US20030232501A1 - Surface pre-treatment for enhancement of nucleation of high dielectric constant materials - Google Patents
Surface pre-treatment for enhancement of nucleation of high dielectric constant materials Download PDFInfo
- Publication number
- US20030232501A1 US20030232501A1 US10/302,752 US30275202A US2003232501A1 US 20030232501 A1 US20030232501 A1 US 20030232501A1 US 30275202 A US30275202 A US 30275202A US 2003232501 A1 US2003232501 A1 US 2003232501A1
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- Prior art keywords
- hafnium
- substrate
- gas
- containing gas
- forming
- Prior art date
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- 239000000463 material Substances 0.000 title claims description 23
- 238000002203 pretreatment Methods 0.000 title description 5
- 230000006911 nucleation Effects 0.000 title description 4
- 238000010899 nucleation Methods 0.000 title description 4
- 239000000758 substrate Substances 0.000 claims abstract description 148
- 239000007789 gas Substances 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 95
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 68
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004140 cleaning Methods 0.000 claims abstract description 24
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 36
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical class [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 30
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 19
- -1 hafnium silicates Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 239000001272 nitrous oxide Substances 0.000 claims description 12
- 230000003746 surface roughness Effects 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical class [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- CEPICIBPGDWCRU-UHFFFAOYSA-N [Si].[Hf] Chemical compound [Si].[Hf] CEPICIBPGDWCRU-UHFFFAOYSA-N 0.000 claims 2
- 238000004891 communication Methods 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 239000003989 dielectric material Substances 0.000 abstract description 10
- 239000010409 thin film Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 65
- 239000000523 sample Substances 0.000 description 47
- 229910000449 hafnium oxide Inorganic materials 0.000 description 24
- 235000012431 wafers Nutrition 0.000 description 14
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 235000019592 roughness Nutrition 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000033444 hydroxylation Effects 0.000 description 5
- 238000005805 hydroxylation reaction Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002470 thermal conductor Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31641—Deposition of Zirconium oxides, e.g. ZrO2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31645—Deposition of Hafnium oxides, e.g. HfO2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31608—Deposition of SiO2
- H01L21/31612—Deposition of SiO2 on a silicon body
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31616—Deposition of Al2O3
- H01L21/3162—Deposition of Al2O3 on a silicon body
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/3165—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation
- H01L21/31683—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation of metallic layers, e.g. Al deposited on the body, e.g. formation of multi-layer insulating structures
Definitions
- Embodiments of the present invention relate to the formation of thin films of high k dielectric materials over substrates for use in manufacturing semiconductor devices, flat-panel display devices, and other electronic devices. More particularly, embodiments of the present invention relate to a surface preparation treatment for the formation of thin films of high dielectric constant materials over substrates.
- High dielectric constant materials such as metal oxides
- metal oxides are one type of thin film being formed over substrates.
- Problems with current methods of forming metal oxide films over substrates include high surface roughness, high crystallinity, and/or poor nucleation of the formed metal oxide film.
- Embodiments of the present invention relate to a surface preparation treatment for the formation of thin films of high k dielectric materials over substrates.
- One embodiment of a method of forming a high k dielectric layer over a substrate includes pre-cleaning a surface of a substrate to remove native oxides, pre-treating the surface of the substrate with a hydroxylating agent, and forming a high k dielectric layer over the surface of the substrate.
- One embodiment of a method of forming a hafnium containing layer over a substrate includes introducing an acid solution to a surface of a substrate, introducing a hydrogen containing gas and an oxygen containing gas to the surface of the substrate, and forming a hafnium containing layer over the substrate.
- FIG. 1 is a flow chart of one embodiment of a method of forming a high k dielectric layer over a substrate
- FIGS. 2 A-C are schematic cross-sectional views of one embodiment of a substrate at certain stages in the method of FIG. 1.
- FIG. 3 is a schematic cross-section view of one embodiment of a single-substrate clean chamber.
- FIG. 4 is a schematic view of one embodiment of an apparatus adapted for rapid thermal processing.
- FIG. 5 is a flow chart of one embodiment of an in-situ steam generation process.
- FIG. 6 is a schematic cross sectional view of one embodiment of a chamber capable of depositing a high k dielectric layer by chemical vapor deposition.
- FIG. 7 is a general chemical structure for one embodiment of a hafnium metal organic precursor.
- FIG. 8 is a schematic top view of one embodiment of an integrated processing system.
- FIGS. 9 A- 9 B are schematic cross-sectional views of embodiments of a hafnium containing layer comprising a plurality of layers formed over a substrate.
- Embodiments of the present invention relate to the formation of high k dielectric materials over substrates.
- High k dielectric materials include hafnium containing materials, aluminum oxides, zirconium oxides, lanthanum oxides, yttrium oxides, tantalum oxides, other suitable materials, composites thereof, combinations thereof.
- Hafnium containing high k dielectric materials include hafnium oxides (e.g., HfO 2 ), hafnium silicates (e.g., HfSiO), hafnium nitrides (e.g., HfN), other suitable materials, composites thereof, and combinations thereof.
- the high k dielectric material preferably comprises hafnium oxides, hafnium silicates, composites thereof, or combinations thereof.
- Substrates include semiconductor wafers and glass substrates and may include materials formed thereover, such as dielectric materials, conductive materials, silicon layers, metal layers, etc.
- FIG. 1 is a flow chart of one embodiment of a method 100 of forming a high k dielectric layer over a substrate.
- step 110 the surface of a substrate is pre-cleaned to remove native oxides which may have formed over the surface of the substrate.
- the surface of the substrate is pre-treated with a hydroxylating agent to perform a controlled hydroxylation of the substrate.
- step 130 a high k dielectric layer is formed thereover.
- FIGS. 2 A-C are schematic cross-sectional views of one embodiment of a silicon substrate 200 at certain stages in the method 100 of FIG. 1.
- the method 100 will be described in reference to formation of a high k dielectric layer comprising a hafnium containing layer.
- FIG. 2A shows the substrate 200 after the surface of the substrate is pre-cleaned to remove native oxides which may have formed over the substrate surface. It is believed that the pre-clean leaves the surface of a substrate with a silicon-hydrogen (Si—H) surface 212 .
- FIG. 2B shows the substrate 200 after the surface of the substrate is pre-treated with a hydroxylating agent. It is believed that the hydroxylating agent converts the Si—H surface 212 of FIG. 2A into a silicon-hydroxy (Si—O—H) surface 214 .
- FIG. 2C shows the substrate 200 after a hafnium containing layer 216 , such as a hafnium oxide layer, has been formed over the surface of the substrate.
- the hafnium containing layer 216 can comprise a single layer or a plurality of layers. If the hafnium containing layer 216 is made of a plurality of layers, each layer may be a different type of hafnium containing material, the same type of hafnium containing material, or combinations thereof.
- FIG. 9A is a schematic cross-sectional view of one embodiment of a hafnium containing layer comprising a hafnium silicate material layer formed over a hafnium oxide material layer.
- FIG. 9B is a schematic cross-sectional view of one embodiment of a hafnium containing layer comprising a plurality of hafnium silicate layers. Each hafnium silicate layer may comprise the same or different proportions of hafnium, silicon, and oxygen atoms.
- an interfacial layer 215 comprising hafnium silicates is formed between the hafnium containing layer 216 and the substrate 200 . It is believed that in formation of the hafnium containing layer 216 , less energy is required to break the bonds of the Si—O—H surface 214 of FIG. 2B to form the hafnium containing layer 216 than directly breaking the bonds of the Si—H surface 212 of FIG. 2A. In addition, the extent of hydroxylation of the surface of the substrate can be controlled, as opposed to hydroxylation by the atmosphere (native oxides), and the thickness of the interfacial layer 215 can be reduced.
- a hafnium containing layer formed by the methods disclosed herein has improved film characteristics.
- the formed hafnium containing layer is amorphous and may be formed over a substrate with minimal formation of an interfacial layer 215 , such as an interfacial layer having a thickness about 13 ⁇ or less, more preferably about 6 ⁇ or less.
- the formed hafnium containing layer has improved nucleation (less islands) over a substrate surface.
- a hafnium containing layer may be formed to a surface roughness (Rms) of less than about 4 ⁇ , preferably less than about 3 ⁇ , and more preferably about 2.55 ⁇ or less.
- pre-cleaning of a substrate surface may be performed by contacting the substrate surface with a cleaning solution in a batch clean system, in a single-substrate clean system, or any other suitable clean system.
