US6090709A
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US
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Methods for chemical vapor deposition and preparation of conformal titanium-based films
Assignee: Gelest Inc
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Filing: 1997-12-12
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Granted: 2000-07-18
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Expires: 2017-12-12
Abstract
Abstract Titanium and titanium nitride layers can be produced by chemical vapor deposition (CVD) processes conducted at temperatures below 475° C. The layers may serve as diffusion and adhesion barriers for ultra-large scale integration (ULSI) microelectronic applications. The processes use a titanium halide precursor, such as titanium tetraiodide, and hydrogen or hydrogen in combination with nitrogen, argon, or ammonia to either produce pure titanium metal films, titanium films which alloy with the underlying silicon, or titanium nitride films. The deposition of titanium metal from titanium halide and hydrogen or the deposition of titanium nitride from titanium halide with nitrogen and hydrogen is achieved with the assistance of a low energy plasma. The process allows smooth and reversible transition between deposition of films of either titanium metal or titanium nitride by introduction or elimination of nitrogen or ammonia.
Inventors
- 👤 Alain E. Kaloyeros
- 👤 Barry C. Arkles
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 01:33
CPC Classifications
H; H10; H10W; H10W20/00; H10W20/01; H10W20/031; H10W20/032; H10W20/033; C; C23; C23C; C23C16/00; C23C16/06; C23C16/08; C23C16/14; C23C16/22; C23C16/30; C23C16/34; H10P; H10P14/00; H10P14/40; H10P14/418; H10P14/42; H10P14/43
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
126 words
A method for depositing multiple layers of titanium-based film onto a substrate by sequential chemical vapor deposition (CVD), comprising the steps of introducing a substrate and a source precursor into a CVD chamber, wherein the source precursor is a vapor of at least one compound of formula (I): Ti(I.sub.4-m-n)(Br.sub.m)(Cl.sub.n) (I) wherein m is 0-4 and n is 0-2; and sequentially depositing onto the substrate at a temperature of about 200-650° C. layers of titanium metal film and titanium nitride film, wherein either the titanium metal film or the titanium nitride film may be deposited first onto the substrate and wherein at least the titanium metal film is deposited in the presence of a plasma, with hydrogen halides or ammonium halides being major byproducts of the deposition.
Claim 2
Independent Claim
126 words
A method for depositing multiple layers of titanium-based film onto a substrate by sequential chemical vapor deposition (CVD), comprising the steps of introducing a substrate and a source precursor into a CVD chamber, wherein the source precursor is a vapor of at least one compound of formula (I): Ti(I.sub.4-m-n)(Br.sub.m)(Cl.sub.n) (I) wherein m is 0-4 and n is 0-2; and sequentially depositing onto the substrate at a temperature of about 200-650° C. layers of titanium metal film and titanium nitride film, wherein either the titanium metal film or the titanium nitride film may be deposited first onto the substrate and wherein at least the titanium metal film is deposited in the presence of a plasma, with hydrogen halides or ammonium halides being major byproducts of the deposition.
Claim 3
Dependent Claim
32 words
The method according to claim 1, wherein a titanium metal film is deposited onto a substrate to provide a coated substrate, and a titanium nitride film is deposited onto the coated substrate.
Claim 4
Dependent Claim
44 words
The method according to claim 1, wherein hydrogen gas is present in the chamber with said vapor and said substrate, and said chamber contains a plasma having a low power density, for a time sufficient to deposit a titanium metal film onto the substrate.
Claim 5
Dependent Claim
32 words
The method according to claim 3, wherein an inert gas selected from the group consisting of argon and xenon is additionally present in the chamber during deposition of the titanium metal film.
Claim 6
Dependent Claim
14 words
The method according to claim 1, wherein the source precursor is titanium tetraiodide vapor.
Claim 7
Dependent Claim
45 words
The method according to claim 1, wherein a nitrogen-containing gas is present in said chamber with said substrate and said vapor, and said chamber contains a plasma having a low power density, for a time sufficient to deposit a titanium nitride film onto the substrate.
Claim 8
Dependent Claim
50 words
The method according to claim 6, wherein the nitrogen-containing gas is selected from the group consisting of (a) hydrogen and at least one of nitrogen, ammonia or hydrazine; (b) nitrogen and at least one of ammonia, argon or xenon; and (c) ammonia and at least one of argon and xenon.
Claim 9
Dependent Claim
22 words
The method according to claim 6, wherein the substrate is maintained at a temperature of about 350° C. to about 475° C.
Claim 10
Dependent Claim
14 words
The method according to claim 7, wherein the nitrogen-containing gas is hydrogen and nitrogen.
Claim 11
Dependent Claim
81 words
The method according to claim 1, wherein during deposition of titanium nitride film the deposition chamber additionally contains a first gas selected from the group consisting of ammonia and hydrazine; and a second gas selected from the group consisting of hydrogen, nitrogen, argon and xenon; and said substrate, said vapor, said first gas and said second gas are reacted under thermal conditions in the absence of a plasma for a time sufficient to deposit a titanium nitride film onto the substrate.
Claim 12
Dependent Claim
18 words
The method according to claim 10, wherein the first gas is ammonia and the second gas is hydrogen.
Claim 13
Dependent Claim
13 words
The method according to claim 1, wherein said substrate is a microelectronics substrate.
Claim 14
Dependent Claim
11 words
The method according to claim 12, wherein said substrate is silicon-containing.
Claim 15
Dependent Claim
15 words
The method according to claim 1, wherein n in formula (I) is equal to zero.
Claim 16
Dependent Claim
24 words
The method according to claim 1, wherein the layers are deposited without transfer of the substrate from the chamber so as to minimize contamination.
