthenium liner;
after depositing the monolayer of zinc, performing a thermal treatment on the substrate, wherein the thermal treatment is configured to cause migration of the zinc to an interface of the ruthenium liner and an oxide layer of the substrate, the migration of the zinc producing an adhesive barrier at the interface that improves adhesion between the ruthenium liner and the oxide layer of the substrate;
repeating the operations of depositing the monolayer of zinc and performing the thermal treatment until a predefined number of cycles is reached.

### Claim 2 (depends on 1)

The method of claim 1, wherein depositing the monolayer of zinc is performed by an underpotential deposition process, the underpotential deposition process including deposition from a plating solution at a potential that avoids electroplating from the plating solution.

### Claim 3 (depends on 1)

The method of claim 1, wherein depositing the monolayer of zinc is performed by an electroless underpotential deposition process.

### Claim 4 (depends on 1)

The method of claim 1, wherein the thermal treatment is defined by annealing at a temperature of approximately 100 to 400 C.

### Claim 5 (depends on 1)

The method of claim 1, wherein the predefined number of cycles is approximately 3 to 10 cycles.

### Claim 6 (depends on 1)

The method of claim 1, wherein the thermal treatment causes bonding of at least a portion of the zinc to oxygen at the interface to form the adhesive barrier.

### Claim 7 (depends on 1)

The method of claim 1, wherein the migration of the zinc causes at least a portion of the zinc to fill grain boundaries of the ruthenium liner that are along the interface.

### Claim 8 (depends on 1)

The method of claim 1, wherein the feature does not include an adhesive layer prior to the deposition of the ruthenium liner.

### Claim 9 (depends on 1)

The method of claim 1, wherein the feature defines an interconnect to an underlying conductor, wherein a portion of the ruthenium liner contacts the underlying conductor.

### Claim 10 (depends on 1)

The method of claim 1, further comprising:
after the predefined number of cycles is reached, depositing a conductive material over the ruthenium liner to fill the feature of the substrate.

### Claim 11 (depends on 10)

The method of claim 10, wherein the conductive material includes copper, cobalt, or ruthenium.