- a single-substrate clean system is an OASIS CLEANTM system available from Applied Materials, Inc. of Santa Clara, Calif.
- the cleaning solution may be a RCA-type cleaning solution or any other suitable cleaning solution which removes native oxides, which may have formed over the substrate surface, and may involve single-step chemistry or multi-step chemistries.
- the substrate surface may be contacted with the cleaning solution for a specified time period.
- FIG. 3 is a schematic cross-section view of one embodiment of a single-substrate clean chamber 300 which may be part of a multi-chamber system.
- the chamber 300 includes a platter 308 with a plurality of acoustic or sonic transducers 302 located thereon.
- the transducers 302 are attached to the bottom surface of platter 308 .
- the transducers 302 create acoustic or sonic waves directed towards the surface of a substrate 306 .
- the substrate 306 is held at a distance above the top surface of platter 308 .
- the substrate 306 is clamped by a plurality of clamps 310 face up and can rotate or spin substrate 306 about it's the substrate's central axis.
- the clamps 310 and substrate 306 are rotated during use whereas platter 308 remains in a fixed position.
- substrate 306 is placed face up and the backside of the substrate faces platter 308 , i.e., the side of the substrate with patterns or features faces towards one or more nozzles 351 which spray cleaning or etching chemicals thereon.
- deionized water (Dl water) is fed through a feed through channel 328 and platter 308 and fills the gap between the backside of substrate 306 and platter 308 to provide a water filled gap 318 through which acoustic waves generated by transducers 302 can travel to substrate 306 .
- cleaning solutions such as SC-1 and SC-2, etchants such as diluted hydrofluoric acid or buffered hydrofluoric acid, and rinsing water such as deionized water are fed through a plurality of nozzles 351 to the top surface of the substrate 306 while the substrate 306 is spun.
- Tanks 323 containing wet processing chemicals such as diluted hydrofluoric acid, de-ionized water, and cleaning solutions are coupled by conduit 354 to nozzles 351 .
- One embodiment of the step 110 (FIG. 1) of pre-cleaning the substrate surface comprises introducing a dilute hydrofluoric acid solution onto the substrate surface for a suitable time period, such as between about 5 seconds and about 1 hour or more, preferably between about 1 minute and about 15 minutes, more preferably about 2 minutes. Any suitable concentration of hydrofluoric acid may be used, preferably between about 1 weight percent and about 49 weight percent hydrofluoric acid, more preferably about 2 weight percent hydrofluoric acid. After introduction of a hydrofluoric acid solution to the substrate, the substrate surface is referred to a HF-last surface.
- one embodiment of step 120 of pre-treating the substrate surface with a hydroxylating agent comprises contacting the surface of the substrate with water vapor generated in a flash in-situ steam generation (ISSG) process.
- the hydroxylating agent be other suitable compounds.
- the pre-treatment of the present invention can be carried out in a rapid thermal heating apparatus, such as, but not limited to, the RTP XE chamber, available from Applied Materials, Inc. of Santa Clara, Calif.
- a rapid thermal heating apparatus is disclosed in U.S. Pat. No. 6,037,273, entitled “Method and Apparatus for Insitu Vapor Generation,” assigned to Applied Materials, Inc.
- FIG. 4 is a schematic view of one embodiment of an apparatus 400 adapted for rapid thermal processing.
- the apparatus 400 includes an evacuated process chamber 413 enclosed by a sidewall 414 and a bottom wall 415 .
- a radiant energy light pipe assembly 418 is positioned over and coupled to window assembly 417 .
- the radiant energy light pipe assembly 418 includes a plurality of tungsten halogen lamps 419 each mounted into a light pipe 421 . Lamps 419 are positioned to adequately cover the entire surface area of substrate 461 .
- a window assembly 417 may be disposed below the light pipe assembly 418 .
- a substrate 461 is supported inside chamber 413 by a support ring 462 which engages the substrate near its edge.
- Support ring 462 is mounted on a rotatable quartz cylinder 463 . By rotating quartz cylinder 463 , support ring 462 and wafer 461 can be caused to rotate.
- the bottom wall 415 of apparatus 400 includes a coated top surface 411 for reflecting energy onto the backside of wafer 461 . Additionally, rapid thermal heating apparatus 400 includes a plurality of fiber optic probes 470 positioned through the bottom wall 415 of apparatus 400 in order to detect the temperature of substrate 461 at a plurality of locations across its bottom surface.
- Rapid thermal heating apparatus 400 includes a gas inlet 469 formed through sidewall 414 for injecting process gas into chamber 413 to allow various processing steps to be carried out in chamber 413 .
- gas inlet 469 Coupled to gas inlet 469 are one or more gas sources.
- gas outlet 468 Positioned on the opposite side of gas inlet 469 , in sidewall 414 , is a gas outlet 468 .
- Gas outlet 468 is coupled to a vacuum source, such as a pump, to exhaust process gas from chamber 413 and to reduce the pressure in chamber 413 .
- the vacuum source maintains a desired pressure while process gas is fed into the chamber during processing.
- FIG. 5 is a flow chart of one embodiment of an ISSG process 500 .
- the ISSG process may be performed in any suitable chamber.
- the ISSG process 500 will be described in reference to substrate processing apparatus 400 as described in FIG. 4 and will be described in reference to a 200 mm diameter substrate.
- the process conditions may vary depending on the apparatus used and the size of the substrate.
- step 510 of the process 500 the substrate 461 is moved into the chamber 413 .
- the substrate 461 is generally transferred into the chamber 413 having a non-reactive gas ambient, such as a nitrogen (N 2 ) ambient, at a transfer pressure between about 1 mtorr and about 100 torr, preferably between about 1 torr and about 10 torr.
- Chamber 413 is then sealed.
- the chamber 413 may be evacuated to a pressure to remove the nitrogen ambient.
- step 520 the substrate 461 is heated or is ramped to a process temperature by applying power to lamps 419 .
- the process temperature may be any suitable temperature, such as between about 400° C. and about 1250° C., preferably between about 700° C. and about 900° C., more preferably between about 775° C. and about 825° C.
- a non-reactive gas such as helium gas or nitrogen gas, may be introduced into the chamber. It is believed that the non-reactive gas acts as a thermal conductor and helps to improve temperature uniformity.
- the non-reactive gas which is used is helium gas introduced at a flow rate between about 0.1 ⁇ m and about 10 slm, preferably about 1 slm.
- helium is a better thermal conductor than N 2 .
- one or more process gases may be introduced during the ramp.
- a hydrogen containing gas is introduced, such as a hydrogen (H 2 ) gas, at a flow rate between about 1 sccm and 20 sccm, preferably about 5 sccm.
- a hydrogen containing gas and an oxygen containing gas are introduced to the chamber 413 .
- the hydrogen containing gas and the oxygen containing gas are introduced to be reacted together to form water vapor (H 2 O) at the desired process temperature.
- the hydrogen containing gas is preferably hydrogen gas (H 2 ), but may be other hydrogen containing gases such as, but not limited to, ammonia (NH 3 ), deuterium, and hydrocarbons, such as methane (CH 4 ).
- the oxygen containing gas is preferably nitrous oxide (N 2 O), but may be other types of oxygen containing gases such as but not limited to oxygen gas (O 2 ).
- N 2 O provides a more controlled hydroxylation of the substrate surface in comparison to the use of O 2 which is more reactive than N 2 O.
- a non-reactive gas such as helium gas, nitrogen gas, or other non-reactive gases, may be introduced during step 530 . It is believed that the non-reactive gas acts as a thermal conductor to help improve temperature uniformity. In addition or alternatively, it is believed that a non-reactive acts to catalyze the in-situ steam generation process by isolating reaction fragments.
- a helium non-reactive gas is preferred over a nitrogen non-reactive gas because it is believed that the helium non-reactive gas is a better thermal conductor and better at catalyzing the ISSG process.
- the hydrogen containing gas and the oxygen containing gas may be introduced at any suitable chamber pressure, such as between about 0.1 Torr and about 200 Torr, preferably between about 1 Torr and about 20 Torr. Any concentration ratio of hydrogen containing gas and oxygen containing gas may be used. Preferably, a high ratio of oxygen containing gas to hydrogen containing gas is used.
- a process gas mixture comprising a ratio of oxygen containing gas to hydrogen containing gas is preferably between about 65:35 and about 99.9:0.1, preferably about 99.5:0.5.
