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US6207557B1
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Method of forming multilayer titanium nitride film by multiple step chemical vapor deposition process and method of manufacturing semiconductor device using the same
Assignee: Samsung Electronics Co Ltd
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Filing: 1999-07-19
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Granted: 2001-03-27
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Expires: 2019-07-19
Abstract
Abstract A method of forming a multilayer titanium nitride film hardly containing any Cl component by a multiple step chemical vapor deposition method, and a method of manufacturing a semiconductor device using the same are provided. In the present invention, a multilayer TiN film is formed by multiple step chemical vapor deposition (CVD) on a semiconductor substrate on which an underlayer is formed. In order to form the multilayer TiN film, an underlayer protective TiN film is formed by forming a first TiN film on the underlayer and NH 3 annealing the first TiN film. A main TiN film is formed by forming a second TiN film on the underlayer protective TiN film and NH 3 annealing the second TiN film. A source gas used in order to form the first TiN film has a smaller TiCl 4 to NH 3 gas flow ratio than a source gas for forming the second TiN film. In order to apply the multilayer TiN film to the fabrication of the semiconductor device, an insulating film having a contact hole is formed on a semiconductor substrate. A Ti film is formed on the inner wall of the contact hole. A multilayer TiN film is formed on the Ti film by the multiple step CVD method. A metal plug is formed on the multilayer TiN film.
Inventors
- 👤 Jang-eun Lee
- 👤 Ju-hyuck Chung
- 👤 Tae-wook Seo
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 02:32
CPC Classifications
H; H10; H10W; H10W20/00; H10W20/01; H10W20/031; H10W20/032; H10W20/047; H10W20/048; H10P; H10P14/00; H10P14/40; H10P14/42; H10P14/43; H10W20/033; H10W20/035; H10W20/052; H10W20/0526
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
162 words
A method of forming titanium nitride composite layer, comprising the steps of: depositing a first titanium nitride layer on a substrate by exposing the substrate to a first composite gas consisting essentially of TiCl 4 and NH 3 at respective first levels that establish a first ratio of TiCl 4 to NH 3 in a range between about 0.02 and 0.05 so that a ratio of chlorine atoms to nitrogen atoms in the first composite gas is in a range between about 0.08 and 0.2; annealing the first titanium nitride layer by exposing the first titanium nitride layer to a gas consisting essentially of NH 3 ; and depositing a second titanium nitride layer on the first titanium nitride layer by exposing the first titanium nitride layer to a second composite gas consisting essentially of TiCl 4 and NH 3 at respective second levels that establish a second ratio of TiCl 4 to NH 3 that is greater than the first ratio.
Claim 2
Independent Claim
162 words
A method of forming titanium nitride composite layer, comprising the steps of: depositing a first titanium nitride layer on a substrate by exposing the substrate to a first composite gas consisting essentially of TiCl 4 and NH 3 at respective first levels that establish a first ratio of TiCl 4 to NH 3 in a range between about 0.02 and 0.05 so that a ratio of chlorine atoms to nitrogen atoms in the first composite gas is in a range between about 0.08 and 0.2; annealing the first titanium nitride layer by exposing the first titanium nitride layer to a gas consisting essentially of NH 3 ; and depositing a second titanium nitride layer on the first titanium nitride layer by exposing the first titanium nitride layer to a second composite gas consisting essentially of TiCl 4 and NH 3 at respective second levels that establish a second ratio of TiCl 4 to NH 3 that is greater than the first ratio.
Claim 3
Dependent Claim
86 words
The method of claim 1 , further comprising the steps of: annealing the second titanium nitride layer by exposing the second titanium nitride layer to a gas consisting essentially of NH 3 ; and depositing a third titanium nitride layer on the second titanium nitride layer by exposing the second titanium nitride layer to a third composite gas containing TiCl 4 and NH 3 at respective third levels that establish a third ratio of TiCl 4 to NH 3 that is less than the second ratio.
Claim 4
Dependent Claim
22 words
The method of claim 2 , wherein the second titanium nitride layer is thicker than the first and third titanium nitride layers.
Claim 5
Dependent Claim
14 words
The method of claim 2 , wherein the first ratio equals the third ratio.
Claim 6
Dependent Claim
34 words
The method of claim 1 , wherein said step of depositing a first titanium nitride layer is preceded by the step of exposing the substrate to a gas consisting essentially of NH 3 .
Claim 7
Dependent Claim
53 words
The method of claim 1 , wherein said step of depositing a first titanium nitride layer is preceded by the step of exposing the substrate to a gas consisting essentially of NH 3 for a duration of about 60 seconds and at a temperature in a range between 530° C. and 680° C.
Claim 8
Independent Claim
138 words
A method of forming titanium nitride composite layer, comprising the steps of: depositing a first titanium nitride layer on a substrate by exposing the substrate to a first composite gas consisting essentially of TiCl 4 and NH 3 at respective first levels that establish a first ratio of TiCl 4 to NH 3 in a range between about 0.02 and 0.05 so that a ratio of chlorine atoms to nitrogen atoms in the first composite gas is in a range between about 0.08 and 0.2; and depositing a second titanium nitride layer on the first titanium nitride layer by exposing the first titanium nitride layer to a second composite gas containing TiCl 4 and NH 3 at respective second levels that establish a second ratio of TiCl 4 to NH 3 that is greater than the first ratio.
