US6113771A
Expired / Lapsed
US
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Electro deposition chemistry
Assignee: Applied Materials Inc
•
Filing: 1998-07-13
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Granted: 2000-09-05
•
Expires: 2018-07-13
Abstract
Abstract The present invention provides plating solutions, particularly metal plating solutions, designed to provide uniform coatings on substrates and to provide substantially defect free filling of small features, e.g., micron scale features and smaller, formed on substrates with none or low supporting electrolyte, i.e., which include no acid, low acid, no base, or no conducting salts, and/or high metal ion, e.g., copper, concentration. Additionally, the plating solutions may contain small amounts of additives which enhance the plated film quality and performance by serving as brighteners, levelers, surfactants, grain refiners, stress reducers, etc.
Inventors
- 👤 Uziel Landau
- 👤 John J. D'Urso
- 👤 David B. Rear
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 17:39
CPC Classifications
C; C25; C25D; C25D5/00; C25D5/60; C25D5/605; C25D5/611; C25D3/00; C25D3/02; C25D3/38; C25D7/00; C25D7/12; C25D7/123
Claims Analysis
Total Claims: 37
Claim 1
Independent Claim
65 words
A method for electrolytic plating of a metal on a semiconductive substrate, comprising: connecting the semiconductive substrate to a negative terminal of an electrical power source; disposing the semiconductive substrate and an anode in a solution comprising metal ions and less than about 0.05 molar concentration of a supporting electrolyte; and electrodepositing the metal onto the semiconductive substrate from the metal ions in the solution.
Claim 2
Independent Claim
65 words
A method for electrolytic plating of a metal on a semiconductive substrate, comprising: connecting the semiconductive substrate to a negative terminal of an electrical power source; disposing the semiconductive substrate and an anode in a solution comprising metal ions and less than about 0.05 molar concentration of a supporting electrolyte; and electrodepositing the metal onto the semiconductive substrate from the metal ions in the solution.
Claim 3
Dependent Claim
10 words
The method of claim 1, wherein the metal is copper.
Claim 4
Dependent Claim
12 words
The method of claim 2, wherein the supporting electrolyte comprises sulfuric acid.
Claim 5
Dependent Claim
12 words
The method of claim 1, wherein the metal ions are copper ions.
Claim 6
Dependent Claim
40 words
The method of claim 4, wherein the copper ions are provided by a copper salt selected from the group consisting of copper sulfate, copper fluoborate, copper gluconate, copper sulfamate, copper sulfonate, copper pyrophosphate, copper chloride, copper cyanide, or mixtures thereof.
Claim 7
Dependent Claim
16 words
The method of claim 5, wherein the copper ion concentration is greater than about 0.8 molar.
Claim 8
Dependent Claim
18 words
The method of claim 1, wherein the substrate has an electronical resistivity between 0.001 and 1000 Ohms/square cm.
Claim 9
Dependent Claim
17 words
The method of claim 1, wherein the solution further comprises one or more additives selected from polyethers.
Claim 10
Dependent Claim
18 words
The method of claim 1, wherein the solution further comprises one or more additives selected from polyalkylene glycols.
Claim 11
Dependent Claim
34 words
The method of claim 1, wherein the solution further comprises one or more additives selected from the group consisting of organic sulfur compounds, salts of organic sulfur compounds, polyelectrolyte derivatives thereof, and mixtures thereof.
Claim 12
Dependent Claim
34 words
The method of claim 1, wherein the solution further comprises one or more additives selected from the group consisting of organic nitrogen compounds, salts of organic nitrogen compounds, polyelectrolyte derivatives thereof, and mixtures thereof.
Claim 13
Dependent Claim
12 words
The method of claim 1, wherein the solution further comprises polar heterocycles.
Claim 14
Dependent Claim
12 words
The method of claim 1, wherein the solution further comprises halide ions.
Claim 15
Independent Claim
96 words
A method for electrolytic plating of copper on a substrate, comprising: connecting the substrate to a negative terminal of an electrical power source; disposing the substrate and an anode in a solution consisting essentially of water, a copper salt, and a supporting electrolyte selected from the group consisting of sulfuric acid, sulfamic acid, fluoboric acid, sulfonic acid, hydrochloric acid, nitric acid, perchloric acid, gluconic acid, and mixtures thereof, wherein the solution comprises less than about 0.05 molar concentration of the supporting electrolyte; and electrodepositing copper metal onto the substrate from the copper salts in the solution.
Claim 16
Independent Claim
96 words
A method for electrolytic plating of copper on a substrate, comprising: connecting the substrate to a negative terminal of an electrical power source; disposing the substrate and an anode in a solution consisting essentially of water, a copper salt, and a supporting electrolyte selected from the group consisting of sulfuric acid, sulfamic acid, fluoboric acid, sulfonic acid, hydrochloric acid, nitric acid, perchloric acid, gluconic acid, and mixtures thereof, wherein the solution comprises less than about 0.05 molar concentration of the supporting electrolyte; and electrodepositing copper metal onto the substrate from the copper salts in the solution.