- the desired process temperature causes the hydrogen containing gas and oxygen containing gas to react to form moisture or steam (H 2 O). Since rapid thermal heating apparatus 400 is a “cold wall” reactor, the only sufficiently hot surfaces in chamber 413 to initiate the reaction is the substrate 461 and support ring 462 . As such, the moisture generating reaction occurs near the surface of substrate 461 . Since it is the temperature of the substrate (and support ring) which initiates or turns “on” the moisture generation reaction, the reaction is said to be thermally controlled by the temperature of wafer 461 (and support ring 462 ). Additionally, the vapor generation reaction is said to be “surface catalyzed” because the heated surface of the substrate is necessary for the reaction to occur.
- the hydrogen containing gas and the oxygen containing gas are introduced at a process temperature for a sufficient period of time to enable the water vapor generated from the reaction of the hydrogen containing gas and the oxygen containing gas to hydroxylate the substrate surface.
- the substrate 461 will typically be held at process temperature for a time period between about 1 minute and about 1 second or less, preferably for a time period of about 10 seconds or less. Process time and temperature are generally dictated by amount of hydroxylation desired and the type and concentrations of the process gases.
- step 540 power to lamps 419 is reduced or turned off to reduce or ramp down the temperature of substrate 461 .
- a purge gas such as nitrogen gas (N 2 ) is fed into the chamber 13 to remove residual process gases. Then, the substrate 461 may be removed from the chamber 413 .
- the present invention has been described with respect to in-situ generation of a vapor of a specific reactive species, water, it is to be appreciated that the teachings of the present invention can be applied to other processes where the temperature of a substrate is used to initiate or catalyze the reaction of reactant gases to form a vapor of a reactive species near the wafer surface.
- the reactive species vapor can then be reacted with the wafer or with films formed thereon to carry out processes such as film growth.
- a reactant gas mixture comprising ammonia (NH 3 ) and oxygen (O 2 ) can be fed into a chamber and then caused to react by heating a wafer to a sufficient temperature to initiate a reaction of the gases to form an oxy-nitride surface.
- NH 3 ammonia
- O 2 oxygen
- a high k dielectric layer may be formed by chemical vapor deposition (including metal-organic chemical vapor deposition, low pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition), atomic layer deposition (ALD), physical vapor deposition, vapor phase epitaxy (VPE), other suitable deposition techniques, and combination of deposition techniques.
- chemical vapor deposition including metal-organic chemical vapor deposition, low pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, atomic layer deposition (ALD), physical vapor deposition, vapor phase epitaxy (VPE), other suitable deposition techniques, and combination of deposition techniques.
- FIG. 6 is a schematic cross sectional view of one embodiment of a chamber 600 capable of depositing a high k dielectric layer, such as hafnium containing layer, by MOCVD.
- Chamber body 610 and heated chamber lid 605 which is hingedly connected to chamber body 610 , together form a processing region 602 is bounded by showerhead 640 , substrate support 650 , and the walls of chamber body 610 .
- Substrate support 650 (shown in the raised position for processing) extends through the bottom of chamber body 610 .
- a slit valve 615 allows substrates to be transferred to and from the processing region 602 .
- a resistive heater Imbedded within substrate support 650 is a resistive heater.
- a thermocouple in thermal contact with substrate support 650 may sense the temperature of substrate support 650 to allow for temperature control of heated substrate support 650 .
- Substrate 601 is supported by the upper surface of support 650 and is heated by the resistive heaters within substrate support 650 to processing temperatures.
- process gases are introduced via conduit 673 , through central bore 630 and flow through blocker plate 637 and showerhead 640 into processing region 602 .
- Pumping passage 603 and outlet port 660 formed within chamber body 610 remove process gas and by-products of processing operations conducted within processing region 602 .
- Metal-organic CVD of hafnium oxide comprises introducing a hafnium organic precursor and introducing an oxygen containing compound to the chamber, such as chamber 600 of FIG. 6.
- a hafnium organic precursor include the compound having the structure of M(NRR′) 4 shown in FIG. 7, wherein at least one of R and R′ is as follows:
- R H, CH 3 , C 2 H 5 , C 3 H 7 , CO, NCO, alkyl, and aryl and
- R H, CH 3 , C 2 H 5 , C 3 H 7 , CO, NCO, alkyl, and aryl.
- R and R′ may or may not be the same.
- both R and R′ are an alkyl group having one to four carbon atoms, and more preferably are the same alkyl group.
- preferred hafnium organic precursors include tetrakis(diethylamido)hafnium (TDEAH) and tetrakis (dimethylamido)hafnium, and most preferably is TDEAH.
- oxygen containing compound include oxygen gas (O 2 ).
- Other oxygen containing compounds may also be used, such as ozone, H 2 O, N 2 O, atomic oxygen (i.e. oxygen plasma).
- One embodiment of a process for depositing hafnium oxide by MOCVD will be described in reference to a 200 mm diameter substrate.
- the process conditions may vary depending on the apparatus used and the size of the substrate.
- One embodiment of depositing hafnium oxide comprises flowing TDEAH onto the substrate surface at a rate between about 1 mg/min and about 50 mg/min, preferably about 7 mg/min, O 2 is flowed onto the wafer surface between about 30 sccm and about 3,000 sccm, preferably 1,000 sccm, and N 2 is flowed onto the wafer surface at a rate between about 30 sccm and about 3,000 sccm, preferably about 1,500 sccm. O 2 , N 2 and TDEAH are introduced onto the wafer surface either simultaneously, sequentially, or a combination thereof.
- the hafnium oxide layer is formed at temperatures in the range between about 225° C. and about 700° C. Preferably, the hafnium oxide layer is formed at about 485° C.
- the pressure in the deposition chamber is in the range between about 1.5 Torr and about 8 Torr, preferably about 4 Torr.
- the process may be performed for a specified time period, preferably about 60 seconds or less.
- the hafnium oxide layer formed has a thickness between about 20 ⁇ and about 50 ⁇ , preferably about 40 ⁇ or less.
- the processes in the formation of a high k dielectric layer as disclosed herein may be carried out in one or more single chamber systems, one or more mainframe systems having a plurality of chambers, and combinations thereof.
- the processes may be performed in separate processing systems or an integrated processing system.
- FIG. 8 is a schematic top view of one embodiment of an integrated system 800 capable of performing the processes disclosed herein.
- the integrated system 800 comprises a cleaning module 810 and a thermal processing/deposition mainframe system 830 .
- the cleaning module 810 is an OASIS CLEANTM system, available from Applied Materials, Inc., located in Santa Clara, Calif.
- the thermal processing/deposition mainframe system 830 is a CENTURA® system and is also commercially available from Applied Materials, Inc., located in Santa Clara, Calif.
- the particular embodiment of the system to perform the process as disclosed herein is provided to illustrate the invention and should not be used to limit the scope of the invention unless otherwise set forth in the claims.
- the cleaning module 810 generally includes one or more substrate cassettes 812 , one or more transfer robots 814 disposed in a substrate transfer region, and one or more single-substrate clean chambers 816 .
- the single-substrate clean chambers 816 may be similar to chamber described in reference to FIG. 3.
- the thermal processing/deposition mainframe system 830 generally includes load lock chambers 832 , a transfer chamber 834 , and processing chambers 836 A, 836 B, 836 C, 836 D.
- the load lock chambers 832 allow for the transfer of substrates into and out from the thermal processing/deposition mainframe system 830 while the transfer chamber 834 remains under a low pressure non-reactive environment.
- the transfer chamber includes a robot 840 having one or more blades which transfers the substrates between the load lock chambers 832 and processing chambers 836 A, 836 B, 836 C, 836 D.
- the transfer region is preferably between 1 mtorr to about 100 torr and preferably comprises a non-reactive gas ambient, such as a N 2 ambient.
- One embodiment of the integrated system 800 configured to form a high k dielectric layer comprises processing chamber 836 B adapted to perform an ISSG process as described above and a processing chamber 836 C, such as a chemical vapor deposition chamber or an atomic layer deposition chamber, adapted to deposit a high dielectric constant material, such as a hafnium containing layer.
- processing chamber 836 B adapted to perform an ISSG process as described above
- a processing chamber 836 C such as a chemical vapor deposition chamber or an atomic layer deposition chamber, adapted to deposit a high dielectric constant material, such as a hafnium containing layer.