Claim 9
Independent Claim
138 words
A method of forming titanium nitride composite layer, comprising the steps of: depositing a first titanium nitride layer on a substrate by exposing the substrate to a first composite gas consisting essentially of TiCl 4 and NH 3 at respective first levels that establish a first ratio of TiCl 4 to NH 3 in a range between about 0.02 and 0.05 so that a ratio of chlorine atoms to nitrogen atoms in the first composite gas is in a range between about 0.08 and 0.2; and depositing a second titanium nitride layer on the first titanium nitride layer by exposing the first titanium nitride layer to a second composite gas containing TiCl 4 and NH 3 at respective second levels that establish a second ratio of TiCl 4 to NH 3 that is greater than the first ratio.
Claim 10
Dependent Claim
87 words
The method of claim 7 , further comprising the steps of: annealing the second titanium nitride layer by exposing the second titanium nitride layer to a gas consisting essentially of NH 3 ; and then depositing a third titanium nitride layer on the second titanium nitride layer by exposing the second titanium nitride layer to a third composite gas containing TiCl 4 and NH 3 at respective third levels that establish a third ratio of TiCl 4 to NH 3 that is less than the second ratio.
Claim 11
Dependent Claim
22 words
The method of claim 8 , wherein the second titanium nitride layer is thicker than the first and third titanium nitride layers.
Claim 12
Dependent Claim
34 words
The method of claim 7 , wherein said step of depositing a first titanium nitride layer is preceded by the step of exposing the substrate to a gas consisting essentially of NH 3 .
Claim 13
Dependent Claim
53 words
The method of claim 7 , wherein said step of depositing a first titanium nitride layer is preceded by the step of exposing the substrate to a gas consisting essentially of NH 3 for a duration of about 60 seconds and at a temperature in a range between 530° C. and 680° C.
Claim 14
Dependent Claim
53 words
The method of claim 7 , wherein said step of depositing a second titanium nitride layer is preceded by the step of annealing the first titanium nitride layer by exposing the first titanium nitride layer to a gas comprising NH 3 at a temperature in a range between 530° C. and 680° C.
Claim 15
Dependent Claim
42 words
The method of claim 12 , further comprising the steps of annealing the second titanium nitride layer by exposing the second titanium nitride layer to a gas comprising NH 3 at a temperature in a range between 530° C. and 680° C.
Claim 16
Dependent Claim
63 words
The method of claim 7 , wherein said step of depositing a second titanium nitride layer is preceded by the step of annealing the first titanium nitride layer by exposing the first titanium nitride layer to a gas comprising NH 3 at a temperature in a range between 530° C. and 680° C. and at a pressure of less than about 3 Torr.
Claim 17
Dependent Claim
53 words
The method of claim 14 , wherein said step of depositing a first titanium nitride layer is preceded by the step of exposing the substrate to a gas consisting essentially of NH 3 at a temperature in a range between 530° C. and 680° C. and at a pressure of about 0.3 Torr.
Claim 18
Independent Claim
222 words
A method of forming a titanium nitride composite layer, comprising the steps of: depositing a first titanium nitride layer on a substrate by exposing the substrate to a first composite gas consisting essentially of TiCl 4 and NH 3 at respective first levels that establish a first ratio of TiCl 4 to NH 3 in a range between about 0.02 and 0.05 so that a ratio of chlorine atoms to nitrogen atoms in the first composite gas is in a range between about 0.08 and 0.2; depositing a second titanium nitride layer on the first titanium nitride layer by exposing the first titanium nitride layer to a second composite gas containing TiCl 4 and NH 3 at respective second levels that establish a second ratio of TiCl 4 to NH 3 that is greater than the first ratio: annealing the second titanium nitride layer by exposing the second titanium nitride layer to a gas consisting essentially of NH 3 ; and then depositing a third titanium nitride layer on the second titanium nitride layer by exposing the second titanium nitride layer to a third composite gas containing TiCl 4 and NH 3 at respective third levels that establish a third ratio of TiCl 4 to NH 3 that is less than the second ratio: wherein the first ratio equals the third ratio.
Claim 19
Independent Claim
222 words
A method of forming a titanium nitride composite layer, comprising the steps of: depositing a first titanium nitride layer on a substrate by exposing the substrate to a first composite gas consisting essentially of TiCl 4 and NH 3 at respective first levels that establish a first ratio of TiCl 4 to NH 3 in a range between about 0.02 and 0.05 so that a ratio of chlorine atoms to nitrogen atoms in the first composite gas is in a range between about 0.08 and 0.2; depositing a second titanium nitride layer on the first titanium nitride layer by exposing the first titanium nitride layer to a second composite gas containing TiCl 4 and NH 3 at respective second levels that establish a second ratio of TiCl 4 to NH 3 that is greater than the first ratio: annealing the second titanium nitride layer by exposing the second titanium nitride layer to a gas consisting essentially of NH 3 ; and then depositing a third titanium nitride layer on the second titanium nitride layer by exposing the second titanium nitride layer to a third composite gas containing TiCl 4 and NH 3 at respective third levels that establish a third ratio of TiCl 4 to NH 3 that is less than the second ratio: wherein the first ratio equals the third ratio.
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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) | 2004-03-26 | 2004-09-25 | 2005-03-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2008-03-26 | 2008-09-25 | 2009-03-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2012-03-26 | 2012-09-25 | 2013-03-27 | $7700.00 | Window Closed / Lapsed |