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US5202152A Expired / Lapsed US ⏱️ 0.0 years remaining

Synthesis of titanium nitride films

Assignee: Cornell Research Foundation Inc
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Filing: 1991-10-25
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Granted: 1993-04-13
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Expires: 2011-10-25
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Abstract

Abstract A substantially stoichiometric film of titanium nitride is provided by heating a substrate upon which a solution containing titanium has been applied at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate in an ammonia atmosphere. The substrate is heated to a temperature at which the titanium in the titanium-containing gel-film is substantially completely transformed to a substantially stoichiometric titanium nitride film, and at a rate of temperature change that is great enough to prevent the formation of nonstoichiometric titanium nitride compounds or other undesired titanium compounds in the resulting titanium nitride film. The invention is particularly suited for use in microelectronic devices.

Inventors

  • 👤 Emmanuel P. Giannelis
  • 👤 Joseph L. Keddie
  • 👤 Y. Y. Shacham-Diamond

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-03 19:36
CPC Classifications
H; H10; H10P; H10P14/00; H10P14/40; H10P14/46

Claims Analysis

Total Claims: 38
Claim 1
Independent Claim 115 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate, in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: applying a solution containing hydrolyzed and condensed titanium alkoxide to the surface of a substrate at a substantially ambient temperature to provide a titanium containing gel-film on the surface of the substrate; and heating the substrate in an ammonia atmosphere to a temperature of at least about 700° C., and at a rate of temperature change of at least about 50° C. per minute for a time sufficient to form a substantially stoichimetric film of titanium nitride.
Claim 2
Independent Claim 115 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate, in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: applying a solution containing hydrolyzed and condensed titanium alkoxide to the surface of a substrate at a substantially ambient temperature to provide a titanium containing gel-film on the surface of the substrate; and heating the substrate in an ammonia atmosphere to a temperature of at least about 700° C., and at a rate of temperature change of at least about 50° C. per minute for a time sufficient to form a substantially stoichimetric film of titanium nitride.
Claim 3
Dependent Claim 26 words
A method according to claim 1 wherein the step of heating the substrate comprises heating the substrate to a temperature of at least about 900° C.
Claim 4
Dependent Claim 31 words
A method according to claim 1 wherein the step of heating the substrate comprises heating the substrate at a rate of temperature change of at least about 70° C. per minute.
Claim 5
Dependent Claim 37 words
A method according to claim 1 further comprising the step of maintaining the heated substrate at the temperature to which it is heated for a time period sufficient for the substantially stoichiometric titanium nitride film to form.
Claim 6
Dependent Claim 31 words
A method according to claim 1 further comprising the step of maintaining the heated substrate at the temperature to which it is heated for between about thirty minutes and one hour.
Claim 7
Dependent Claim 38 words
A method according to claim 1 further comprising the step of cooling the heated substrate to substantially ambient temperature at a rate of temperature change substantially equal to the rate of temperature change used to heat the substrate.
Claim 8
Dependent Claim 40 words
A method according to claim 1 further comprising the step of predensifying the titanium containing gel-film on the surface of a substrate upon which the titanium alkoxide containing solution has been applied prior to the step of heating the substrate.
Claim 9
Dependent Claim 126 words
A method according to claim 7 wherein the step of predensifying the titanium containing gel-film comprises: heating the substrate upon which the titanium alkoxide containing solution has been applied to provide a gel-film containing titanium on the surface of the substrate to a temperature of from about 400° C. to about 900° C. by rapid thermal annealing so that the rate of temperature change exceeds about 1000° C. per minute in hydrogen gas; maintaining the heated substrate at the temperature to which it is heated for at least about 1 second to about 60 minutes; and cooling the heated substrate and densified gel-film to substantially ambient temperature at a rate of temperature change substantially equal to the rate of temperature change used to heat the substrate.
