US6399208B1
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Source reagent composition and method for chemical vapor deposition formation or ZR/HF silicate gate dielectric thin films
Assignee: Advanced Technology Materials Inc
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Filing: 1999-10-07
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Granted: 2002-06-04
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Expires: 2019-10-07
Abstract
Abstract A precursor composition for forming a zirconium and/or hafnium silicate film on a substrate, e.g., by chemical vapor deposition (CVD). Illustrative precursor compositions include (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the M/Si ratio in the deposited silicate thin film. The precursor composition may contain a solvent medium, so that the composition is adapted for liquid delivery CVD, to form stable thin-film gate dielectrics for fabrication of microelectronic devices.
Inventors
- 👤 Thomas H. Baum
- 👤 Witold Paw
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 01:38
CPC Classifications
C; C23; C23C; C23C16/00; C23C16/22; C23C16/30; C23C16/40; C23C16/401; C07; C07F; C07F7/00; C07F7/003; C09; C09D; C09D1/00; H; H10; H10D; H10D64/00; H10D64/01; H10D64/013; H10D64/01302; H10D64/01332; H10D64/01336; H10D64/01342
Claims Analysis
Total Claims: 75
Claim 1
Independent Claim
457 words
A CVD precursor composition for forming a metal silicate film on a substrate, such precursor composition including a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof; (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si ratio in the deposited silicate thin film; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the second precursor silicon compound or complex is a gas at STP and wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one b-diketonate ligand, such precursor metal compound or complex further containing silicon; (g) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand comprising a formula: wherein each R′ is independently selected from the group consisting of C 4 -C 8 alkyl, halo and C 1 -C 8 haloalkyl, such precursor metal compound or complex optionally further containing silicon; (h) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (i) compatible mixtures of any two or more of the foregoing species (a)-(h).
Claim 2
Dependent Claim
457 words
A CVD precursor composition for forming a metal silicate film on a substrate, such precursor composition including a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof; (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si ratio in the deposited silicate thin film; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the second precursor silicon compound or complex is a gas at STP and wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one b-diketonate ligand, such precursor metal compound or complex further containing silicon; (g) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand comprising a formula: wherein each R′ is independently selected from the group consisting of C 4 -C 8 alkyl, halo and C 1 -C 8 haloalkyl, such precursor metal compound or complex optionally further containing silicon; (h) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (i) compatible mixtures of any two or more of the foregoing species (a)-(h).
Claim 3
Dependent Claim
13 words
The CVD precursor composition of claim 1 , further comprising a solvent medium.
Claim 4
Dependent Claim
43 words
The CVD precursor composition of claim 2 , wherein the solvent is selected from the group consisting of ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclic ethers, and compatible combinations of two or more of the foregoing.
Claim 5
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (a).
Claim 6
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (b).
Claim 7
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (c).
Claim 8
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (d).
Claim 9
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (e).
Claim 10
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (f).
Claim 11
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (g).
Claim 12
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (h).
Claim 13
Dependent Claim
13 words
The CVD precursor composition of claim 1 , comprising a source reagent (i).
Claim 14
Dependent Claim
87 words
The CVD precursor composition of claim 1 , comprising a metal β-diketonate source reagent selected from the group consisting of those of the formula: wherein: M is Zr or Hf; each R is independently selected from the group consisting of C 1 -C 8 alkyl and trialkylsilyl whose alkyl substituents are each independently selected from the group consisting of C 1 -C 8 alkyl; and each R′ is independently selected from the group consisting of C 1 -C 8 alkyl, halo and C 1 -C 8 haloalkyl.
Claim 15
Dependent Claim
12 words
The CVD precursor composition of claim 13 , wherein M is Zr.
Claim 16
Dependent Claim
12 words
The CVD precursor composition of claim 13 , wherein M is Hf.
Claim 17
Dependent Claim
29 words
The CVD precursor composition of claim 13 , wherein the source reagent comprises a β-diketonate moiety selected from the group consisting of acac, tfac, hfac, thd, tod, and fod.
Claim 18
Dependent Claim
20 words
The CVD precursor composition of claim 13 , wherein each R is t-butyl or trimethylsilyl and each R′ is t-butyl.
Claim 19
Dependent Claim
34 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises a single source compound selected from the group consisting of Zr bis(trimethylsiloxide) bis(thd), tetrakis(trimethylsiloxide) zirconium, tetrakis(trimethylsiloxide) hafnium, and Hf bis(trimethylsiloxide) bis(thd).
Claim 20
Dependent Claim
22 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises an aliphatic alcoxide of hafnium, and a Si-containing precursor.
