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US6706115B2
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Method for preparing metal nitride thin films
Assignee: ASM International NV
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Filing: 2002-03-15
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Granted: 2004-03-16
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Expires: 2022-03-15
Abstract
Abstract Methods for producing metal nitride thin layers having low resistivity by means of atomic layer deposition processes comprising alternate surface reactions of metal and nitrogen source materials include using nitrogen source materials that have better reducing properties than ammonia and 1,1-dimethyl hydrazine. Suitable compounds for that purpose include those in which a hydrocarbon group bound to nitrogen, when dissociating in a homolytic manner, generates a radical that serves as a reducing agent and reacts further to generate atomic hydrogen. The nitride thin layers produced are especially suitable for use as diffusion barrier layers in integrated circuits.
Inventors
- 👤 Markku Leskelä
- 👤 Mikko Ritala
- 👤 Petra Alén
- 👤 Marika Juppo
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 00:53
CPC Classifications
C; C23; C23C; C23C16/00; C23C16/44; C23C16/455; C23C16/45523; C23C16/45525; C23C16/45553; C23C16/22; C23C16/30; C23C16/34; H; H10; H10P; H10P14/00; H10P14/40; H10P14/418
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
73 words
A method of growing transition metal nitride thin films by an atomic layer deposition (ALD) process in which a nitride thin film is grown on a substrate by means of alternate surface reactions of metal and nitrogen source materials, wherein the nitrogen source material comprises a compound having a hydrocarbon, amino or silyl group bound to nitrogen, and wherein hydrolytic dissociation of the hydrocarbon, amino or silyl group from nitrogen generates a radical.
Claim 2
Independent Claim
73 words
A method of growing transition metal nitride thin films by an atomic layer deposition (ALD) process in which a nitride thin film is grown on a substrate by means of alternate surface reactions of metal and nitrogen source materials, wherein the nitrogen source material comprises a compound having a hydrocarbon, amino or silyl group bound to nitrogen, and wherein hydrolytic dissociation of the hydrocarbon, amino or silyl group from nitrogen generates a radical.
Claim 3
Dependent Claim
14 words
The method of claim 1 , wherein the radical serves as a reducing agent.
Claim 4
Dependent Claim
15 words
The method of claim 1 , wherein the radical reacts further to generate atomic hydrogen.
Claim 5
Dependent Claim
48 words
The method of claim 1 , wherein the nitrogen source material comprises a compound of formula (I) NR x H 3-x (I) wherein R is a hydrocarbon, amino or silyl group, each R can be the same or different, and X is an integer 1, 2 or 3.
Claim 6
Dependent Claim
15 words
The method of claim 4 , wherein at least one R is a hydrocarbon group.
Claim 7
Dependent Claim
22 words
The method of claim 4 , wherein the bond energy between the amine and the hydrocarbon group is less than 460 kJ/mol.
Claim 8
Dependent Claim
28 words
The method of claim 4 , wherein at least one R is a substituted or unsubstituted cyclic, linear or branched alkyl, alkenul, allyl, aryl, alkylaryl, or arylalkyl group.
Claim 9
Dependent Claim
21 words
The method of claim 4 , wherein at least one R is a linear or branched C 1 -C 10 alkyl.
Claim 10
Dependent Claim
15 words
The method of claim 8 , wherein at least one R is a tertiary alkyl.
Claim 11
Dependent Claim
26 words
The method of claim 1 , wherein the nitrogen source material additionally comprises a compound selected from the group consisting of ammonia, hydrazine and hydrazine derivatives.
Claim 12
Dependent Claim
111 words
The method of claim 1 , wherein the metal source material comprises a compound of formula (II) MX n L z (II) wherein: M is a transition metal; each X is a negatively charged ligand selected from the group consisting of halides, hydrides, alkylamides, alkoxides, aryloxides, alkyls, cyclopentadienyls and β-diketonates; n is an integer indicating the number of ligands X, wherein when each ligand has a charge of −1, n is the same as the oxidation state of metal in the source material MX n ; L is a neutral adduct ligand binding to M at one or more of its atoms; and z is an integer from 0 to 4.
Claim 13
Dependent Claim
29 words
The method of claim 11 , wherein the metal M belongs to one of groups 3, 4, 5, 6, 7, 8, 9,10, 11 and 12 of the periodic table.
