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Patent US6277263B1 successfully refreshed from Google Patents.
US6277263B1
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US
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Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
Assignee: Applied Materials Inc
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Filing: 1999-08-31
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Granted: 2001-08-21
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Expires: 2019-08-31
Abstract
Abstract This invention employs a novel approach to the copper metallization of a workpiece, such as a semiconductor workpiece. In accordance with the invention, an alkaline electrolytic copper bath is used to electroplate copper onto a seed layer, electroplate copper directly onto a barrier layer material, or enhance an ultra-thin copper seed layer which has been deposited on the barrier layer using a deposition process such as PVD. The resulting copper layer provides an excellent conformal copper coating that fills trenches, vias, and other microstructures in the workpiece. When used for seed layer enhancement, the resulting copper seed layer provide an excellent conformal copper coating that allows the microstructures to be filled with a copper layer having good uniformity using electrochemical deposition techniques. Further, copper layers that are electroplated in the disclosed manner exhibit low sheet resistance and are readily annealed at low temperatures.
Inventors
- 👤 LinLin Chen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 11:25
CPC Classifications
H; H10; H10P; H10P14/00; H10P14/20; C; C25; C25D; C25D7/00; C25D7/12; C25D7/123; C23; C23C; C23C28/00; C23C28/30; C23C28/32; C23C28/322; C23C28/34; C25D3/00; C25D3/02; C25D3/38; C25D5/00; C25D5/10; C25D5/627; H10P14/40; H10P14/46; H10P14/47; H10W; H10W20/00; H10W20/01; H10W20/031; H10W20/032; H10W20/033; H10W20/041; H10W20/042; H10W20/043; H10W20/056; H05; H05K; H05K3/00; H05K3/40; H05K3/42; H05K3/423; H10W20/0425
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
146 words
A process for applying a metal structure to a workpiece comprising: providing a first electroplating bath including a source of metal ions as a principal metal species to be deposited during subsequent electroplating, boric acid, and a metal ion complexing agent; providing a workpiece on which one or more microelectronic devices are to be formed; exposing at least one surface of the workpiece to the first electroplating bath; providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species onto the at least one surface of the workpiece in an electrolytic first deposition process; and depositing additional metal of the same principal metal species onto the metal deposited in the first deposition process using a second deposition process that is different than the first electrolytic deposition process.
Claim 2
Dependent Claim
146 words
A process for applying a metal structure to a workpiece comprising: providing a first electroplating bath including a source of metal ions as a principal metal species to be deposited during subsequent electroplating, boric acid, and a metal ion complexing agent; providing a workpiece on which one or more microelectronic devices are to be formed; exposing at least one surface of the workpiece to the first electroplating bath; providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species onto the at least one surface of the workpiece in an electrolytic first deposition process; and depositing additional metal of the same principal metal species onto the metal deposited in the first deposition process using a second deposition process that is different than the first electrolytic deposition process.
Claim 3
Dependent Claim
15 words
The process of claim 1 , wherein the source of metal ions comprises copper sulfate.
Claim 4
Dependent Claim
20 words
The process of claim 2 , wherein the copper sulfate is included at a level of 0.03 to 0.25 M.
Claim 5
Dependent Claim
15 words
The process of claim 1 , wherein the first electroplating bath comprises an alkaline bath.
Claim 6
Dependent Claim
17 words
The process of claim 4 , wherein the alkaline bath has a pH of at least 9.0.
Claim 7
Dependent Claim
32 words
The process of claim 5 , wherein the alkaline bath is pH adjusted with an alkaline agent selected from the group consisting of potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and sodium hydroxide.
Claim 8
Dependent Claim
17 words
The process of claim 5 , wherein the second deposition process occurs in an acidic electrolytic bath.
Claim 9
Dependent Claim
17 words
The process of claim 1 , wherein the second deposition process occurs in an acidic electrolytic bath.