- a processing chamber 836 C such as a chemical vapor deposition chamber or an atomic layer deposition chamber, adapted to deposit a high dielectric constant material, such as a hafnium containing layer.
- Other embodiments of the system 800 are within the scope of the present invention. For example, the position of a particular processing chamber on the system may be altered.
- Each silicon substrate comprised 200 mm diameter wafers.
- Sample 1 was pre-cleaned using a hydrofluoric acid solution to form a HF-last surface.
- a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 ⁇ over the substrate surface at a temperature of about 325° C.
- the roughness of the hafnium oxide surface of Sample 1 was measured to have a Rms (nm) of 0.580, a Ra (nm) of 0.45 and a Rmax (nm) of 10.01.
- Samples 2-5 were pre-cleaned using a hydrofluoric acid solution to form a HF-last surface. Thereafter, Samples 2-5 were pre-treated with a rapid thermal oxidation (RTO) process in an O 2 ambient.
- Sample 2 was pre-treated with a RTO process at a temperature of about 900° C. for a time period of about 10 seconds.
- Sample 3 was pre-treated with a RTO process at a temperature of about 900° C. for a time period of about 5 seconds.
- Sample 4 was pre-treated with a RTO process at a temperature of about 850° C. for a time period of about 10 seconds.
- Sample 5 was pre-treated with a RTO process at a temperature of about 850° C.
- Sample 6 was pre-cleaned using a hydrofluoric acid solution to form a HF-last surface. Thereafter, Sample 6 was pre-treated with an oxygen (O 2 ) soak. A layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 ⁇ over the substrate surface at a temperature of about 325° C. The roughness of the hafnium oxide surface of Sample 6 was measured to have a Rms (nm) of 0.714, a Ra (nm) of 0.567, and a Rmax (nm) of 6.618. Samples 6 had a higher surface roughness in comparison to Sample 1.
- Samples 7-9 were pre-treated with a high dose decoupled plasma nitridation. Thereafter, for Sample 7, a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 ⁇ over the substrate surface at a temperature of about 325° C.
- Sample 8 was cleaned using a hydrofluoric acid solution to form a HF-last surface and a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 ⁇ over the substrate surface at a temperature of about 325° C.
- Sample 9 was cleaned using a hydrofluoric acid solution to form a HF-last surface and treated with a rapid thermal oxidation process at a temperature about 900° C.
- Samples 10-12 were pre-treated with a low dose decoupled plasma nitridation process. Thereafter, for Sample 10, a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 ⁇ over the substrate surface at a temperature of about 325° C. Sample 11 was cleaned using a hydrofluoric acid solution and a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 ⁇ at a temperature of about 325° C. Sample 12 was pre-cleaned using a hydrofluoric acid solution to form a HF-last surface and treated with a rapid thermal oxidation process at a temperature of about 900° C.
- Sample 12 a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 ⁇ over the substrate surface at a temperature of about 325° C.
- the roughnesses of the hafnium oxide surface of Samples 10-12 were measured and are shown below in Table 3.
- Sample 10 had a slightly higher surface roughness in comparison to Sample 1 while Sample 11 had a slightly lower surface roughness in comparison to Sample 1 and while Sample 12 had a lower surface roughness in comparison to Sample 1.
- TABLE 3 Rms (nm) Ra (nm) Rmax (nm) Sample 10 0.593 0.470 5.521 Sample 11 0.573 4.455 4.971 Sample 12 0.266 0.210 2.773
- Samples 13-15 were pre-cleaned using a hydrofluoric acid solution to form a HF-last surface. Thereafter, Samples 13-15 were pre-treated with an ISSG process utilizing H 2 gas and N 2 O gas. Sample 13 was pre-treated in the ISSG process for a time period of about 4 seconds. Sample 14 was pre-treated in the ISSG process for a time period of about 6 seconds. Sample 15 was pre-treated in the ISSG process for a time period of about 8 seconds. A layer of hafnium oxide was deposited by MOCVD over the substrate surface to a thickness of about 40 ⁇ at a temperature of about 325° C. over each of the Samples 13-15.
Abstract
Embodiments of the present invention relate to a surface preparation treatment for the formation of thin films of high k dielectric materials over substrates. One embodiment of a method of forming a high k dielectric layer over a substrate includes pre-cleaning a surface of a substrate to remove native oxides, pre-treating the surface of the substrate with a hydroxylating agent, and forming a high k dielectric layer over the surface of the substrate. One embodiment of a method of forming a hafnium containing layer over a substrate includes introducing an acid solution to a surface of a substrate, introducing a hydrogen containing gas and an oxygen containing gas to the surface of the substrate, and forming a hafnium containing layer over the substrate.
Description
- This application claims benefit of U.S. Provisional Patent Application Serial No. 60/388,928, filed Jun. 14, 2002, which is herein incorporated by reference.
- 1. Field of the Invention
- Embodiments of the present invention relate to the formation of thin films of high k dielectric materials over substrates for use in manufacturing semiconductor devices, flat-panel display devices, and other electronic devices. More particularly, embodiments of the present invention relate to a surface preparation treatment for the formation of thin films of high dielectric constant materials over substrates.
- 2. Description of the Related Art
- In the field of semiconductor processing, flat-panel display processing or other electronic device processing, chemical vapor deposition has played an important role in forming films on substrates. As the geometries of electronic devices continue to shrink and the density of devices continues to increase, the size and aspect ratio of the features are becoming more aggressive, e.g., feature sizes of 0.07 microns and aspect ratios of 10 or greater are being considered. Accordingly, conformal deposition of materials to form these devices is becoming increasingly important.
- High dielectric constant materials, such as metal oxides, are one type of thin film being formed over substrates. Problems with current methods of forming metal oxide films over substrates include high surface roughness, high crystallinity, and/or poor nucleation of the formed metal oxide film.
- Therefore, there is a need for improved processes and apparatuses for forming high k dielectric materials over substrates.
- Embodiments of the present invention relate to a surface preparation treatment for the formation of thin films of high k dielectric materials over substrates. One embodiment of a method of forming a high k dielectric layer over a substrate includes pre-cleaning a surface of a substrate to remove native oxides, pre-treating the surface of the substrate with a hydroxylating agent, and forming a high k dielectric layer over the surface of the substrate. One embodiment of a method of forming a hafnium containing layer over a substrate includes introducing an acid solution to a surface of a substrate, introducing a hydrogen containing gas and an oxygen containing gas to the surface of the substrate, and forming a hafnium containing layer over the substrate.
- So that the manner in which the above recited features, advantages and objects of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
- It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
- FIG. 1 is a flow chart of one embodiment of a method of forming a high k dielectric layer over a substrate
- FIGS.2A-C are schematic cross-sectional views of one embodiment of a substrate at certain stages in the method of FIG. 1.
- FIG. 3 is a schematic cross-section view of one embodiment of a single-substrate clean chamber.
- FIG. 4 is a schematic view of one embodiment of an apparatus adapted for rapid thermal processing.
- FIG. 5 is a flow chart of one embodiment of an in-situ steam generation process.
- FIG. 6 is a schematic cross sectional view of one embodiment of a chamber capable of depositing a high k dielectric layer by chemical vapor deposition.
- FIG. 7 is a general chemical structure for one embodiment of a hafnium metal organic precursor.
- FIG. 8 is a schematic top view of one embodiment of an integrated processing system.
- FIGS.9A-9B are schematic cross-sectional views of embodiments of a hafnium containing layer comprising a plurality of layers formed over a substrate.
- Embodiments of the present invention relate to the formation of high k dielectric materials over substrates. High k dielectric materials include hafnium containing materials, aluminum oxides, zirconium oxides, lanthanum oxides, yttrium oxides, tantalum oxides, other suitable materials, composites thereof, combinations thereof. Hafnium containing high k dielectric materials include hafnium oxides (e.g., HfO2), hafnium silicates (e.g., HfSiO), hafnium nitrides (e.g., HfN), other suitable materials, composites thereof, and combinations thereof. The high k dielectric material preferably comprises hafnium oxides, hafnium silicates, composites thereof, or combinations thereof. Substrates include semiconductor wafers and glass substrates and may include materials formed thereover, such as dielectric materials, conductive materials, silicon layers, metal layers, etc.