Claim 10
Dependent Claim 29 words
A method according to claim 7, wherein the step heating the substrate upon which the titanium containing solution has been applied comprises heating the substrate by rapid thermal annealing.
Claim 11
Dependent Claim 23 words
A method according to claim 1 wherein the step of applying a solution containing titanium alkoxide comprises spraying the solution onto the substrate.
Claim 12
Dependent Claim 23 words
A method according to claim 1 wherein the step of applying a solution containing titanium alkoxide comprises dipping the solution onto the substrate.
Claim 13
Dependent Claim 24 words
A method according to claim 1 wherein the step of applying a solution containing titanium alkoxide comprises spin coating the solution onto the substrate.
Claim 14
Dependent Claim 39 words
A method according to claim 12 wherein the step of spin coating the solution onto the substrate comprises the step of pouring the solution on the substrate and spinning the substrate at rate of about 1000 to 6000 rpm.
Claim 15
Dependent Claim 36 words
A method according to claim 1 wherein the step of applying a solution containing titanium alkoxide to the surface of a substrate comprises the step of applying the solution to the surface of a metal substrate.
Claim 16
Dependent Claim 36 words
A method according to claim 1 wherein the step of applying a solution containing titanium alkoxide to the surface of a substrate comprises the step of applying the solution to the surface of a non-metal substrate.
Claim 17
Dependent Claim 37 words
A method according to claim 15 wherein the step of applying a solution containing titanium alkoxide to the surface of a non-metal substrate comprises the step of applying the solution to the surface of a silicon wafer.
Claim 18
Dependent Claim 36 words
A method according to claim 1 wherein the step of applying a solution containing titanium alkoxide to the surface of a substrate comprises the step of applying the solution to the surface of a ceramic substrate.
Claim 19
Dependent Claim 36 words
A method according to claim 1 wherein the step of applying a solution containing titanium alkoxide to the surface of a substrate comprises the step of applying the solution to the surface of a glass substrate.
Claim 20
Independent Claim 36 words
A method according to claim I wherein the step of applying a solution containing titanium alkoxide to the surface of a substrate comprises the step of applying the solution to the surface of a polymer substrate.
Claim 21
Dependent Claim 34 words
A method according to claim 1 wherein the step of heating the substrate in an ammonia atmosphere comprises the step of heating the substrate in an ammonia atmosphere of at least about 99.99% ammonia.
Claim 22
Independent Claim 175 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: applying a solution of hydrolyzed and condensed titanium alkoxide in solvent, in which the titanium alkoxide has the formula Ti(OR) 4 , wherein R is an alkyl group having 1 to 6 carbon atoms, and in which the solvent is selected from the group consisting of aliphatic, cycloaliphatic and aromatic compounds containing from 1 to 20 carbon atoms and at least one functional group consisting of ether and hydroxyl, to the surface of a substrate at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate; and heating the substrate in an ammonia atmosphere to a temperature of at least about 700° C., and at a rate of temperature change of at least about 50° C. per minute for a time sufficient to form a substantially stoichimetric film of titanium nitride.
Claim 23
Independent Claim 175 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: applying a solution of hydrolyzed and condensed titanium alkoxide in solvent, in which the titanium alkoxide has the formula Ti(OR) 4 , wherein R is an alkyl group having 1 to 6 carbon atoms, and in which the solvent is selected from the group consisting of aliphatic, cycloaliphatic and aromatic compounds containing from 1 to 20 carbon atoms and at least one functional group consisting of ether and hydroxyl, to the surface of a substrate at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate; and heating the substrate in an ammonia atmosphere to a temperature of at least about 700° C., and at a rate of temperature change of at least about 50° C. per minute for a time sufficient to form a substantially stoichimetric film of titanium nitride.
Claim 24
Dependent Claim 72 words
A method according to claim 21 wherein the step of applying a solution of titanium alkoxide in solvent comprises the step of applying a solution of titanium alkoxide in which the titanium alkoxide has the formula Ti(OR) 4 , wherein R is an alkyl group having 2 to 4 carbon atom s, and in which the solvent is selected from the group consisting of C 2 -C 5 saturated or unsaturated alcohols.
