US6576053B1
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Method of forming thin film using atomic layer deposition method
Assignee: Samsung Electronics Co Ltd
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Filing: 2000-10-06
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Granted: 2003-06-10
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Expires: 2020-10-06
Abstract
Abstract In a method of forming a thin film using an atomic layer deposition (ALD) method, a thin film is formed on a substrate in cycles. Each cycle includes injecting a first reactant including an atom that forms the thin film and a ligand into a reaction chamber that includes the substrate, purging the first reactant, injecting a second reactant into the reaction chamber, and purging the second reactant. The thin film is formed by a chemical reaction between the atom that forms the thin film and a second reactant whose binding energy with respect to the atom that forms the thin film is larger than the binding energy of the ligand with respect to the atom that forms the thin film and the generation of by-products is prevented. The generation of a hydroxide by-product in the thin film is suppressed by using a material that does not include a hydroxide as the second reactant, purging the second reactant, and reacting the second reactant with a third reactant that includes hydroxide. After purging the second reactant, the third reactant for removing impurities and improving the stoichiometry of the thin film is injected and purged. In this way, it is possible to obtain a thin film that does not include impurities and whose stoichiometry is excellent.
Inventors
- 👤 Yeong-kwan Kim
- 👤 Young-wook Park
- 👤 Jae-soon Lim
- 👤 Sung-Je Choi
- 👤 Sang-in Lee
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 01:01
CPC Classifications
H; H10; H10P; H10P14/00; H10P14/60; H10P14/63; H10P14/6326; H10P14/6328; H10P14/6334; H10P14/6339; C; C30; C30B; C30B25/00; C30B25/02; C30B29/00; C30B29/10; C30B29/16; C30B29/20; H10P14/69; H10P14/692; H10P14/6921; H10P14/69215; H10P14/6938; H10P14/6939; H10P14/69392; H10P14/69393; H10P14/69394; H10P14/69395; H10P14/69396; H10P14/694; H10P14/6943; H10P14/69433; H10P14/69391; H10P14/69397; H10P14/69398
Claims Analysis
Total Claims: 38
Claim 1
Independent Claim
174 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; injecting a second reactant into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products; and purging the reaction chamber with a second inert gas, after injecting the second reactant, to remove any of the second reactant that is physisorbed onto the substrate, wherein the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom.
Claim 2
Independent Claim
174 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; injecting a second reactant into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products; and purging the reaction chamber with a second inert gas, after injecting the second reactant, to remove any of the second reactant that is physisorbed onto the substrate, wherein the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom.
Claim 3
Dependent Claim
31 words
A method of forming a thin film, as recited in claim 1 , wherein the first reactant comprises Al(CH 3 ) 3 and the second reactant comprises an activated oxidizing agent.
Claim 4
Dependent Claim
23 words
A method of forming a thin film, as recited in claim 1 , wherein the first and second inert gases are the same.
Claim 5
Dependent Claim
63 words
A method of forming a thin film, as recited in claim 1 , wherein the injecting of the first reactant into the reaction chamber, the purging of the reaction chamber with a first inert gas, the injecting of the second reactant into the reaction chamber, and the purging of the reaction chamber with a second inert gas, are repeated a plurality of times.
Claim 6
Independent Claim
151 words
A method of forming a thin film using an ALD method, comprising: placing a substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemically adsorbed onto the substrate; purging the reaction chamber with a first inert gas to remove any first reactant that is only physisorbed over the substrate; injecting a second reactant into the reaction chamber to chemically exchange a first portion of the chemisorbed first reactant and to form a metal-oxygen atomic layer film; purging the reaction chamber with a second inert gas to remove any of the second reactant that is physisorbed over the substrate; and injecting a third reactant into the reaction chamber to form a metal oxide film in units of atomic layers by chemically exchanging a second portion of the chemisorbed first reactant, wherein the second reactant does not contain a hydroxide.
Claim 7
Independent Claim
151 words
A method of forming a thin film using an ALD method, comprising: placing a substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemically adsorbed onto the substrate; purging the reaction chamber with a first inert gas to remove any first reactant that is only physisorbed over the substrate; injecting a second reactant into the reaction chamber to chemically exchange a first portion of the chemisorbed first reactant and to form a metal-oxygen atomic layer film; purging the reaction chamber with a second inert gas to remove any of the second reactant that is physisorbed over the substrate; and injecting a third reactant into the reaction chamber to form a metal oxide film in units of atomic layers by chemically exchanging a second portion of the chemisorbed first reactant, wherein the second reactant does not contain a hydroxide.
Claim 8
Dependent Claim
31 words
A method of forming a thin film, as recited in claim 5 , wherein the injecting of the third reactant into the reaction chamber operates to prevent the generation of hydroxide.