- FIG. 1 is a flow chart of one embodiment of a
method 100 of forming a high k dielectric layer over a substrate. Instep 110, the surface of a substrate is pre-cleaned to remove native oxides which may have formed over the surface of the substrate. Instep 120, the surface of the substrate is pre-treated with a hydroxylating agent to perform a controlled hydroxylation of the substrate. Instep 130, a high k dielectric layer is formed thereover. - Not wishing to be bound by theory unless explicitly set forth in the claims, FIGS.2A-C are schematic cross-sectional views of one embodiment of a
silicon substrate 200 at certain stages in themethod 100 of FIG. 1. For clarity of description, themethod 100 will be described in reference to formation of a high k dielectric layer comprising a hafnium containing layer. - FIG. 2A shows the
substrate 200 after the surface of the substrate is pre-cleaned to remove native oxides which may have formed over the substrate surface. It is believed that the pre-clean leaves the surface of a substrate with a silicon-hydrogen (Si—H)surface 212. FIG. 2B shows thesubstrate 200 after the surface of the substrate is pre-treated with a hydroxylating agent. It is believed that the hydroxylating agent converts the Si—H surface 212 of FIG. 2A into a silicon-hydroxy (Si—O—H)surface 214. FIG. 2C shows thesubstrate 200 after ahafnium containing layer 216, such as a hafnium oxide layer, has been formed over the surface of the substrate. - The
hafnium containing layer 216 can comprise a single layer or a plurality of layers. If thehafnium containing layer 216 is made of a plurality of layers, each layer may be a different type of hafnium containing material, the same type of hafnium containing material, or combinations thereof. For example, FIG. 9A is a schematic cross-sectional view of one embodiment of a hafnium containing layer comprising a hafnium silicate material layer formed over a hafnium oxide material layer. In another example, FIG. 9B is a schematic cross-sectional view of one embodiment of a hafnium containing layer comprising a plurality of hafnium silicate layers. Each hafnium silicate layer may comprise the same or different proportions of hafnium, silicon, and oxygen atoms. - In reference to FIGS.2A-C, it is believed that during formation of the
hafnium containing layer 216 aninterfacial layer 215 comprising hafnium silicates is formed between thehafnium containing layer 216 and thesubstrate 200. It is believed that in formation of thehafnium containing layer 216, less energy is required to break the bonds of the Si—O—H surface 214 of FIG. 2B to form thehafnium containing layer 216 than directly breaking the bonds of the Si—H surface 212 of FIG. 2A. In addition, the extent of hydroxylation of the surface of the substrate can be controlled, as opposed to hydroxylation by the atmosphere (native oxides), and the thickness of theinterfacial layer 215 can be reduced. - It has been observed that a hafnium containing layer formed by the methods disclosed herein has improved film characteristics. The formed hafnium containing layer is amorphous and may be formed over a substrate with minimal formation of an
interfacial layer 215, such as an interfacial layer having a thickness about 13 Å or less, more preferably about 6 Å or less. In addition, the formed hafnium containing layer has improved nucleation (less islands) over a substrate surface. In certain embodiments, a hafnium containing layer may be formed to a surface roughness (Rms) of less than about 4 Å, preferably less than about 3 Å, and more preferably about 2.55 Å or less. - Pre-Clean
- Referring to step110 of FIG. 1, pre-cleaning of a substrate surface may be performed by contacting the substrate surface with a cleaning solution in a batch clean system, in a single-substrate clean system, or any other suitable clean system. One example of a single-substrate clean system is an OASIS CLEAN™ system available from Applied Materials, Inc. of Santa Clara, Calif. The cleaning solution may be a RCA-type cleaning solution or any other suitable cleaning solution which removes native oxides, which may have formed over the substrate surface, and may involve single-step chemistry or multi-step chemistries. The substrate surface may be contacted with the cleaning solution for a specified time period.
- FIG. 3 is a schematic cross-section view of one embodiment of a single-substrate
clean chamber 300 which may be part of a multi-chamber system. Thechamber 300 includes aplatter 308 with a plurality of acoustic orsonic transducers 302 located thereon. Thetransducers 302 are attached to the bottom surface ofplatter 308. Thetransducers 302 create acoustic or sonic waves directed towards the surface of asubstrate 306. - The
substrate 306 is held at a distance above the top surface ofplatter 308. Thesubstrate 306 is clamped by a plurality ofclamps 310 face up and can rotate or spinsubstrate 306 about it's the substrate's central axis. Inchamber 300, theclamps 310 andsubstrate 306 are rotated during use whereasplatter 308 remains in a fixed position. Additionally, inchamber 300,substrate 306 is placed face up and the backside of the substrate facesplatter 308, i.e., the side of the substrate with patterns or features faces towards one ormore nozzles 351 which spray cleaning or etching chemicals thereon. - During use, deionized water (Dl water) is fed through a feed through
channel 328 andplatter 308 and fills the gap between the backside ofsubstrate 306 andplatter 308 to provide a water filledgap 318 through which acoustic waves generated bytransducers 302 can travel tosubstrate 306. - Additionally during use, cleaning solutions such as SC-1 and SC-2, etchants such as diluted hydrofluoric acid or buffered hydrofluoric acid, and rinsing water such as deionized water are fed through a plurality of
nozzles 351 to the top surface of thesubstrate 306 while thesubstrate 306 is spun.Tanks 323 containing wet processing chemicals such as diluted hydrofluoric acid, de-ionized water, and cleaning solutions are coupled byconduit 354 tonozzles 351. - Other aspects and embodiments of a single-substrate clean system are disclosed in U.S. patent application Ser. No. 09/891,849, entitled “Method and Apparatus for Wafer Cleaning, filed Jun. 25, 2001 and in U.S. patent application Ser. No. 09/891,791, entitled “Wafer Spray Configurations for a Single Wafer Processing Apparatus,” filed Jun. 25, 2001, both of which are herein incorporated by reference in their entirety to the extent not inconsistent with the present disclosure.
- One embodiment of the step110 (FIG. 1) of pre-cleaning the substrate surface, which may be performed in the apparatus as described in reference to FIG. 3 or may be performed in other batch clean systems or single-substrate clean systems, comprises introducing a dilute hydrofluoric acid solution onto the substrate surface for a suitable time period, such as between about 5 seconds and about 1 hour or more, preferably between about 1 minute and about 15 minutes, more preferably about 2 minutes. Any suitable concentration of hydrofluoric acid may be used, preferably between about 1 weight percent and about 49 weight percent hydrofluoric acid, more preferably about 2 weight percent hydrofluoric acid. After introduction of a hydrofluoric acid solution to the substrate, the substrate surface is referred to a HF-last surface.