Claim 25
Dependent Claim 100 words
A method according to claim 21 wherein the step of applying a solution of titanium alkoxide in solvent comprises the step of applying a solution of titanium alkoxide in which the titanium alkoxide is selected from the group consisting of titanium (IV) ethoxide, titanium (IV) n-propoxide, titanium (IV) i-propoxide, titanium (IV) n-butoxide, titanium (IV) s-butoxide, and titanium (IV) t-butoxide, titanium(IV) isoamyloxide and titanium (IV) n-capryloxide, and in which the solvent is selected from the group consisting of ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol, t-butanol, vinyl alcohol, allyl alcohol, crotyl alcohol, 1-butene-4-ol, 3-butene-2-ol, methanol, cyclohexanol, dibutylether, phenol, benzyl alcohol, tertahydrafuran and dodecanol.
Claim 26
Dependent Claim 37 words
A method according to claim 21 wherein the step of applying a solution containing titanium alkoxide in solvent to the surface of a substrate comprises the step of applying a solution of titanium (IV) ethoxide and t-butanol.
Claim 27
Dependent Claim 46 words
A method according to claim 21 wherein the step of applying a solution of titanium alkoxide in solvent comprises the step of applying a solution of titanium alkoxide in solvent in which the solvent comprises from about 40% to about 90% by volume of the solution.
Claim 28
Dependent Claim 40 words
A method according to claim 21 further comprising the step of adding between about 0.001 and 2 moles of an acid per mole of alkoxide to the titanium alkoxide solution before applying the solution to the surface of a substrate.
Claim 29
Dependent Claim 38 words
A method according to claim 26 wherein the step of adding an acid to the titanium alkoxide solution comprises the step of adding an acid selected from the group consisting of hydrochloric acid, nitric acid and acetic acid.
Claim 30
Dependent Claim 55 words
A method according to claim 21 further comprising the step of heating the substrate on which the titanium alkoxide solution has been applied to a temperature of about 10° C. to about 70° C. for a time period of about 0.5 to about 48 hours prior to the step of heating the substrate in ammonia.
Claim 31
Dependent Claim 55 words
A method according to claim 21 further comprising the step of heating the substrate on which the titanium alkoxide solution has been applied to a temperature of about 25° C. to about 65° C. for a time period of about 0.75 to about 2.5 hours prior to the step of heating the substrate in ammonia.
Claim 32
Independent Claim 250 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices on the surface of a substrate, the method comprising: applying a solution containing a hydrolyzed and condensed titanium alkoxide in solvent, in which the titanium alkoxide has the formula Ti(OR) 4 , wherein R is an alkyl having 1 to 6 carbon atoms, and in which the solvent is selected from the group consisting of aliphatic, cycloaliphatic and aromatic compounds containing from 1 to 20 carbon atoms and at least one functional group consisting of ether and hydroxyl, to the surface of a substrate at a substantially ambient temperature to provide a titanium-containing gel-film on the surface of the substrate; predensifying the titanium containing gel-film on the surface of a substrate upon which the titanium containing solution has been applied; cooling the predensified gel-film on the surface of the substrate to substantially ambient temperature; heating the substrate in an ammonia atmosphere to a temperature of at least about 700° C. and at a rate of temperature change of at least about 50° C. per minute; maintaining the heated substrate at the temperature to which it is heated for at least about thirty minutes to about six hours; and cooling the heated substrate to substantially ambient temperature at a rate of temperature change substantially equal to the rate of temperature change used to heat the substrate.
Claim 33
Independent Claim 250 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices on the surface of a substrate, the method comprising: applying a solution containing a hydrolyzed and condensed titanium alkoxide in solvent, in which the titanium alkoxide has the formula Ti(OR) 4 , wherein R is an alkyl having 1 to 6 carbon atoms, and in which the solvent is selected from the group consisting of aliphatic, cycloaliphatic and aromatic compounds containing from 1 to 20 carbon atoms and at least one functional group consisting of ether and hydroxyl, to the surface of a substrate at a substantially ambient temperature to provide a titanium-containing gel-film on the surface of the substrate; predensifying the titanium containing gel-film on the surface of a substrate upon which the titanium containing solution has been applied; cooling the predensified gel-film on the surface of the substrate to substantially ambient temperature; heating the substrate in an ammonia atmosphere to a temperature of at least about 700° C. and at a rate of temperature change of at least about 50° C. per minute; maintaining the heated substrate at the temperature to which it is heated for at least about thirty minutes to about six hours; and cooling the heated substrate to substantially ambient temperature at a rate of temperature change substantially equal to the rate of temperature change used to heat the substrate.
