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US6482740B2
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Method of growing electrical conductors by reducing metal oxide film with organic compound containing -OH, -CHO, or -COOH
Assignee: ASM International NV
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Filing: 2001-05-15
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Granted: 2002-11-19
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Expires: 2021-05-15
Abstract
Abstract This invention relates to manufacturing of integrated circuits (ICs) and especially conductive layers suitable for use in an IC. According to the preferred method a metal oxide thin film is deposited on a substrate surface and reduced thereafter essentially into a metallic form with an organic reducing agent. The metal oxide is preferably deposited according to the principles of atomic layer deposition (ALD) using a metal source chemical and an oxygen source chemical. The reduction step is preferably carried out in an ALD reactor using one or more vaporized organic compounds that contain at least one functional group selected from the group consisting of -OH, -CHO and -COOH.
Inventors
- 👤 Pekka J. Soininen
- 👤 Kai-Erik Elers
- 👤 Suvi Haukka
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 01:09
CPC Classifications
H; H10; H10W; H10W20/00; H10W20/01; H10W20/031; H10W20/032; H10W20/033; H10P; H10P50/00; H10P14/00; H10P14/40; H10P14/42; H10P14/43; H10P14/432; H10P70/00; H10P70/20; H10P70/27; H10P95/00; H10W20/042; H10W20/043; H10W20/052; H10W20/0523; H10W20/056; H10W20/064; H10W20/071; H10W20/074; H10W20/076; H10W20/077; H10W20/081; H10W20/093; H10W20/094; H10W20/084; H10W72/00; H10W72/50; H10W72/551; H10W72/552; H10W72/5525; H10W90/00; H10W90/701; H10W90/731; H10W90/736; H10W90/751; H10W90/756
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
58 words
A method of producing a conductive thin film, comprising: depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process; and at least partially reducing said metal oxide thin film with one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO and —COOH.
Claim 2
Independent Claim
58 words
A method of producing a conductive thin film, comprising: depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process; and at least partially reducing said metal oxide thin film with one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO and —COOH.
Claim 3
Dependent Claim
15 words
The method of claim 1 , wherein the organic compounds are in the vapor phase.
Claim 4
Dependent Claim
71 words
The method of claim 1 , wherein the metal oxide thin film is selected from the group consisting of ReO 2 , Re 2 O 5 , ReO 3 , RuO 2 , OsO 2 , CoO, Co 3 O 4 , Rh 2 O 3 , RhO 2 , IrO 2 , NiO, PdO, PtO 2 , Cu 2 O, CuO, Ag 2 O and Au 2 O 3 .
Claim 5
Dependent Claim
72 words
The method of claim 1 , wherein the ALD process comprises feeding into the reaction chamber and contacting the substrate with alternating vapor phase pulses of at least one first source chemical comprising a compound capable of adsorbing no more than a monolayer of metal species on the substrate and at least one second source chemical comprising a compound capable of oxidizing the metal species on the substrate into the metal oxide.
Claim 6
Dependent Claim
44 words
The method of claim 4 , wherein the first source chemical is Cu(thd) 2 and the second source chemical is selected from the group consisting of ozone (O 3 ), oxygen (O 2 ) and a mixture of O 3 and O 2 .
Claim 7
Dependent Claim
43 words
The method of claim 4 , wherein the first source chemical is CuCl and the second source chemical is selected from the group consisting of ozone (O 3 ), oxygen (O 2 ) and a mixture of O 3 and O 2 .
Claim 8
Dependent Claim
28 words
The method of claim 4 , wherein the first source chemical is anhydrous metal nitrate and the second source chemical is vaporized aqueous solution of NH 3 .
Claim 9
Dependent Claim
33 words
The method of claim 4 , wherein the first source chemical is anhydrous copper nitrate (Cu(NO 3 ) 2 ) and the second source chemical is vaporized aqueous solution of NH 3 .
Claim 10
Dependent Claim
44 words
The method of claim 4 , wherein the first source chemical is Co(thd) 3 and the second source chemical is selected from the group consisting of ozone (O 3 ), oxygen (O 2 ), and a mixture of O 3 and O 2 .
Claim 11
Dependent Claim
44 words
The method of claim 4 , wherein the first source chemical is Pd(thd) 3 and the second source chemical is selected from the group consisting of ozone (O 3 ), oxygen (O 2 ), and a mixture of O 3 and O 2 .
Claim 12
Dependent Claim
29 words
The method of claim 4 , wherein the first source chemical is bis(ethylcyclopentadienyl)ruthenium ((EtCp) 2 Ru) and the second source chemical is a mixture of oxygen and water gases.
Claim 13
Dependent Claim
102 words
The method of claim 1 , wherein the vaporized organic compound used for reducing the metal oxide is an organic compound containing at least one alcohol (—OH) group, said organic compound selected from the group consisting of primary alcohols; secondary alcohols; tertiary alcohols; polyhydroxy alcohols; cyclic alcohols which have an —OH group attached to at least one carbon atom which is part of a ring of 1-10 carbon atoms; aromatic alcohols having at least one —OH group attached either to the benzene ring or to a carbon atom in a side-chain attached to benzene ring; halogenated alcohols; and other derivatives of alcohols.