- Pre-Treatment
- Referring to FIG. 1, one embodiment of
step 120 of pre-treating the substrate surface with a hydroxylating agent comprises contacting the surface of the substrate with water vapor generated in a flash in-situ steam generation (ISSG) process. In other embodiments, the hydroxylating agent be other suitable compounds. The pre-treatment of the present invention can be carried out in a rapid thermal heating apparatus, such as, but not limited to, the RTP XE chamber, available from Applied Materials, Inc. of Santa Clara, Calif. One embodiment of a rapid thermal heating apparatus is disclosed in U.S. Pat. No. 6,037,273, entitled “Method and Apparatus for Insitu Vapor Generation,” assigned to Applied Materials, Inc. of Santa Clara, Calif., which is a Continuation-In-Part Application to U.S. patent application Ser. No. 08/893,774, both of which are incorporated by reference in their entirety to the extent not inconsistent with the present disclosure. Another suitable rapid thermal heating apparatus and its method of operation is set forth in U.S. Pat. No. 5,155,336, entitled “Rapid Thermal Heating Apparatus and Method,” filed Oct. 24, 1991, which is herein incorporated by reference in its entirety to the extent not inconsistent with the present disclosure. Additionally, other types of thermal reactors may be utilized such as the Epi or Poly Centura single wafer “cold wall” reactor by Applied Materials, Inc. of Santa Clara, Calif. - FIG. 4 is a schematic view of one embodiment of an
apparatus 400 adapted for rapid thermal processing. Theapparatus 400 includes an evacuatedprocess chamber 413 enclosed by asidewall 414 and abottom wall 415. A radiant energylight pipe assembly 418 is positioned over and coupled towindow assembly 417. The radiant energylight pipe assembly 418 includes a plurality oftungsten halogen lamps 419 each mounted into alight pipe 421.Lamps 419 are positioned to adequately cover the entire surface area ofsubstrate 461. Awindow assembly 417 may be disposed below thelight pipe assembly 418. - A
substrate 461 is supported insidechamber 413 by asupport ring 462 which engages the substrate near its edge.Support ring 462 is mounted on arotatable quartz cylinder 463. By rotatingquartz cylinder 463,support ring 462 andwafer 461 can be caused to rotate. - The
bottom wall 415 ofapparatus 400 includes a coatedtop surface 411 for reflecting energy onto the backside ofwafer 461. Additionally, rapidthermal heating apparatus 400 includes a plurality of fiber optic probes 470 positioned through thebottom wall 415 ofapparatus 400 in order to detect the temperature ofsubstrate 461 at a plurality of locations across its bottom surface. - Rapid
thermal heating apparatus 400 includes agas inlet 469 formed throughsidewall 414 for injecting process gas intochamber 413 to allow various processing steps to be carried out inchamber 413. Coupled togas inlet 469 are one or more gas sources. Positioned on the opposite side ofgas inlet 469, insidewall 414, is agas outlet 468.Gas outlet 468 is coupled to a vacuum source, such as a pump, to exhaust process gas fromchamber 413 and to reduce the pressure inchamber 413. The vacuum source maintains a desired pressure while process gas is fed into the chamber during processing. - FIG. 5 is a flow chart of one embodiment of an
ISSG process 500. The ISSG process may be performed in any suitable chamber. For clarity of description, theISSG process 500 will be described in reference tosubstrate processing apparatus 400 as described in FIG. 4 and will be described in reference to a 200 mm diameter substrate. The process conditions may vary depending on the apparatus used and the size of the substrate. - In
step 510 of theprocess 500, thesubstrate 461 is moved into thechamber 413. Thesubstrate 461 is generally transferred into thechamber 413 having a non-reactive gas ambient, such as a nitrogen (N2) ambient, at a transfer pressure between about 1 mtorr and about 100 torr, preferably between about 1 torr and about 10 torr.Chamber 413 is then sealed. Thechamber 413 may be evacuated to a pressure to remove the nitrogen ambient. - In
step 520, thesubstrate 461 is heated or is ramped to a process temperature by applying power tolamps 419. The process temperature may be any suitable temperature, such as between about 400° C. and about 1250° C., preferably between about 700° C. and about 900° C., more preferably between about 775° C. and about 825° C. During at least a portion ofstep 520, a non-reactive gas, such as helium gas or nitrogen gas, may be introduced into the chamber. It is believed that the non-reactive gas acts as a thermal conductor and helps to improve temperature uniformity. Preferably, the non-reactive gas which is used is helium gas introduced at a flow rate between about 0.1 μm and about 10 slm, preferably about 1 slm. Not wishing to be bound by theory unless explicitly set forth in the claims, it is believed that helium is a better thermal conductor than N2. In addition or alternatively, one or more process gases may be introduced during the ramp. Preferably, a hydrogen containing gas is introduced, such as a hydrogen (H2) gas, at a flow rate between about 1 sccm and 20 sccm, preferably about 5 sccm. - In
step 530, at the desired process temperature, a hydrogen containing gas and an oxygen containing gas are introduced to thechamber 413. The hydrogen containing gas and the oxygen containing gas are introduced to be reacted together to form water vapor (H2O) at the desired process temperature. The hydrogen containing gas is preferably hydrogen gas (H2), but may be other hydrogen containing gases such as, but not limited to, ammonia (NH3), deuterium, and hydrocarbons, such as methane (CH4). The oxygen containing gas is preferably nitrous oxide (N2O), but may be other types of oxygen containing gases such as but not limited to oxygen gas (O2). It is believed that N2O provides a more controlled hydroxylation of the substrate surface in comparison to the use of O2 which is more reactive than N2O. A non-reactive gas, such as helium gas, nitrogen gas, or other non-reactive gases, may be introduced duringstep 530. It is believed that the non-reactive gas acts as a thermal conductor to help improve temperature uniformity. In addition or alternatively, it is believed that a non-reactive acts to catalyze the in-situ steam generation process by isolating reaction fragments. A helium non-reactive gas is preferred over a nitrogen non-reactive gas because it is believed that the helium non-reactive gas is a better thermal conductor and better at catalyzing the ISSG process. - The hydrogen containing gas and the oxygen containing gas may be introduced at any suitable chamber pressure, such as between about 0.1 Torr and about 200 Torr, preferably between about 1 Torr and about 20 Torr. Any concentration ratio of hydrogen containing gas and oxygen containing gas may be used. Preferably, a high ratio of oxygen containing gas to hydrogen containing gas is used. For example, a process gas mixture comprising a ratio of oxygen containing gas to hydrogen containing gas is preferably between about 65:35 and about 99.9:0.1, preferably about 99.5:0.5.
- The desired process temperature causes the hydrogen containing gas and oxygen containing gas to react to form moisture or steam (H2O). Since rapid
thermal heating apparatus 400 is a “cold wall” reactor, the only sufficiently hot surfaces inchamber 413 to initiate the reaction is thesubstrate 461 andsupport ring 462. As such, the moisture generating reaction occurs near the surface ofsubstrate 461. Since it is the temperature of the substrate (and support ring) which initiates or turns “on” the moisture generation reaction, the reaction is said to be thermally controlled by the temperature of wafer 461 (and support ring 462). Additionally, the vapor generation reaction is said to be “surface catalyzed” because the heated surface of the substrate is necessary for the reaction to occur. - The hydrogen containing gas and the oxygen containing gas are introduced at a process temperature for a sufficient period of time to enable the water vapor generated from the reaction of the hydrogen containing gas and the oxygen containing gas to hydroxylate the substrate surface. The
substrate 461 will typically be held at process temperature for a time period between about 1 minute and about 1 second or less, preferably for a time period of about 10 seconds or less. Process time and temperature are generally dictated by amount of hydroxylation desired and the type and concentrations of the process gases. - In
step 540, power tolamps 419 is reduced or turned off to reduce or ramp down the temperature ofsubstrate 461. Simultaneously, a purge gas, such as nitrogen gas (N2), is fed into the chamber 13 to remove residual process gases. Then, thesubstrate 461 may be removed from thechamber 413. - Although the present invention has been described with respect to in-situ generation of a vapor of a specific reactive species, water, it is to be appreciated that the teachings of the present invention can be applied to other processes where the temperature of a substrate is used to initiate or catalyze the reaction of reactant gases to form a vapor of a reactive species near the wafer surface. The reactive species vapor can then be reacted with the wafer or with films formed thereon to carry out processes such as film growth. For example, a reactant gas mixture comprising ammonia (NH3) and oxygen (O2) can be fed into a chamber and then caused to react by heating a wafer to a sufficient temperature to initiate a reaction of the gases to form an oxy-nitride surface. High K Dielectric Layer Formation
- Referring to step130 of FIG. 1, a high k dielectric layer may be formed by chemical vapor deposition (including metal-organic chemical vapor deposition, low pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition), atomic layer deposition (ALD), physical vapor deposition, vapor phase epitaxy (VPE), other suitable deposition techniques, and combination of deposition techniques.
- One embodiment of a chamber capable to deposit a high k dielectric layer by MOCVD is disclosed in U.S. patent application Ser. No. 09/179,921, which is incorporated by reference in its entirety to the extent not inconsistent with the present disclosure.
- FIG. 6 is a schematic cross sectional view of one embodiment of a
chamber 600 capable of depositing a high k dielectric layer, such as hafnium containing layer, by MOCVD.Chamber body 610 andheated chamber lid 605, which is hingedly connected tochamber body 610, together form aprocessing region 602 is bounded byshowerhead 640,substrate support 650, and the walls ofchamber body 610. Substrate support 650 (shown in the raised position for processing) extends through the bottom ofchamber body 610. Aslit valve 615 allows substrates to be transferred to and from theprocessing region 602. - Imbedded within
substrate support 650 is a resistive heater. A thermocouple in thermal contact withsubstrate support 650 may sense the temperature ofsubstrate support 650 to allow for temperature control ofheated substrate support 650.Substrate 601 is supported by the upper surface ofsupport 650 and is heated by the resistive heaters withinsubstrate support 650 to processing temperatures. - Turning now to gas delivery features of
chamber 600, process gases are introduced viaconduit 673, throughcentral bore 630 and flow throughblocker plate 637 andshowerhead 640 intoprocessing region 602. Pumpingpassage 603 andoutlet port 660 formed withinchamber body 610 remove process gas and by-products of processing operations conducted withinprocessing region 602. - For illustration purposes, deposition of a high k dielectric layer will be described in reference to MOCVD of a hafnium oxide layer. Metal-organic CVD of hafnium oxide comprises introducing a hafnium organic precursor and introducing an oxygen containing compound to the chamber, such as
chamber 600 of FIG. 6. Examples of a hafnium organic precursor include the compound having the structure of M(NRR′)4 shown in FIG. 7, wherein at least one of R and R′ is as follows: - R=H, CH3, C2H5, C3H7, CO, NCO, alkyl, and aryl and
- R=H, CH3, C2H5, C3H7, CO, NCO, alkyl, and aryl.