Claim 34
Independent Claim 236 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: applying a solution containing hydrolyzed and condensed titanium (IV) ethoxide and t-butanol to the surface of a substrate at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate; predensifying the titanium containing gel-film on the surface of a substrate upon which the titanium containing solution has been applied by heating the substrate to a temperature of from about 400° C. to about 900° C. by rapid thermal annealing so that the rate of temperature change exceeds about 1000° C. per minute in hydrogen gas; cooling the heated predensified gel-film on the surface of the substrate to substantially ambient temperature at a rate of temperature change substantially equal to the rate of heating; heating the substrate in an ammonia atmosphere to a temperature of at least about 900° C. and at a rate of temperature change of at least about 70° C. per minute; maintaining the heated substrate at the temperature to which it is heated for between about thirty minutes and one hour; and cooling the heated substrate to substantially ambient temperature at a rate of temperature change substantially equal to the rate of temperature change used to heat the substrate.
Claim 35
Independent Claim 236 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: applying a solution containing hydrolyzed and condensed titanium (IV) ethoxide and t-butanol to the surface of a substrate at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate; predensifying the titanium containing gel-film on the surface of a substrate upon which the titanium containing solution has been applied by heating the substrate to a temperature of from about 400° C. to about 900° C. by rapid thermal annealing so that the rate of temperature change exceeds about 1000° C. per minute in hydrogen gas; cooling the heated predensified gel-film on the surface of the substrate to substantially ambient temperature at a rate of temperature change substantially equal to the rate of heating; heating the substrate in an ammonia atmosphere to a temperature of at least about 900° C. and at a rate of temperature change of at least about 70° C. per minute; maintaining the heated substrate at the temperature to which it is heated for between about thirty minutes and one hour; and cooling the heated substrate to substantially ambient temperature at a rate of temperature change substantially equal to the rate of temperature change used to heat the substrate.
Claim 36
Independent Claim 112 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: heating a substrate upon which a hydrolyzed and condensed solution containing titanium has been applied at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate, and in an ammonia atmosphere to a temperature of at least about 700° C., and at a rate of temperature change of at least about 50° C. per minute for a time sufficient to form a substantially stoichimetric film of titanium nitride.
Claim 37
Independent Claim 112 words
A method of producing a substantially stoichiometric film of titanium nitride on the surface of a substrate in which the film is particularly suitable for diffusion barriers and planarization and interconnect materials in electronic devices, the method comprising: heating a substrate upon which a hydrolyzed and condensed solution containing titanium has been applied at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate, and in an ammonia atmosphere to a temperature of at least about 700° C., and at a rate of temperature change of at least about 50° C. per minute for a time sufficient to form a substantially stoichimetric film of titanium nitride.
Claim 38
Dependent Claim 40 words
A method according to claim 32 further comprising the step of predensifying the titanium containing the gel-film on the surface of a substrate upon which the titanium containing solution has been applied prior to the step of heating the substrate.

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1996-04-12 1996-10-12 1997-04-13 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 2000-04-12 2000-10-12 2001-04-13 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2004-04-12 2004-10-12 2005-04-13 $7700.00 Window Closed / Lapsed

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