Claim 10
Dependent Claim
25 words
The process of claim 1 , wherein metal is deposited in the second deposition process at a higher rate than in the first deposition process.
Claim 11
Dependent Claim
16 words
The process of claim 1 , wherein the first electroplating bath comprises a conformality increasing agent.
Claim 12
Dependent Claim
14 words
The process of claim 10 , wherein the conformality increasing agent comprises ethylene glycol.
Claim 13
Dependent Claim
23 words
The process of claim 1 , further comprising depositing a barrier layer on the surface of the workpiece before the firm deposition process.
Claim 14
Dependent Claim
20 words
The process of claim 12 , wherein metal is plated directly onto the barrier layer in the first deposition process.
Claim 15
Dependent Claim
24 words
The process of claim 12 , further comprising depositing an ultra-thin seed layer of metal onto the barrier layer before the first deposition process.
Claim 16
Dependent Claim
23 words
The process of claim 1 , wherein the complexing agent is selected from the group consisting of ED, EDTA, and a polycarboxylic acid.
Claim 17
Dependent Claim
13 words
The process of claim 15 , wherein the complexing agent is citric acid.
Claim 18
Dependent Claim
171 words
A process for applying a metal structure to a workpiece comprising: providing a first electroplating bath including copper sulfate as a source of principal metal species to be deposited during subsequent electroplating, a buffer agent, a metal ion complexing agent, and an alkaline agent in an amount to adjust the pH of the first electroplating bath to a pH of at least 9.0; providing a workpiece on which one or more microelectronic devices are to be formed; exposing at least one surface of the workpiece to the first electroplating bath; providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species onto the at least one surface of the workpiece in an electrolytic first deposition process at a first deposition rate; and depositing additional metal onto the metal deposited in the first deposition process using a second deposition process at a second deposition rate that is higher than the first deposition rate.
Claim 19
Dependent Claim
171 words
A process for applying a metal structure to a workpiece comprising: providing a first electroplating bath including copper sulfate as a source of principal metal species to be deposited during subsequent electroplating, a buffer agent, a metal ion complexing agent, and an alkaline agent in an amount to adjust the pH of the first electroplating bath to a pH of at least 9.0; providing a workpiece on which one or more microelectronic devices are to be formed; exposing at least one surface of the workpiece to the first electroplating bath; providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species onto the at least one surface of the workpiece in an electrolytic first deposition process at a first deposition rate; and depositing additional metal onto the metal deposited in the first deposition process using a second deposition process at a second deposition rate that is higher than the first deposition rate.
Claim 20
Dependent Claim
155 words
A process for applying a metal structure to a workpiece comprising: providing a workpiece on which one or more microelectronic devices are to be formed; depositing a barrier layer on at least one surface of a workpiece; providing a first electroplating bath including copper sulfate as a source of principal metal species to be deposited during subsequent electroplating, a buffer agent, a metal ion complexing agent, an alkaline agent in an amount to adjust the pH of the first electroplating bath to a pH of at least 9.0 and a conformality increasing agent; exposing the least one surface of the workpiece including the barrier layer to the first electroplating bath; and providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species directly onto the barrier layer of the workpiece in an electrolytic first deposition process.
Claim 21
Dependent Claim
155 words
A process for applying a metal structure to a workpiece comprising: providing a workpiece on which one or more microelectronic devices are to be formed; depositing a barrier layer on at least one surface of a workpiece; providing a first electroplating bath including copper sulfate as a source of principal metal species to be deposited during subsequent electroplating, a buffer agent, a metal ion complexing agent, an alkaline agent in an amount to adjust the pH of the first electroplating bath to a pH of at least 9.0 and a conformality increasing agent; exposing the least one surface of the workpiece including the barrier layer to the first electroplating bath; and providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species directly onto the barrier layer of the workpiece in an electrolytic first deposition process.