Claim 9
Dependent Claim
46 words
A method of forming a thin film, as recited in claim 5 , wherein the first reactant is a metal reactant, the second reactant is N 2 O, O 2 , O 3 , or CO 2 , and the third reactant is an oxidizing gas.
Claim 10
Dependent Claim
41 words
A method of forming a thin film, as recited in claim 5 , wherein the temperature of the reaction chamber is maintained to be between 100 and 400° C. from the injecting the first reactant to the injecting the third reactant.
Claim 11
Dependent Claim
141 words
A method of forming a thin film, as recited in claim 5 , wherein the metal oxide film comprises a material selected from the group consisting of an Al 2 O 3 film, a TiO 2 film, a ZrO 2 film, an HfO 2 film, a Ta 2 O 5 film, an Nb 2 O 5 film, a CeO 2 film, a Y 2 O 3 film, an SiO 2 film, an In 2 O 3 film, an RuO 2 film, an IrO 2 film, an SrTiO 3 film, a PbTiO 3 film, an SrRuO 3 film, a CaRuO 3 film, a (Ba,Sr)TiO 3 film, a Pb(Zr,Ti)O 3 film, a (Pb,La)(Zr,Ti)O 3 film, an (Sr,Ca)RuO 3 film, a (Ba,Sr)RuO 3 film, an In 2 O 3 (ITO) film doped with Sn, and an I 2 O 3 film doped with Zr.
Claim 12
Dependent Claim
47 words
A method of forming a thin film, as recited in claim 5 , wherein a dangling bond on a surface of the substrate is terminated by injecting an oxidizing gas into the reaction chamber before injecting the first reactant, and wherein the substrate is a silicon substrate.
Claim 13
Dependent Claim
44 words
A method of forming a thin film, as recited in claim 5 , further comprising purging the reaction chamber with a third inert gas after injecting the third reactant into the reaction chamber, to remove any of the third reactant physisorbed over the substrate.
Claim 14
Dependent Claim
24 words
A method of forming a thin film, as recited in claim 11 , wherein the first, second, and third inert gases are the same.
Claim 15
Dependent Claim
84 words
A method of forming a thin film, as recited in claim 11 , wherein the injecting of the first reactant into the reaction chamber, the purging of the reaction chamber with the first inert gas, the injecting of the second reactant into the reaction chamber, the purging of the reaction chamber with the second inert gas, the injecting of the third reactant into the reaction chamber, and the purging of the reaction chamber with the third inert gas, are repeated a plurality of times.
Claim 16
Dependent Claim
48 words
A method of forming a thin film, as recited in claim 11 , further comprising injecting a fourth reactant into the reaction chamber, after purging of the reaction chamber with the third inert gas, to remove any impurities and to improve the stoichiometry of the metal oxide film.
Claim 17
Dependent Claim
20 words
A method of forming a thin film, as recited in claim 14 , wherein the fourth reactant is ozone gas.
Claim 18
Dependent Claim
24 words
A method of forming a thin film, as recited in claim 11 , wherein the first, second, and third inert gases are the same.
Claim 19
Dependent Claim
85 words
A method of forming a thin film, as recited in claim 16 , wherein the from the injecting of the first reactant into the reaction chamber, the purging of the reaction chamber with the first purge gas, the injecting of the second reactant into the reaction chamber, the purging of the reaction chamber with the second purge gas, the injecting of the third reactant into the reaction chamber, the purging of the reaction chamber with the third purge gas, are repeated a plurality of times.
Claim 20
Independent Claim
140 words
A method of forming a thin film using an ALD method, comprising: loading a substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemically adsorbed into the substrate; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed over the substrate; injecting a second reactant into the reaction chamber to form the thin film in units of atomic layers by chemically exchanging the first reactant to further contribute to the formation of the second reactant; purging the reaction chamber with a second inert gas to remove any of the second reactant that is physisorbed over the substrate; and injecting a third reactant into the reaction chamber to remove impurities and improving the stoichiometry of the thin film.
Claim 21
Independent Claim
140 words
A method of forming a thin film using an ALD method, comprising: loading a substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemically adsorbed into the substrate; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed over the substrate; injecting a second reactant into the reaction chamber to form the thin film in units of atomic layers by chemically exchanging the first reactant to further contribute to the formation of the second reactant; purging the reaction chamber with a second inert gas to remove any of the second reactant that is physisorbed over the substrate; and injecting a third reactant into the reaction chamber to remove impurities and improving the stoichiometry of the thin film.
Claim 22
Dependent Claim
30 words
A method of forming a thin film, as recited in claim 18 , wherein the first reactant comprises a metal reactant and the second and third reactants comprise oxidizing gases.
Claim 23
Dependent Claim
32 words
A method of forming a thin film, as recited in claim 18 , wherein the thin film comprises a metal oxide film formed of a single atomic oxide or a composite oxide.
