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US6010969A
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Method of depositing films on semiconductor devices by using carboxylate complexes
Assignee: Micron Technology Inc
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Filing: 1996-10-02
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Granted: 2000-01-04
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Expires: 2016-10-02
Abstract
Abstract A method of forming a film on a substrate using chemical vapor deposition techniques and carboxylate complexes. The complexes and method are particularly suitable for the preparation of semiconductor structures.
Inventors
- 👤 Brian A. Vaartstra
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 01:08
CPC Classifications
H; H10; H10P; H10P14/00; H10P14/60; H10P14/66; H10P14/668; C; C23; C23C; C23C16/00; C23C16/22; C23C16/30; C23C16/40; C23C16/44; C23C16/448; C23C16/4486; H10P14/63; H10P14/6326; H10P14/6328; H10P14/6334; H10P14/69; H10P14/692; H10P14/6938; H10P14/6939; H10P14/69393; H10P14/69398
Claims Analysis
Total Claims: 56
Claim 1
Independent Claim
157 words
A method of manufacturing a semiconductor structure comprising: providing a semiconductor substrate or substrate assembly; providing a precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5; and vaporizing the precursor and directing it toward the semiconductor substrate or substrate assembly using a chemical vapor deposition technique to form a film on a surface of the semiconductor substrate or substrate assembly.
Claim 2
Independent Claim
157 words
A method of manufacturing a semiconductor structure comprising: providing a semiconductor substrate or substrate assembly; providing a precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5; and vaporizing the precursor and directing it toward the semiconductor substrate or substrate assembly using a chemical vapor deposition technique to form a film on a surface of the semiconductor substrate or substrate assembly.
Claim 3
Dependent Claim
17 words
The method of claim 1 wherein the precursor is vaporized in the presence of a carrier gas.
Claim 4
Dependent Claim
17 words
The method of claim 2 wherein the precursor is vaporized in the presence of a reaction gas.
Claim 5
Dependent Claim
48 words
The method of claim 3 wherein: the carrier gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof, and the reaction gas is selected from the group consisting of oxygen, nitrous oxide, ammonia, water vapor, hydrogen sulfide, hydrogen selenide, hydrogen telluride, and mixtures thereof.
Claim 6
Dependent Claim
21 words
The method of claim 4 wherein the film is a film of an oxide, sulfide, nitride, selenide, telluride, or mixture thereof.
Claim 7
Dependent Claim
17 words
The method of claim 1 wherein the film is an oxide film and forms a dielectric layer.
Claim 8
Dependent Claim
12 words
The method of claim 1 wherein the precursor is a liquid precursor.
Claim 9
Dependent Claim
20 words
The method of claim 7 wherein the chemical vapor deposition technique comprises flash vaporization, bubbling, microdroplet formation, or combinations thereof.
Claim 10
Dependent Claim
31 words
The method of claim 1 wherein M is selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, Group IVB, Group VA, Group VB, and the lanthanides.
Claim 11
Dependent Claim
13 words
The method of claim 1 wherein x=0 to 4 and z=0 to 2.
Claim 12
Dependent Claim
9 words
The method of claim 1 wherein n+=1 to 8.
Claim 13
Dependent Claim
24 words
The method of claim 1 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )organic group.
Claim 14
Dependent Claim
34 words
The method of claim 1 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 10 )organic group.
Claim 15
Dependent Claim
14 words
The method of claim 13 wherein each organic group is a heteroatom-free organic group.
Claim 16
Dependent Claim
54 words
The method of claim 1 wherein the precursor comprises a carboxylate complex of the formula (Formula III): M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n-1.
Claim 17
Dependent Claim
74 words
The method of claim 1 wherein the precursor comprises a carboxylate complex of the formula (Formula IV): M.sup.n+ (OC(O)R.sup.1).sub.u {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, and the lanthanides; each R is 1a1 or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z=1 to 5.
Claim 18
Independent Claim
173 words
A method of manufacturing a memory device structure comprising: providing a substrate having a first electrode thereon; providing a precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5; and forming a first electrode on the substrate; vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a dielectric layer comprising an oxide film on the first electrode of the substrate; and forming a second electrode on the dielectric layer.
Claim 19
Independent Claim
173 words
A method of manufacturing a memory device structure comprising: providing a substrate having a first electrode thereon; providing a precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5; and forming a first electrode on the substrate; vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a dielectric layer comprising an oxide film on the first electrode of the substrate; and forming a second electrode on the dielectric layer.
Claim 20
Dependent Claim
12 words
The method of claim 17 wherein the substrate is a silicon wafer.
Claim 21
Dependent Claim
13 words
The method of claim 17 wherein the oxide film forms a ferroelectric layer.
Claim 22
Dependent Claim
31 words
The method of claim 17 wherein M is selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, Group IVB, Group VA, Group VB, and the lanthanides.
Claim 23
Dependent Claim
21 words
The method of claim 20 wherein M is selected from the group consisting of Ba, Sr, Nb, Ta, Ti, and Bi.
Claim 24
Dependent Claim
13 words
The method of claim 17 wherein x=0 to 4 and z=0 to 2.
Claim 25
Dependent Claim
9 words
The method of claim 17 wherein n+=1 to 8.
Claim 26
Dependent Claim
24 words
The method of claim 17 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )organic group.
Claim 27
Dependent Claim
13 words
The method of claim 24 wherein each organic group is a nonaromatic group.