Claim 22
Dependent Claim
26 words
The process of claim 18 , wherein the alkaline agent is selected from the group consisting of potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and sodium hydroxide.
Claim 23
Dependent Claim
46 words
The process of claim 18 , further comprising depositing additional metal onto the metal deposited in the first deposition process using a second deposition process at a second deposition rate that is higher than a rate at which metal is deposited in the first deposition process.
Claim 24
Dependent Claim
17 words
The process of claim 20 , wherein the second deposition process occurs in an acidic electrolytic bath.
Claim 25
Dependent Claim
14 words
The process of claim 18 , wherein the conformality increasing agent comprises ethylene glycol.
Claim 26
Dependent Claim
23 words
The process of claim 18 , wherein the complexing agent is selected from the group consisting of ED, EDTA, and a polycarboxylic acid.
Claim 27
Dependent Claim
13 words
The process of claim 23 , wherein the complexing agent is citric acid.
Claim 28
Dependent Claim
13 words
The process of claim 18 , wherein the buffer agent comprises boric acid.
Claim 29
Dependent Claim
132 words
A process for applying a metal structure to a workpiece comprising: providing a first electroplating bath including a source of metal ions as a principal metal species to be deposited during subsequent electroplating, boric acid, a metal ion complexing agent and an alkaline agent in an amount sufficient to raise the pH of the bath to at least 9.0; providing a workpiece on which one or more microelectronic devices are to be formed; exposing at least one surface of the workpiece to the first electroplating bath; and providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species onto the at least one surface of the workpiece in an electrolytic first deposition process.
Claim 30
Dependent Claim
132 words
A process for applying a metal structure to a workpiece comprising: providing a first electroplating bath including a source of metal ions as a principal metal species to be deposited during subsequent electroplating, boric acid, a metal ion complexing agent and an alkaline agent in an amount sufficient to raise the pH of the bath to at least 9.0; providing a workpiece on which one or more microelectronic devices are to be formed; exposing at least one surface of the workpiece to the first electroplating bath; and providing electroplating power between the at least one surface of the workpiece and an anode disposed in electrical contact with the first electroplating bath to electroplate the principal metal species onto the at least one surface of the workpiece in an electrolytic first deposition process.
Claim 31
Dependent Claim
96 words
A copper electroplating solution comprising copper sulfate at a level of 0.03 to 0.5 Molar, boric acid at a level of 0.01 to 0.5 Molar, a complexing agent selected from the group consisting of ED, EDTA, and a polycarboxylic acid at a level for a molar ratio of complexing agent to copper sulfate in the range of 1 to 4, and an alkaline agent in an amount sufficient to increase the pH of the solution to at least 9.0, the solution being formulated so as to be suitable for electrodeposition of copper onto a microelectronic workpiece.
Claim 32
Dependent Claim
96 words
A copper electroplating solution comprising copper sulfate at a level of 0.03 to 0.5 Molar, boric acid at a level of 0.01 to 0.5 Molar, a complexing agent selected from the group consisting of ED, EDTA, and a polycarboxylic acid at a level for a molar ratio of complexing agent to copper sulfate in the range of 1 to 4, and an alkaline agent in an amount sufficient to increase the pH of the solution to at least 9.0, the solution being formulated so as to be suitable for electrodeposition of copper onto a microelectronic workpiece.
Claim 33
Dependent Claim
13 words
The solution of claim 27 , wherein the complexing agent is citric acid.
Claim 34
Dependent Claim
10 words
The solution of claim 27 , further comprising ethylene glycol.
Claim 35
Dependent Claim
22 words
The solution of claim 29 , wherein the ethylene glycol is included at the level of greater than 0 to 1.0 Molar.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 2004-08-20 | 2005-02-19 | 2005-08-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2008-08-20 | 2009-02-19 | 2009-08-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2012-08-20 | 2013-02-19 | 2013-08-21 | $7700.00 | Window Closed / Lapsed |