- R and R′ may or may not be the same. Preferably, both R and R′ are an alkyl group having one to four carbon atoms, and more preferably are the same alkyl group. Examples of preferred hafnium organic precursors include tetrakis(diethylamido)hafnium (TDEAH) and tetrakis (dimethylamido)hafnium, and most preferably is TDEAH. Examples of an oxygen containing compound include oxygen gas (O2). Other oxygen containing compounds may also be used, such as ozone, H2O, N2O, atomic oxygen (i.e. oxygen plasma).
- One embodiment of a process for depositing hafnium oxide by MOCVD will be described in reference to a 200 mm diameter substrate. The process conditions may vary depending on the apparatus used and the size of the substrate. One embodiment of depositing hafnium oxide comprises flowing TDEAH onto the substrate surface at a rate between about 1 mg/min and about 50 mg/min, preferably about 7 mg/min, O2 is flowed onto the wafer surface between about 30 sccm and about 3,000 sccm, preferably 1,000 sccm, and N2 is flowed onto the wafer surface at a rate between about 30 sccm and about 3,000 sccm, preferably about 1,500 sccm. O2, N2 and TDEAH are introduced onto the wafer surface either simultaneously, sequentially, or a combination thereof.
- The hafnium oxide layer is formed at temperatures in the range between about 225° C. and about 700° C. Preferably, the hafnium oxide layer is formed at about 485° C. The pressure in the deposition chamber is in the range between about 1.5 Torr and about 8 Torr, preferably about 4 Torr. The process may be performed for a specified time period, preferably about 60 seconds or less. Preferably, the hafnium oxide layer formed has a thickness between about 20 Å and about 50 Å, preferably about 40 Å or less.
- Processing System
- The processes in the formation of a high k dielectric layer as disclosed herein may be carried out in one or more single chamber systems, one or more mainframe systems having a plurality of chambers, and combinations thereof. The processes may be performed in separate processing systems or an integrated processing system.
- FIG. 8 is a schematic top view of one embodiment of an
integrated system 800 capable of performing the processes disclosed herein. Theintegrated system 800 comprises acleaning module 810 and a thermal processing/deposition mainframe system 830. As shown in the figure, thecleaning module 810 is an OASIS CLEAN™ system, available from Applied Materials, Inc., located in Santa Clara, Calif. The thermal processing/deposition mainframe system 830 is a CENTURA® system and is also commercially available from Applied Materials, Inc., located in Santa Clara, Calif. The particular embodiment of the system to perform the process as disclosed herein is provided to illustrate the invention and should not be used to limit the scope of the invention unless otherwise set forth in the claims. - The
cleaning module 810 generally includes one ormore substrate cassettes 812, one ormore transfer robots 814 disposed in a substrate transfer region, and one or more single-substrateclean chambers 816. The single-substrateclean chambers 816 may be similar to chamber described in reference to FIG. 3. - The thermal processing/
deposition mainframe system 830 generally includesload lock chambers 832, atransfer chamber 834, andprocessing chambers load lock chambers 832 allow for the transfer of substrates into and out from the thermal processing/deposition mainframe system 830 while thetransfer chamber 834 remains under a low pressure non-reactive environment. The transfer chamber includes arobot 840 having one or more blades which transfers the substrates between theload lock chambers 832 andprocessing chambers processing chambers deposition mainframe system 830 if not necessary for the particular process to be performed by thesystem 830. The transfer region is preferably between 1 mtorr to about 100 torr and preferably comprises a non-reactive gas ambient, such as a N2 ambient. - It is believed that it is advantageous to perform the pre-treatment step120 (FIG. 1) and the high k dielectric layer formation 130 (FIG. 1) on a mainframe system to reduce the formation of native oxides and/or contamination of the pre-treated surface of a substrate prior to formation of the high k dielectric layer. Exposing the substrate to air between the
pre-treatment step 120 and the high kdielectric layer formation 130 may reduce the effectiveness of nucleation thereover of high k dielectric materials. It is optional to have thecleaning module 810 coupled withmainframe system 830 as shown in FIG. 8 to further reduce the formation of native oxides over and/or contamination of substrates between cleaning steps and other processing steps. Of course, I n other embodiments, cleaning steps may be performed in a cleaning module separate from the thermal processing/deposition mainframe system. - One embodiment of the
integrated system 800 configured to form a high k dielectric layer comprisesprocessing chamber 836B adapted to perform an ISSG process as described above and aprocessing chamber 836C, such as a chemical vapor deposition chamber or an atomic layer deposition chamber, adapted to deposit a high dielectric constant material, such as a hafnium containing layer. Other embodiments of thesystem 800 are within the scope of the present invention. For example, the position of a particular processing chamber on the system may be altered. - Various samples of silicon substrates were processed. Each silicon substrate comprised 200 mm diameter wafers.
-
Sample 1 was pre-cleaned using a hydrofluoric acid solution to form a HF-last surface. A layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 Å over the substrate surface at a temperature of about 325° C. The roughness of the hafnium oxide surface ofSample 1 was measured to have a Rms (nm) of 0.580, a Ra (nm) of 0.45 and a Rmax (nm) of 10.01. - Samples 2-5 were pre-cleaned using a hydrofluoric acid solution to form a HF-last surface. Thereafter, Samples 2-5 were pre-treated with a rapid thermal oxidation (RTO) process in an O2 ambient.
Sample 2 was pre-treated with a RTO process at a temperature of about 900° C. for a time period of about 10 seconds. Sample 3 was pre-treated with a RTO process at a temperature of about 900° C. for a time period of about 5 seconds. Sample 4 was pre-treated with a RTO process at a temperature of about 850° C. for a time period of about 10 seconds. Sample 5 was pre-treated with a RTO process at a temperature of about 850° C. for a time period of about 5 seconds. A layer of hafnium oxide was deposited by MOCVD over the substrate surface to a thickness of about 40 Å at a temperature of about 325° C. over each of the Samples 2-5. The roughnesses of the hafnium oxide surfaces of Samples 2-5 were measured and are shown below in Table 1. Samples 2-5 had lower surface roughnesses in comparison toSample 1.TABLE 1 Rms (nm) Ra (nm) Rmax (nm) Sample 20.386 0.306 3.724 Sample 3 0.387 0.307 3.812 Sample 4 0.394 0.313 3.678 Sample 5 0.393 0.311 3.882 - Sample 6 was pre-cleaned using a hydrofluoric acid solution to form a HF-last surface. Thereafter, Sample 6 was pre-treated with an oxygen (O2) soak. A layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 Å over the substrate surface at a temperature of about 325° C. The roughness of the hafnium oxide surface of Sample 6 was measured to have a Rms (nm) of 0.714, a Ra (nm) of 0.567, and a Rmax (nm) of 6.618. Samples 6 had a higher surface roughness in comparison to
Sample 1. - Samples 7-9 were pre-treated with a high dose decoupled plasma nitridation. Thereafter, for Sample 7, a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 Å over the substrate surface at a temperature of about 325° C. Sample 8 was cleaned using a hydrofluoric acid solution to form a HF-last surface and a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 Å over the substrate surface at a temperature of about 325° C. Sample 9 was cleaned using a hydrofluoric acid solution to form a HF-last surface and treated with a rapid thermal oxidation process at a temperature about 900° C. The roughnesses of the surfaces of the Samples 7-9 were measured and are shown in Table 2. Note that a layer of hafnium oxide was not deposited over Sample 9. Sample 7 had a slightly higher surface roughness in comparison to
Sample 1 while Sample 8 had a slightly lower surface roughness in comparison toSample 1.TABLE 2 Rms (nm) Ra (nm) Rmax (nm) Sample 7 0.611 0.483 5.439 Sample 8 0.539 0.425 4.899 Sample 9 0.265 0.209 2.680 - Samples 10-12 were pre-treated with a low dose decoupled plasma nitridation process. Thereafter, for
Sample 10, a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 Å over the substrate surface at a temperature of about 325° C. Sample 11 was cleaned using a hydrofluoric acid solution and a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 Å at a temperature of about 325° C. Sample 12 was pre-cleaned using a hydrofluoric acid solution to form a HF-last surface and treated with a rapid thermal oxidation process at a temperature of about 900° C. Then, for Sample 12, a layer of hafnium oxide was deposited by MOCVD to a thickness of about 40 Å over the substrate surface at a temperature of about 325° C. The roughnesses of the hafnium oxide surface of Samples 10-12 were measured and are shown below in Table 3.Sample 10 had a slightly higher surface roughness in comparison toSample 1 while Sample 11 had a slightly lower surface roughness in comparison toSample 1 and while Sample 12 had a lower surface roughness in comparison toSample 1.TABLE 3 Rms (nm) Ra (nm) Rmax (nm) Sample 100.593 0.470 5.521 Sample 11 0.573 4.455 4.971 Sample 12 0.266 0.210 2.773 - Samples 13-15 were pre-cleaned using a hydrofluoric acid solution to form a HF-last surface. Thereafter, Samples 13-15 were pre-treated with an ISSG process utilizing H2 gas and N2O gas. Sample 13 was pre-treated in the ISSG process for a time period of about 4 seconds. Sample 14 was pre-treated in the ISSG process for a time period of about 6 seconds. Sample 15 was pre-treated in the ISSG process for a time period of about 8 seconds. A layer of hafnium oxide was deposited by MOCVD over the substrate surface to a thickness of about 40 Å at a temperature of about 325° C. over each of the Samples 13-15. The roughnesses of the hafnium oxide surface of Samples 13-15 were measured and are shown below in Table 4. Samples 13-15 had much lower surface roughnesses in comparison to
Sample 1.TABLE 4 Rms (nm) Ra (nm) Rmax (nm) Sample 13 0.255 0.201 2.688 Sample 14 0.262 0.206 2.654 Sample 15 0.260 0.204 2.498 - While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (41)
1. A method of forming a high dielectric constant layer over a substrate, comprising:
pre-cleaning a surface of a substrate to remove native oxides;
pre-treating the surface of the substrate with an hydroxylating agent; and
forming a high dielectric constant layer over the surface of the substrate.