Claim 17
Independent Claim
104 words
A method for chemical vapor deposition (CVD) of a titanium metal film onto a substrate, comprising introducing to a deposition chamber the following components: (a) a microelectronics substrate; (b) a vapor of a compound having the formula (I): Ti(I.sub.4-m)(Br.sub.m) (I) wherein m is 0-4; and (c) at least one of a carrier gas and an auxiliary gas for said vapor; and maintaining the substrate at a temperature of about 200 to 650° C. in the presence of a plasma for a time sufficient to deposit a titanium metal film onto the substrate, with hydrogen halides or ammonium halides being major byproducts of the deposition.
Claim 18
Independent Claim
104 words
A method for chemical vapor deposition (CVD) of a titanium metal film onto a substrate, comprising introducing to a deposition chamber the following components: (a) a microelectronics substrate; (b) a vapor of a compound having the formula (I): Ti(I.sub.4-m)(Br.sub.m) (I) wherein m is 0-4; and (c) at least one of a carrier gas and an auxiliary gas for said vapor; and maintaining the substrate at a temperature of about 200 to 650° C. in the presence of a plasma for a time sufficient to deposit a titanium metal film onto the substrate, with hydrogen halides or ammonium halides being major byproducts of the deposition.
Claim 19
Dependent Claim
22 words
The method according to claim 16, wherein the substrate is maintained at a temperature of about 350° C. to about 475° C.
Claim 20
Dependent Claim
15 words
The method according to claim 16, wherein the compound of formula (I) is titanium tetraiodide.
Claim 21
Dependent Claim
24 words
The method according to claim 16, wherein the substrate is a silicon or silicon dioxide wafer useful in the manufacture of a ULSI device.
Claim 22
Dependent Claim
14 words
The method according to claim 16, wherein the plasma has a low power density.
Claim 23
Independent Claim
85 words
A method for chemical vapor deposition (CVD) of a titanium nitride film onto a substrate, comprising introducing to a deposition chamber the following components: (a) a microelectronics substrate; (b) a vapor of a compound having the formula: TiI 4 ; and (c) at least one nitrogen-containing gas; and maintaining the substrate at a temperature of about 200 to 650° C. for a time sufficient to deposit a titanium nitride film onto the substrate, with hydrogen iodides or ammonium iodides being major byproducts of the deposition.
Claim 24
Independent Claim
85 words
A method for chemical vapor deposition (CVD) of a titanium nitride film onto a substrate, comprising introducing to a deposition chamber the following components: (a) a microelectronics substrate; (b) a vapor of a compound having the formula: TiI 4 ; and (c) at least one nitrogen-containing gas; and maintaining the substrate at a temperature of about 200 to 650° C. for a time sufficient to deposit a titanium nitride film onto the substrate, with hydrogen iodides or ammonium iodides being major byproducts of the deposition.
Claim 25
Dependent Claim
57 words
The method according to claim 21, wherein the nitrogen-containing gas is selected from the group consisting of: (a) hydrogen and at least one of nitrogen and ammonia and at least one of argon and xenon; (b) nitrogen and at least one of ammonia, argon and xenon; and (c) ammonia and at least one of argon and xenon.
Claim 26
Dependent Claim
14 words
The method according to claim 22, wherein the nitrogen-containing gas is hydrogen and nitrogen.
Claim 27
Dependent Claim
18 words
The method according to claim 21, wherein the deposition is carried out in the presence of a plasma.
Claim 28
Dependent Claim
23 words
The method according to claim 21, wherein the substrate is a silicon or silicon dioxide wafer useful in the manufacture of ULSI devices.
Claim 29
Independent Claim
94 words
A method for forming a conformal layer of a titanium-containing compound, comprising the steps of providing a silicon-containing substrate having formed thereon a via having sidewalls and a bottom wall, wherein the sidewalls are spaced apart less than 0.1 microns; providing a vapor of a compound containing TiI 4 ; maintaining said silicon-containing substrate at a temperature of about 200 to 650° for a selected period of time; and depositing on said sidewalls and said bottom wall a substantially continuous titanium-based film, with hydrogen iodides or ammonium iodides being major byproducts of the deposition.
Claim 30
Independent Claim
94 words
A method for forming a conformal layer of a titanium-containing compound, comprising the steps of providing a silicon-containing substrate having formed thereon a via having sidewalls and a bottom wall, wherein the sidewalls are spaced apart less than 0.1 microns; providing a vapor of a compound containing TiI 4 ; maintaining said silicon-containing substrate at a temperature of about 200 to 650° for a selected period of time; and depositing on said sidewalls and said bottom wall a substantially continuous titanium-based film, with hydrogen iodides or ammonium iodides being major byproducts of the deposition.
Claim 31
Dependent Claim
41 words
The method according to claim 26, wherein the step of maintaining said silicon containing substrate at a temperature of about 200 to 650° C., includes the step of maintaining the silicon-containing substrate at a temperature of about 350 to 475° C.
Claim 32
Dependent Claim
36 words
The method according to claim 26, wherein said step of depositing a substantially continuous titanium-based film includes the step of forming a titanium-based film having a thickness of between about 50 angstroms and about 1500 anstroms.
Claim 33
Dependent Claim
36 words
The method according to claim 26, wherein the step of providing a silicon-containing substrate includes the step of providing a substrate having formed thereon a via with an aspect ratio of between about 3:1 and 6:1.
Claim 34
Dependent Claim
17 words
The method according to claim 21 wherein the temperature for maintaining the substrate is about 350-475° C.
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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) | 2003-07-18 | 2004-01-17 | 2004-07-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2007-07-18 | 2008-01-17 | 2008-07-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2011-07-18 | 2012-01-17 | 2012-07-18 | $7700.00 | Window Closed / Lapsed |