Claim 14
Dependent Claim
24 words
The method of claim 1 , wherein the metal source material is selected from the group consisting of halides and alkylamides of transition metals.
Claim 15
Dependent Claim
41 words
The method of claim 1 , wherein the metal source material is selected from the group consisting of TaCl 5 , TaBr 5 and TaI 5 and the nitrogen source material is selected from the group consisting of tert-butylamine and allylamine.
Claim 16
Dependent Claim
41 words
The method of claim 1 , wherein the metal source material is selected from the group consisting of TiCl 4 , TiBr 4 and TiI 4 and the nitrogen source material is selected from the group consisting of tert-butylamine and allylamine.
Claim 17
Independent Claim
99 words
A method of producing an electrically conductive diffusion barrier layer between a conductor and an isolation layer on a substrate comprising integrated circuits, the method comprising: introducing the substrate into the reaction space of a reactor; and growing a conductive metal nitride layer on the substrate by an atomic layer deposition (ALD) process comprising alternate surface reactions of metal and nitrogen source materials, wherein the nitrogen source material comprises a compound having a hydrocarbon, amino or silyl group attached to the nitrogen and wherein dissociation of the hydrocarbon, amino or silyl group from the nitrogen generates a reducing agent.
Claim 18
Independent Claim
99 words
A method of producing an electrically conductive diffusion barrier layer between a conductor and an isolation layer on a substrate comprising integrated circuits, the method comprising: introducing the substrate into the reaction space of a reactor; and growing a conductive metal nitride layer on the substrate by an atomic layer deposition (ALD) process comprising alternate surface reactions of metal and nitrogen source materials, wherein the nitrogen source material comprises a compound having a hydrocarbon, amino or silyl group attached to the nitrogen and wherein dissociation of the hydrocarbon, amino or silyl group from the nitrogen generates a reducing agent.
Claim 19
Dependent Claim
13 words
The method of claim 16 , wherein the reducing agent is a radical.
Claim 20
Dependent Claim
21 words
The method of claim 16 , wherein the dissociation directly produces a radical that decomposes further to generate the reducing agent.
Claim 21
Dependent Claim
13 words
The method of claim 18 , wherein the reducing agent is atomic hydrogen.
Claim 22
Independent Claim
92 words
A method of producing a conductive TaN diffusion barrier layer on a substrate comprising integrated circuits, said method comprising: introducing the substrate into the reaction space of a reactor; and growing a conductive metal nitride thin layer on the substrate by an atomic layer deposition (ALD) process comprising alternate surface reactions of tantalum and nitrogen source materials, wherein the nitrogen source comprises a compound having such a hydrocarbon, amino or silyl group attached to the nitrogen and wherein dissociation of the hydrocarbon, amino or silyl group from the nitrogen generates a radical.
Claim 23
Independent Claim
92 words
A method of producing a conductive TaN diffusion barrier layer on a substrate comprising integrated circuits, said method comprising: introducing the substrate into the reaction space of a reactor; and growing a conductive metal nitride thin layer on the substrate by an atomic layer deposition (ALD) process comprising alternate surface reactions of tantalum and nitrogen source materials, wherein the nitrogen source comprises a compound having such a hydrocarbon, amino or silyl group attached to the nitrogen and wherein dissociation of the hydrocarbon, amino or silyl group from the nitrogen generates a radical.
Claim 24
Dependent Claim
14 words
The method of claim 20 , wherein the radical serves as a reducing agent.
Claim 25
Dependent Claim
16 words
The method of claim 20 , wherein the radical reacts further and generates a second radical.
Claim 26
Dependent Claim
14 words
The method of claim 20 , wherein the radical reacts further and atomic hydrogen.
Claim 27
Dependent Claim
44 words
The method of claim 20 , wherein the tantalum source material is selected from the group consisting of tantalum pentachloride, tantalum pentaiodide and tantalum pentabromide and the nitrogen source material comprises a compound selected from the group consisting of tert-butyl amine and allyl amine.
Claim 28
Dependent Claim
14 words
The method of claim 24 , wherein the nitrogen source material additionally comprises ammonia.
Claim 29
Dependent Claim
16 words
The method of claim 16 , wherein growing comprises lining trenches and vias in the substrate.
Claim 30
Dependent Claim
14 words
The method of claim 16 , which is part of a dual damascence process.
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