Claim 21
Dependent Claim
17 words
The CVD precursor composition of claim 19 , wherein the Si-containing precursor comprises a silicon alcoxide ligand.
Claim 22
Dependent Claim
29 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises (1) a first metal- and silicon-containing precursor, and (2) a metal-containing/silicon-free precursor or a metal-free/silicon-containing precursor.
Claim 23
Dependent Claim
18 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises tetrakis(trimethylsiloxide) zirconium and tetrakis(t-butoxide) zirconium.
Claim 24
Dependent Claim
11 words
The CVD precursor composition of claim 22 , further comprising octane.
Claim 25
Dependent Claim
18 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises tetrakis(trimethylsiloxide) hafnium and tetrakis(t-butoxide) hafnium.
Claim 26
Dependent Claim
47 words
The CVD precursor composition of claim 1 , comprising a first source reagent containing silicon and a second source reagent containing Zr or Hf, wherein the first and second source reagents contain compatible ligands which do not undergo ligand exchange reaction under precursor vaporization and deposition conditions.
Claim 27
Dependent Claim
49 words
The CVD precursor composition of claim 1 , comprising a first source reagent containing silicon, a second source reagent containing Zr or Hf, and a solvent, wherein the first and second source reagents contain compatible ligands which do not undergo ligand exchange reaction under precursor vaporization and deposition conditions.
Claim 28
Dependent Claim
18 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises tetrakis(t-butoxy) zirconium and tetrakis(t-butoxy) silane.
Claim 29
Dependent Claim
55 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises alcoxides of Zr and/or Hf and alcoxides of Si, wherein the same alcoxide ligand species selected from the group consisting of methoxides, ethoxides, i-propoxides, t-butoxides, and trialkylsiloxides, are present in each of the alcoxides of Zr and/or Hf and alcoxides of Si.
Claim 30
Dependent Claim
41 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises metal alcoxide β-diketonate mixtures in which one of the metal alcoxide β-diketonate precursors contains silicon, and a second of the metal alcoxide β-diketonate precursors does not contain silicon.
Claim 31
Dependent Claim
42 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises a mixture of Zr(O—SiMe 3 ) 2 (thd) 2 and a silicon-free precursor selected from the group consisting of bis(alcoxide) bis(thd) zirconium, tetrakis(thd) zirconium and oxo zirconium bis(thd) dimer.
Claim 32
Dependent Claim
23 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises Zr(O—SiMe 3 ) 2 (thd) 2 and Zr(thd) 4 .
Claim 33
Dependent Claim
23 words
The CVD precursor composition of claim 1 , wherein the source reagent comprises Zr(O—SiMe 3 ) 2 (thd) 2 and [O═Zr(thd) 2 ].
Claim 34
Dependent Claim
32 words
The CVD precursor composition of claim 1 , comprising a source reagent selected from the group consisting of those of the formulae: wherein R is t-butyl or trimethylsilyl and R′ is t-butyl.
Claim 35
Dependent Claim
70 words
The CVD precursor composition of claim 1 , comprising a source reagent selected from the group consisting of those of the formulae: wherein each R is independently selected from the group consisting of methyl, ethyl, i-propyl, n-butyl and trimethylsilyl, and each R′ is independently selected from the group consisting of alkyl, halo, and haloalkyl wherein the alkyl substituent is selected from the group consisting of methyl, ethyl, i-propyl, and n-butyl.
Claim 36
Independent Claim
516 words
A method of forming a metal silicate gate dielectric film on a substrate, comprising vaporizing a precursor composition to form a precursor vapor, and contacting the precursor vapor with a substrate at elevated temperature to deposit the metal silicate gate dielectric film on the substrate, wherein the precursor composition includes a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof; (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /S 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand, such precursor metal compound or complex optionally further containing silicon; (g) the precursor metal compound or complex (d) wherein the second precursor silicon compound or complex not containing such metal M is a gas at STP and the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (h) the precursor metal compound or complex (e) not containing silicon, in combination with a second silicon-containing precursor compound or complex; (i) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (j) compatible mixtures of any two or more of the foregoing species (a)-(i).
Claim 37
Independent Claim
516 words
A method of forming a metal silicate gate dielectric film on a substrate, comprising vaporizing a precursor composition to form a precursor vapor, and contacting the precursor vapor with a substrate at elevated temperature to deposit the metal silicate gate dielectric film on the substrate, wherein the precursor composition includes a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof; (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /S 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand, such precursor metal compound or complex optionally further containing silicon; (g) the precursor metal compound or complex (d) wherein the second precursor silicon compound or complex not containing such metal M is a gas at STP and the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (h) the precursor metal compound or complex (e) not containing silicon, in combination with a second silicon-containing precursor compound or complex; (i) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (j) compatible mixtures of any two or more of the foregoing species (a)-(i).