Claim 17
Dependent Claim
35 words
The method of claim 14, wherein the copper salt is selected from the group consisting of copper sulfate, copper fluoborate, copper gluconate, copper sulfamate, copper sulfonate, copper pyrophosphate, copper chloride, copper cyanide, or mixtures thereof.
Claim 18
Dependent Claim
17 words
The method of claim 14, wherein the copper salt has a concentration greater than about 0.8 molar.
Claim 19
Dependent Claim
12 words
The method of claim 14, wherein the supporting electrolyte comprises sulfuric acid.
Claim 20
Dependent Claim
86 words
A solution for electroplating copper onto a substrate, comprising: water; greater than about 0.8 molar concentration of a copper salt selected from the group consisting of copper sulfate, copper flouroborate, copper gluconate, copper sulfamate, copper pyrophosphate, copper chloride, copper cyanide, and mixtures thereof; and a supporting electrolyte selected from the group consisting of sulfuric acid, sulfamic acid, fluoboric acid, sulfonic acid, hydrochloric acid, nitric acid, perchloric acid, gluconic acid, and mixtures thereof, wherein the solution comprises less than about 0.05 molar concentration of the supporting electrolyte.
Claim 21
Dependent Claim
86 words
A solution for electroplating copper onto a substrate, comprising: water; greater than about 0.8 molar concentration of a copper salt selected from the group consisting of copper sulfate, copper flouroborate, copper gluconate, copper sulfamate, copper pyrophosphate, copper chloride, copper cyanide, and mixtures thereof; and a supporting electrolyte selected from the group consisting of sulfuric acid, sulfamic acid, fluoboric acid, sulfonic acid, hydrochloric acid, nitric acid, perchloric acid, gluconic acid, and mixtures thereof, wherein the solution comprises less than about 0.05 molar concentration of the supporting electrolyte.
Claim 22
Dependent Claim
12 words
The solution of claim 18, wherein the supporting electrolyte is an acid.
Claim 23
Dependent Claim
12 words
The solution of claim 18, wherein the supporting electrolyte is sulfuric acid.
Claim 24
Independent Claim
42 words
A method for forming a metal film on a semiconductive substrate, comprising: electrodepositing a metal onto the semiconductive substrate using an electrolyte that contains greater than about 0.8 M of metal ions and about 0.05 M or less of a supporting electrolyte.
Claim 25
Independent Claim
42 words
A method for forming a metal film on a semiconductive substrate, comprising: electrodepositing a metal onto the semiconductive substrate using an electrolyte that contains greater than about 0.8 M of metal ions and about 0.05 M or less of a supporting electrolyte.
Claim 26
Dependent Claim
20 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of ethers and polyethers.
Claim 27
Dependent Claim
17 words
The method of claim 22, wherein the ethers comprise ethylene glycol and the polyethers comprise polyalkylene glycols.
Claim 28
Dependent Claim
14 words
The method of claim 21, wherein the electrolyte comprises greater than 0.85M copper concentration.
Claim 29
Dependent Claim
28 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of organic sulfur compounds and their corresponding salts and polyelectrolyte derivatives thereof.
Claim 30
Dependent Claim
28 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of organic nitrogen compounds and their corresponding salts and polyelectrolyte derivatives thereof.
Claim 31
Dependent Claim
19 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of quaternary amines.
Claim 32
Dependent Claim
19 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of polar heterocycles.
Claim 33
Dependent Claim
58 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of aromatic heterocycles of the following formnula: R'--R--R" where R is a nitrogen and/or sulfur containing aromatic heterocyclic compound, and R' and R" are the same or different and can be only 1 to 4 carbon, nitrogen, and/or sulfur containing organic group.
Claim 34
Dependent Claim
61 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of organic disulfide compounds of the general formula R--S--S--R' where R is a group with 1 to 6 carbon atoms and water soluble groups and R' is the same as R or a different group with 1 to 6 carbon atoms and water soluble groups.
Claim 35
Dependent Claim
25 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of activated sulfur compounds of the general formula S═C--R'.
Claim 36
Dependent Claim
40 words
The method of claim 31, where R is an organic group having from 0 to 6 carbon atoms and nitrogen, and R' is the same as R or a different group having from 0 to 6 carbon atoms and nitrogen.
Claim 37
Dependent Claim
19 words
The method of claim 21, wherein the electrolyte further comprises additives selected from the group consisting of halide ions.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2003-09-05 | 2004-03-06 | 2004-09-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2007-09-05 | 2008-03-06 | 2008-09-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2011-09-05 | 2012-03-06 | 2012-09-05 | $7700.00 | Window Closed / Lapsed |