Selective electroless electrochemical atomic layer deposition in an aqueous solution without external voltage bias

• US 10,640,874 B2
• Filed: 08/03/2018
• Issued: 05/05/2020
• Est. Priority Date: 08/14/2017
• Status: Active Grant

• Current Assignee: Lam Research Corporation
• Original Assignee: Lam Research Corporation
• Inventors: Joi, Aniruddha, Venkatraman, Kailash, Dordi, Yezdi
• Primary Examiner(s): Yuan, Dah-Wei D.
• Assistant Examiner(s): Law, Nga Leung V
• Application Number:
  US16/054,428
• Publication Number:
  US 20190048472A1
• Time in Patent Office: Days
• Field of Search: 427 979, 427 995, 427304, 427305, 427306, 427437, 4274431, 427438
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 18/02 by thermal decomposition
• CPC Class Codes: C23C 18/08 characterised by the deposition of metallic material
• CPC Class Codes: C23C 18/1608 from pretreatment step, i.e. selective pre-treatment
• CPC Class Codes: C23C 18/1619 Apparatus for electroless plating
• CPC Class Codes: C23C 18/1632 Features specific for the apparatus, e.g. layout of cells and of its equipment, multiple cells
• CPC Class Codes: C23C 18/1675 Process conditions
• CPC Class Codes: C23C 18/168 Control of temperature, e.g. temperature of bath, substrate
• CPC Class Codes: C23C 18/1683 Control of electrolyte composition, e.g. measurement, adjustment regeneration of bath C23C18/1617
• CPC Class Codes: C23C 18/34 using reducing agents
• CPC Class Codes: C23C 18/40 using reducing agents
• CPC Class Codes: C23C 18/44 using reducing agents
• CPC Class Codes: C23C 18/52 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
• CPC Class Codes: C23C 18/54 Contact plating, i.e. electroless electrochemical plating
• CPC Class Codes: C23F 3/04 Heavy metals
• CPC Class Codes: H01L 21/02074 the processing being a planarization of conductive layers
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/288 from a liquid, e.g. electrolytic deposition
• CPC Class Codes: H01L 21/6723 comprising at least one plating chamber electroless plating apparatuses C23C, electroplating apparatuses C25D
• CPC Class Codes: H01L 21/76846 Layer combinations
• CPC Class Codes: H01L 21/76849 : the layer being positioned on top of the main fill metal
• CPC Class Codes: H05K 3/187 : means therefor, e.g. baths, apparatus
• CPC Class Codes: H05K 3/422 : characterised by electroless plating method; pretreatment therefor

Abstract

A method of performing electroless electrochemical atomic layer deposition is provided and includes: providing a substrate including an exposed upper metal layer; exposing the substrate to a first precursor solution to create a sacrificial metal monolayer on the exposed upper metal layer via underpotential deposition, where the first precursor solution is an aqueous solution including a reducing agent; subsequent to the forming of the sacrificial metal monolayer, rinsing the substrate; subsequent to the rinsing of the substrate, exposing the substrate to a second precursor solution to replace the sacrificial metal monolayer with a first deposition layer; and subsequent to replacing the sacrificial metal monolayer with the first deposition layer, rinsing the substrate. The exposure of the substrate to the first precursor solution and the exposure of the substrate to the second precursor solution are electroless processes.

Claims

1. A method of performing electroless electrochemical atomic layer deposition comprising:

providing a substrate including an exposed upper metal layer;

exposing the substrate to a first precursor solution to create a sacrificial metal monolayer on the exposed upper metal layer via underpotential deposition, wherein the first precursor solution is an aqueous solution including a reducing agent;

subsequent to the forming of the sacrificial metal monolayer, rinsing the substrate;

subsequent to the rinsing of the substrate, exposing the substrate to a second precursor solution to replace the sacrificial metal monolayer with a first deposition layer; and

subsequent to replacing the sacrificial metal monolayer with the first deposition layer, rinsing the substrate,

wherein the exposure of the substrate to the first precursor solution and the exposure of the substrate to the second precursor solution are electroless processes.

2. The method of claim 1, wherein the first precursor solution includes zinc sulfate.

3. The method of claim 1, wherein the first precursor solution includes a metal salt, carboxylic acid, the reducing agent, and a pH adjuster.

4. The method of claim 3, wherein:

the metal salt includes zinc sulfate; and

the pH adjuster includes ammonium hydroxide.

5. The method of claim 1, wherein:

the first precursor solution includes a metal salt, carboxylic acid, the reducing agent, and a pH adjuster;

the metal salt includes zinc sulfate;

the reducing agent includes titanium; and

the pH adjuster includes ammonium hydroxide.

6. The method of claim 1, wherein the first precursor solution includes:

a first predetermined amount of a first mixture of zinc sulfate and ammonium hydroxide;

a second predetermined amount of a second mixture of titanium chloride and ammonium citrate; and

a third predetermined amount of ammonium hydroxide in addition to the ammonium hydroxide included in the first mixture.

7. The method of claim 1, wherein the sacrificial metal monolayer includes zinc.

8. The method of claim 1, wherein the reducing agent includes titanium.

9. The method of claim 1, wherein the second precursor solution includes an aqueous solution of salt and metal ions.

10. The method of claim 1, wherein the second precursor solution includes copper sulfate.

11. The method of claim 1, wherein the second precursor solution includes ruthenium nitrosyl sulfate or ruthenium nitrosyl chloride.

12. The method of claim 1, wherein the second precursor solution includes chloroplatinic acid.

13. The method of claim 1, wherein the second precursor solution includes a metal salt.

14. The method of claim 13, wherein the metal salt includes copper, rutenhium or platinum.

15. The method of claim 1, wherein the second precursor solution includes a surface limited redox replacement electrolyte.

16. The method of claim 15, wherein the surface limited redox replacement electrolyte includes copper sulfate, citric acid, and sulfuric acid.

17. The method of claim 1, wherein the first deposition layer includes copper, cobalt, ruthenium, or platinum.

18. The method of claim 1, further comprising:

detecting at least one of a current level or a voltage at a surface of the exposed upper metal layer via a probe; and

based on the at least one of the current level or the voltage, adjusting at least one of a pH level, a concentration of the first precursor solution, or a temperature to maintain the at least one of the current level within a first predetermined range or the voltage within a second predetermined range for electroless electrochemical atomic layer deposition of the sacrificial metal monolayer.

19. The method of claim 18, comprising, based on the at least one of the current level or the voltage, adjusting the pH level to be between 9 and 10, wherein the pH level is a pH level of the first precursor solution.

20. The method of claim 18, wherein:

the first precursor solution includes titanium chloride and zinc sulfate; and

the pH level, an amount of the titanium chloride, an amount of the zinc sulfate and the temperature are adjusted to maintain the at least one of the current level within the first predetermined range or the voltage within the second predetermined range for electroless electrochemical atomic layer deposition of the sacrificial metal monolayer.