Claim 38
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition further comprises a solvent medium.
Claim 39
Dependent Claim
44 words
The method of claim 36 , wherein the solvent medium comprises a solvent selected from the group consisting of ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclic ethers, and compatible combinations of two or more of the foregoing.
Claim 40
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (a).
Claim 41
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (b).
Claim 42
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (c).
Claim 43
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (d).
Claim 44
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (e).
Claim 45
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (f).
Claim 46
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (g).
Claim 47
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (h).
Claim 48
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (i).
Claim 49
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (i).
Claim 50
Dependent Claim
15 words
The method of claim 35 , wherein the precursor composition comprises a source reagent (j).
Claim 51
Dependent Claim
90 words
The method of claim 35 , wherein the precursor composition comprises a metal alcoxide β-diketonate source reagent selected from the group consisting of those of the formula: wherein: M is Zr or Hf; each R is independently selected from the group consisting of C 1 -C 8 alkyl and trialkylsilyl whose alkyl substituents are each independently selected from the group consisting of C 1 -C 8 alkyl; and each R′ is independently selected from the group consisting of C 1 -C 8 alkyl, halo and C 1 -C 8 haloalkyl.
Claim 52
Dependent Claim
10 words
The method of claim 49 , wherein M is Zr.
Claim 53
Dependent Claim
10 words
The method of claim 49 , wherein M is Hf.
Claim 54
Dependent Claim
27 words
The method of claim 49 , wherein the source reagent comprises a β-diketonate moiety selected from the group consisting of acac, tfac, hfac, thd, tod, and fod.
Claim 55
Dependent Claim
18 words
The method of claim 49 , wherein each R is t-butyl or trimethylsilyl and each R′ is t-butyl.
Claim 56
Dependent Claim
46 words
The method of claim 35 , wherein the precursor composition comprises a single source compound selected from the group consisting of Zr(OSiMe 3 ) 2 (thd) 2 , Zr(OSiMe 3 ) 4 , Hf(OSiMe 3 ) 4 , and Hf(OSiMe 3 ) 2 (thd) 2 .
Claim 57
Dependent Claim
20 words
The method of claim 35 , wherein the precursor composition comprises an aliphatic alcoxide of hafnium, and a Si-containing precursor.
Claim 58
Dependent Claim
15 words
The method of claim 55 , wherein the Si-containing precursor comprises a silicon alcoxide ligand.
Claim 59
Dependent Claim
27 words
The method of claim 35 , wherein the precursor composition comprises (1) a first metal- and silicon-containing precursor, and (2) a metal-containing/silicon-free precursor or a metal-free/silicon-containing precursor.
Claim 60
Dependent Claim
19 words
The method of claim 35 , wherein the precursor composition comprises Zr(OSiMe 3 ) 4 and Zr(OtBU) 4 .
Claim 61
Dependent Claim
9 words
The method of claim 58 , further comprising octane.
Claim 62
Dependent Claim
19 words
The method of claim 35 , wherein the precursor composition comprises Hf(OSiMe 3 ) 4 and Hf(O-tBu) 4 .
Claim 63
Dependent Claim
49 words
The method of claim 35 , wherein the precursor composition comprises a first source reagent containing silicon and a second source reagent containing Zr or Hf; wherein the first and second source reagents contain compatible ligands which do not undergo ligand exchange reaction under precursor vaporization and deposition conditions.
Claim 64
Dependent Claim
17 words
The method of claim 35 , wherein the precursor composition comprises Zr(O-tBu) 4 and Si(O-tBu) 4 .
Claim 65
Dependent Claim
53 words
The method of claim 35 , wherein the precursor composition comprises alcoxides of Zr and/or Hf and alcoxides of Si, wherein the same alcoxide ligand species selected from the group consisting of methoxides, ethoxides, i-propoxides, t-butoxides, and trialkylsiloxides, are present in each of the alcoxides of Zr and/or Hf and alcoxides of Si.
Claim 66
Dependent Claim
39 words
The method of claim 35 , wherein the precursor composition comprises metal alcoxide β-diketonate mixtures in which one of the metal alcoxide β-diketonate precursors contains silicon, and a second of the metal alcoxide β-diketonate precursors does not contain silicon.
Claim 67
Dependent Claim
40 words
The method of claim 35 , wherein the precursor composition comprises a mixture of Zr(OSiMe 3 ) 2 (thd) 2 , and a silicon-free precursor selected from the group consisting of Zr(alcoxide) 2 (thd) 2 , and Zr(thd) 4 .