Claim 28
Dependent Claim
34 words
The method of claim 17 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 10 )organic group.
Claim 29
Dependent Claim
15 words
The method of claim 26 wherein each group organic group is a heteroatom-free organic group.
Claim 30
Dependent Claim
54 words
The method of claim 17 wherein the precursor comprises a carboxylate complex of the formula (Formula III): M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n-1.
Claim 31
Dependent Claim
74 words
The method of claim 17 wherein the precursor comprises a carboxylate complex of the formula (Formula IV): M.sup.n+ (OC(O)R.sup.1).sub.u {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, and the lanthanides; each R is H or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z=1 to 5.
Claim 32
Dependent Claim
22 words
The method of claim 17 wherein the precursor is a liquid precursor which is vaporized in the presence of a carrier gas.
Claim 33
Dependent Claim
17 words
The method of claim 30 wherein the precursor is vaporized in the presence of a reaction gas.
Claim 34
Dependent Claim
48 words
The method of claim 31 wherein: the carrier gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof; and the reaction gas is selected from the group consisting of oxygen, nitrous oxide, ammonia, water vapor, hydrogen sulfide, hydrogen selenide, hydrogen telluride, and mixtures thereof.
Claim 35
Independent Claim
144 words
A method of forming a film on a substrate comprising: providing a substrate; providing a precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5, and vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a film on the substrate.
Claim 36
Independent Claim
144 words
A method of forming a film on a substrate comprising: providing a substrate; providing a precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5, and vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a film on the substrate.
Claim 37
Dependent Claim
17 words
The method of claim 33 wherein the precursor is vaporized in the presence of a carrier gas.
Claim 38
Dependent Claim
17 words
The method of claim 34 wherein the precursor is vaporized in the presence of a reaction gas.
Claim 39
Dependent Claim
48 words
The method of claim 35 wherein: the carrier gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof, and the reaction gas is selected from the group consisting of oxygen, nitrous oxide, ammonia, water vapor, hydrogen sulfide, hydrogen selenide, hydrogen telluride, and mixtures thereof.
Claim 40
Dependent Claim
21 words
The method of claim 36 wherein the film is a film of an oxide, sulfide, nitride, selenide, telluride, or mixture thereof.
Claim 41
Dependent Claim
12 words
The method of claim 37 wherein the film is an oxide film.
Claim 42
Dependent Claim
18 words
The method of claim 38 wherein the oxide film forms a ferroelectric layer in a ferroelectric memory device.
Claim 43
Dependent Claim
12 words
The method of claim 33 wherein the substrate comprises a silicon substrate.
Claim 44
Dependent Claim
26 words
The method of claim 33 wherein the precursor is a liquid precursor and the step of vaporizing comprises flash vaporization, bubbling, microdroplet formation, or combinations thereof.
Claim 45
Dependent Claim
31 words
The method of claim 33 wherein M is selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, Group IVB, Group VA, Group VB, and the lanthanides.
Claim 46
Dependent Claim
13 words
The method of claim 33 wherein x=0 to 4 and z=0 to 2.
Claim 47
Dependent Claim
9 words
The method of claim 33 wherein n+=1 to 8.
Claim 48
Dependent Claim
24 words
The method of claim 33 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )organic group.
Claim 49
Dependent Claim
24 words
The method of claim 45 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )aliphatic group.
Claim 50
Dependent Claim
24 words
The method of claim 46 wherein each R 1 and R 2 group is independently H or a (C 1 -C 8 )alkyl moiety.
Claim 51
Dependent Claim
34 words
The method of claim 33 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 10 )aliphatic group.
Claim 52
Dependent Claim
34 words
The method of claim 46 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 5 )alkyl moiety.
Claim 53
Dependent Claim
54 words
The method of claim 33 wherein the precursor comprises a carboxylate complex of the formula (Formula III): M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n-1.
Claim 54
Dependent Claim
74 words
The method of claim 33 wherein the precursor comprises a carboxylate complex of the formula (Formula IV): M.sup.n+ (OC(O)R.sup.1).sub.u {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, and the lanthanides; each R is H or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z=1 to 5.
Claim 55
Independent Claim
152 words
A method of forming a film on a substrate comprising: providing a substrate; providing a liquid precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.x N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5; and generating microdroplets of the liquid precursor; vaporizing the microdroplets using a heated carrier gas; and directing the vaporized microdroplets toward the substrate to form a film on the substrate.
Claim 56
Independent Claim
152 words
A method of forming a film on a substrate comprising: providing a substrate; providing a liquid precursor comprising at least one carboxylate complex having a formula selected from the group of: M.sup.n+ (OC(O)R.sup.1).sub.u (OR.sup.2).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.w N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula I), M.sup.n+ (OC(O)R.sup.1).sub.u (O).sub.v {(R.sup.3)(R.sup.4)N[(CH.sub.2).sub.x N(R.sup.5)].sub.x (CH.sub.2).sub.y N(R.sup.6)(R.sup.7)}.sub.z (Formula II), and combinations thereof, wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n-1; w=1 to 5; x=0 to 8; y=1 to 5; z=0 to 5; and u+v=n for Formula I or u+2v=n for Formula II; with the proviso that at least one carboxylate complex has a formula wherein z=1 to 5; and generating microdroplets of the liquid precursor; vaporizing the microdroplets using a heated carrier gas; and directing the vaporized microdroplets toward the substrate to form a film on the substrate.
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