Claim 14
Dependent Claim
39 words
The method of claim 12 , wherein said primary alcohols are primary alcohols according to the general formula (I) R 1 —OH (I) wherein R 1 is a linear or branched C 1 -C 20 alkyl or alkenyl group.
Claim 15
Dependent Claim
25 words
The method of claim 13 , wherein each R 1 is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Claim 16
Dependent Claim
39 words
The method of claim 12 , wherein said secondary alcohols are secondary alcohols according to formula (II) wherein each R 1 is selected independently from the group of linear or branched C 1 -C 20 alkyl and alkenyl groups.
Claim 17
Dependent Claim
25 words
The method of claim 15 , wherein each R 1 is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Claim 18
Dependent Claim
41 words
The method of claim 12 , wherein said tertiary alcohols are tertiary alcohols according to the general formula (III) wherein each R 1 is selected independently from the group of linear or branched C 1 -C 20 alkyl and alkenyl groups.
Claim 19
Dependent Claim
25 words
The method of claim 17 , wherein each R 1 is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Claim 20
Dependent Claim
31 words
The method of claim 12 , wherein said cyclic alcohols have an —OH group attached to at least one carbon atom which is part of a ring of 5-6 carbon atoms.
Claim 21
Dependent Claim
121 words
The method of claim 1 , wherein the vaporized organic compound used for reducing the metal oxide is a compound containing at least one aldehyde (—CHO) group, said reducing agent being selected from the group consisting of: compounds having the general formula (V) R 3 —CHO (V) wherein R 3 is hydrogen or linear or branched C 1 -C 20 alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl; and compounds having the general formula (VI) OHC—R 4 —CHO (VI) wherein R 4 is a linear or branched C 1 -C 20 saturated or unsaturated hydrocarbon or R 4 is zero, when the aldehyde groups are bonded to each other; and halogenated aldehydes; and other derivatives of aldehydes.
Claim 22
Dependent Claim
86 words
The method of claim 1 , wherein the vaporized organic compound used for reducing the metal oxide is a compound containing at least one carboxylic acid (—COOH) group, said reducing agent being selected from the group consisting of: compounds having the general formula (VII) R 5 COOH (VII) wherein R 5 is hydrogen or linear or branched C 1 -C 20 alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl; and polycarboxylic acids; and halogenated carboxylic acids; and other derivatives of carboxylic acids.
Claim 23
Independent Claim
141 words
A method of producing a conductive thin film comprising the steps of: A. placing a substrate in a chamber; B. exposing the substrate to a gaseous first reactant, wherein the first reactant adsorbs no more than a monolayer of metal species on the substrate; C. removing gases from the chamber; D. exposing the substrate to a second gaseous reactant comprising a compound that is capable of oxidizing the adsorbed metal species on the substrate into metal oxide; E. removing gases from the chamber; F. repeating the above steps B through E at least three times to form a metal oxide film; and G. following step F, exposing the substrate to one or more organic compounds that contains at least one functional group selected from the group consisting of —OH, —CHO and —COOH and that reduces the metal oxide film to metal.
Claim 24
Independent Claim
141 words
A method of producing a conductive thin film comprising the steps of: A. placing a substrate in a chamber; B. exposing the substrate to a gaseous first reactant, wherein the first reactant adsorbs no more than a monolayer of metal species on the substrate; C. removing gases from the chamber; D. exposing the substrate to a second gaseous reactant comprising a compound that is capable of oxidizing the adsorbed metal species on the substrate into metal oxide; E. removing gases from the chamber; F. repeating the above steps B through E at least three times to form a metal oxide film; and G. following step F, exposing the substrate to one or more organic compounds that contains at least one functional group selected from the group consisting of —OH, —CHO and —COOH and that reduces the metal oxide film to metal.
Claim 25
Dependent Claim
15 words
The method of claim 22 , wherein the organic compound is in the vapor phase.
Claim 26
Dependent Claim
26 words
The method of claim 22 , wherein in step F, steps B through E are repeated at least 10 times to form a metal oxide film.
Claim 27
Dependent Claim
27 words
The method of claim 22 , wherein steps B through G are repeated at least twice to increase the thickness of the conductive film on the substrate.
Claim 28
Independent Claim
63 words
A method of producing a conductive thin film comprising: depositing a metal oxide thin film of at least 1 nm thickness on a substrate; and reducing said metal oxide thin film to metal by exposing the metal oxide thin film to one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO and —COOH.
Claim 29
Independent Claim
63 words
A method of producing a conductive thin film comprising: depositing a metal oxide thin film of at least 1 nm thickness on a substrate; and reducing said metal oxide thin film to metal by exposing the metal oxide thin film to one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO and —COOH.
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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) | 2005-11-18 | 2006-05-20 | 2006-11-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2009-11-18 | 2010-05-20 | 2010-11-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2013-11-18 | 2014-05-20 | 2014-11-19 | $7700.00 | Window Closed / Lapsed |