Claim 68
Dependent Claim
21 words
The method of claim 35 , wherein the precursor composition comprises Zr(O—SiMe 3 ) 2 (thd) 2 and Zr(thd) 4 .
Claim 69
Dependent Claim
34 words
The method of claim 35 , wherein the precursor composition comprises a source reagent selected from the group consisting of those of the formulae: wherein R is t-butyl or trimethylsilyl and R′ is t-butyl.
Claim 70
Dependent Claim
72 words
The method of claim 35 , wherein the precursor composition comprises a source reagent selected from the group consisting of those of the formulae: wherein each R is independently selected from the group consisting of methyl, ethyl, i-propyl, n-butyl and trimethylsilyl, and each R′ is independently selected from the group consisting of alkyl, halo, and haloalkyl wherein the alkyl substituent is selected from the group consisting of methyl, ethyl, i-propyl, and n-butyl.
Claim 71
Dependent Claim
66 words
The method of claim 35 , wherein the precursor composition comprises incompatible metal and silicon precursors, and the step of contacting the precursor vapor with a substrate at elevated temperature to deposit on the substrate the metal silicate gate dielectric film comprises pulsed chemical vapor deposition, in which the incompatible precursors are separated both temporally and spatially to limit particle formation and undesired ligand exchange reactions.
Claim 72
Dependent Claim
474 words
A CVD precursor vapor composition for forming a metal silicate film on a substrate, such precursor vapor composition including a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof, (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand, such precursor metal compound or complex optionally farther containing silicon; (g) the precursor metal compound or complex (d) wherein the second precursor silicon compound or complex not containing such metal M is a gas at STP and the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (h) the precursor metal compound or complex (e) not containing silicon, in combination with a second silicon-containing precursor compound or complex; (i) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (j) compatible mixtures of any two or more of the foregoing species (a)-(i).
Claim 73
Dependent Claim
474 words
A CVD precursor vapor composition for forming a metal silicate film on a substrate, such precursor vapor composition including a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof, (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand, such precursor metal compound or complex optionally farther containing silicon; (g) the precursor metal compound or complex (d) wherein the second precursor silicon compound or complex not containing such metal M is a gas at STP and the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired Mx/Si1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (h) the precursor metal compound or complex (e) not containing silicon, in combination with a second silicon-containing precursor compound or complex; (i) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (j) compatible mixtures of any two or more of the foregoing species (a)-(i).
Claim 74
Dependent Claim
486 words
A metal silicate thin film deposited on a substrate via CVD from a precursor composition including a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof; (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand, such precursor metal compound or complex optionally further containing silicon; (g) the precursor metal compound or complex (d) wherein the second precursor silicon compound or complex not containing such metal M is a gas at STP and the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (h) the precursor metal compound or complex (e) not containing silicon, in combination with a second silicon-containing precursor compound or complex; (i) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (j) compatible mixtures of any two or more of the foregoing species (a)-(i).
Claim 75
Dependent Claim
486 words
A metal silicate thin film deposited on a substrate via CVD from a precursor composition including a source reagent selected from the group consisting of: (a) single source precursors for forming zirconium silicate thin films, wherein the precursor is a compound or coordinated complex containing Zr, O and Si as constituents thereof; (b) single source precursors for forming hafnium silicate thin films, wherein the precursor is a compound or coordinated complex containing Hf, O and Si as constituents thereof; (c) a precursor mixture comprising (1) a first precursor metal compound or complex including a silicon alcoxide (siloxide) ligand coordinated to a metal M, wherein M=Zr or Hf and (2) a second precursor metal compound or complex including an aliphatic alcoxide ligand coordinated to a metal M, wherein M=Zr or Hf, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (d) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex not containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (e) a precursor mixture comprising (1) a first precursor metal compound or complex including a metal M, wherein M=Zr or Hf and (2) a second precursor silicon compound or complex additionally containing such metal M, wherein the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M/Si M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (f) a precursor metal compound or complex including a metal M, wherein M=Zr or Hf, at least one alcoxide ligand and at least one β-diketonate ligand, such precursor metal compound or complex optionally further containing silicon; (g) the precursor metal compound or complex (d) wherein the second precursor silicon compound or complex not containing such metal M is a gas at STP and the relative proportions of the first and second precursors relative to one another are employed to controllably establish the desired M x /Si 1−x ratio in the deposited silicate thin film wherein x is from 0.01 to 0.99; (h) the precursor metal compound or complex (e) not containing silicon, in combination with a second silicon-containing precursor compound or complex; (i) the precursor metal compound or complex (e) further containing silicon, in combination with a second non-silicon-containing precursor metal compound or complex including a metal M, wherein M=Zr or Hf; and (j) compatible mixtures of any two or more of the foregoing species (a)-(i).
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