Claim 24
Dependent Claim
73 words
A method of forming a thin film, as recited in claim 20 , wherein the single atomic oxide comprises a material selected from the group consisting of Al 2 O 3 , TiO 2 , Ta 2 O 5 , ZrO 2 , HfO 2 , Nb 2 O 5, CeO 2 , Y 2 O 3 , SiO 2 , In 2 O 3 , RuO 2 , and IrO 2 .
Claim 25
Dependent Claim
73 words
A method of forming a thin film, as recited in claim 20 , wherein the composite oxide comprises a material selected from the group consisting of SrTiO 3 , PbTiO 3 , SrRuO 3 , CaRuO 3 , (Ba,Sr)TiO 3 , Pb(Zr,Ti)O 3 , (Pb,La) (Zr,Ti)O 3 , (Sr,Ca)RuO 3 , In 2 O 3 doped with Sn, In 2 O 3 doped with Fe, and In 2 O 3 doped with Zr.
Claim 26
Dependent Claim
30 words
A method of forming a thin film, as recited in claim 18 , wherein the first reactant is a metal reactant and the second and third reactants are nitriding gases.
Claim 27
Dependent Claim
32 words
A method of forming a thin film, as recited in claim 18 , wherein the thin film comprises a metal nitride film formed of a single atomic nitride or a composite nitride.
Claim 28
Dependent Claim
42 words
A method of forming a thin film, as recited in claim 24 , wherein the single atomic nitride comprises a material selected from the group consisting of SiN, NbN, ZrN, TiN, TaN, Ya 3 N 5 , AIN, GaN, WN, and BN.
Claim 29
Dependent Claim
33 words
A method of forming a thin film, as recited in claim 24 , wherein the composite nitride comprises a material selected from the group consisting of WBN, WSiN, TiSiN, TaSiN, AlSiN, and AlTiN.
Claim 30
Dependent Claim
42 words
A method of forming a thin film, as recited in claim 18 , further comprising purging the reaction chamber with a third inert gas, after injecting the third reactant, to remove any of the third reactant that is physisorbed over the substrate.
Claim 31
Dependent Claim
49 words
A method of forming a thin film, as recited in claim 18 , wherein a dangling bond on a surface of the substrate is terminated by injecting oxidizing gas or nitriding gas into the reaction chamber before injecting the first reactant, and wherein the substrate is a silicon substrate.
Claim 32
Dependent Claim
43 words
A method of forming a thin film, as recited in claim 18 , wherein the temperature of the reaction chamber is maintained to be between 100 and 400° C. from the injecting of the first reactant to the injecting of the third reactant.
Claim 33
Independent Claim
160 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; and injecting a second reactant, comprising an activated oxidizing agent, into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products, wherein the activated oxidizing agent comprises O 3 and the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom.
Claim 34
Independent Claim
160 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; and injecting a second reactant, comprising an activated oxidizing agent, into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products, wherein the activated oxidizing agent comprises O 3 and the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom.
Claim 35
Independent Claim
218 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; injecting a second reactant into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products; and purging the reaction chamber with a second inert gas, after injecting the second reactant, to remove any of the second reactant that is physisorbed onto the substrate, wherein the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom, wherein the first reactant comprises Al(CH 3 ) 3 and the second reactant comprises an activated oxidizing agent, and wherein the activated oxidizing agent comprises a material selected from the group consisting of O 3 , O 2 plasma, and N 2 O plasma.
Claim 36
Independent Claim
218 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; injecting a second reactant into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products; and purging the reaction chamber with a second inert gas, after injecting the second reactant, to remove any of the second reactant that is physisorbed onto the substrate, wherein the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom, wherein the first reactant comprises Al(CH 3 ) 3 and the second reactant comprises an activated oxidizing agent, and wherein the activated oxidizing agent comprises a material selected from the group consisting of O 3 , O 2 plasma, and N 2 O plasma.
Claim 37
Independent Claim
166 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant, comprising Al(CH 3 ) 3 , into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; and injecting a second reactant, comprising an activated oxidizing agent, into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products, wherein the activated oxidizing agent comprises O 3 and the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom.
Claim 38
Independent Claim
166 words
A method of forming a thin film over a substrate using atomic layer deposition (ALD), comprising: placing the substrate into a reaction chamber; injecting a first reactant, comprising Al(CH 3 ) 3 , into the reaction chamber so that a portion of the first reactant is chemisorbed onto the substrate, the first reactant including a thin film atom and a ligand; purging the reaction chamber with a first inert gas to remove any of the first reactant that is only physisorbed onto the substrate; and injecting a second reactant, comprising an activated oxidizing agent, into the reaction chamber to form the thin film in atomic layers by a chemical reaction between the thin film atom and the second reactant, and to remove the ligand without generating by-products, wherein the activated oxidizing agent comprises O 3 and the binding energy of the second reactant with respect to the thin film atom is larger than the binding energy of the ligand with respect to the thin film atom.
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