2. The method of claim 1 , wherein pre-cleaning comprises introducing an acid solution to the surface of the substrate.
3. The method of claim 2 , wherein the acid solution comprises a hydrofluoric acid solution.
4. The method of claim 1 , wherein the hydroxylating agent comprises water vapor.
5. The method of claim 4 , wherein a water vapor is generated from a hydrogen containing gas and an oxygen containing gas.
6. The method of claim 5 , wherein the hydrogen containing gas is hydrogen (H2) gas and wherein the oxygen containing gas is nitrous oxide (N2O) gas.
7. The method of claim 1 , wherein the high dielectric constant layer comprises a material selected from the group including hafnium containing materials, aluminum oxides, zirconium oxides, lanthanum oxides, yttrium oxides, tantalum oxides, composites thereof, and combinations thereof.
8. The method of claim 1 , wherein the high dielectric constant layer comprises a material selected from the group including hafnium oxides, hafnium silicates, hafnium nitrides, hafnium aluminates, hafnium silicon oxynitrides, composites thereof, and combinations thereof.
9. The method of claim 1 , wherein the high dielectric constant layer comprises hafnium oxides, compositions thereof, or combinations thereof.
10. The method of claim 1 , wherein the high dielectric constant layer comprises hafnium silicates, composites thereof, or combinations thereof.
11. The method of claim 1 , wherein forming the high dielectric constant layer comprises introducing a metal precursor and an oxygen containing compound.
12. The method of claim 1 , wherein forming the high dielectric constant layer comprises a deposition technique selected from the group comprising chemical vapor deposition, atomic layer deposition, and physical vapor deposition.
13. A method of forming a hafnium containing layer over a substrate, comprising:
introducing an acid solution to a surface of a substrate;
introducing a hydrogen containing gas and an oxygen containing gas to the surface of the substrate; and
forming a hafnium containing layer over the substrate.
14. The method of claim 13 , wherein the hafnium containing layer comprises a material selected from the group including hafnium oxides, hafnium silicates, hafnium nitrides, hafnium aluminates, hafnium silicon oxynitrides, composites thereof, and combinations thereof.
15. The method of claim 13 , wherein the hafnium containing layer comprises hafnium oxides, composites thereof, or combinations thereof.
16. The method of claim 13 , wherein the hafnium containing layer comprises hafnium silicates, composites thereof, or combinations thereof.
17. The method of claim 13 , wherein the acid solution comprises a hydrofluoric acid solution.
18. The method of claim 13 , wherein the hydrogen containing gas is hydrogen (H2) gas and wherein the oxygen containing gas is nitrous oxide (N2O) gas.
19. The method of claim 13 , wherein the ratio of oxygen containing gas to hydrogen containing gas is between about 65:35 and about 99.9:0.1.
20. The method of claim 13 , further comprising introducing a non-reactive gas during the step of introducing a hydrogen containing gas and an oxygen containing gas.
21. The method of claim 20 , wherein the non-reactive gas comprises helium gas.
22. The method of claim 13 , wherein the substrate is at a temperature between about 400° C. and about 1,250° C. during the step of introducing a hydrogen containing gas and an oxygen containing gas.
23. The method of claim 13 , wherein the substrate is at a temperature between about 700° C. and about 900° C. during the step of introducing a hydrogen containing gas and an oxygen containing gas.
24. The method of claim 13 , wherein the hydrogen containing gas and the oxygen containing gas are introduced to the surface of the substrate for a time period of about 1 minute or less.
25. The method of claim 13 , wherein the hydrogen containing gas and the oxygen containing gas are introduced to the surface of the substrate for a time period of about 10 seconds or less.
26. The method of claim 13 , wherein forming a hafnium containing layer comprises introducing a hafnium precursor and an oxygen containing compound.
27. A structure, comprising:
a substrate;
an interfacial layer formed over the substrate, the interfacial layer having a thickness of about 13 Å or less; and
one or more hafnium containing layers formed over the interfacial layer.
28. The structure of claim 27 , wherein the interfacial layer has a thickness of about 6 Å or less.
29. The structure of claim 27 , wherein the hafnium containing layer is amorphous.
30. The structure of claim 27 , wherein the hafnium containing layer has a surface roughness (Rms) of about 0.4 nm or less.
31. The structure of claim 27 , wherein the hafnium containing layer has a surface roughness (Rms) of about 0.3 nm or less.
32. The structure of claim 27 , wherein the one or more hafnium containing layers are formed to a combined thickness of about 50 Å or less.
33. The structure of claim 27 , wherein the hafnium containing layer is formed to a thickness of about 40 Å or less.
34. An integrated system for forming a hafnium containing high dielectric constant layer over a substrate, comprising:
one or more rapid thermal processing chambers adapted to generate steam by introducing a hydrogen containing gas and an oxygen containing gas;
one or more deposition chambers adapted to deposit a hafnium containing layer;
a transfer chamber in communication with the rapid thermal processing chambers and the deposition chambers; and
one or more load lock chambers.
35. The system of claim 34 , wherein the rapid thermal processing chambers are adapted to introducing hydrogen (H2) gas and nitrous oxide (N2O) gas to generate steam.
36. The system of claim 34 , wherein the deposition chambers are adapted to form a hafnium containing layer by introducing a hafnium precursor and an oxygen containing gas.
37. The system of claim 34 , further comprising a cleaning module in communication with the load lock chambers.
38. The system of claim 37 , wherein the cleaning module comprises one or more single-substrate clean chambers.
39. A method of forming a hafnium containing layer on a substrate, comprising:
remove native oxides from a surface of the substrate;
hydroxylating the surface of the substrate to form a hydroxylated surface; and
forming a hafnium containing layer over the hydroxylated surface.
40. The method of claim 39 , wherein forming a hafnium containing layer comprises forming an interfacial layer to a thickness of about 13 Å or less.
41. The method of claim 39 , wherein forming a hafnium containing layer comprises forming an interfacial layer to a thickness of about 6 Å or less.
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US12/794,047 US8071167B2 (en) | 2002-06-14 | 2010-06-04 | Surface pre-treatment for enhancement of nucleation of high dielectric constant materials |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4693208A (en) * | 1985-07-15 | 1987-09-15 | Dainippon Screen Mfg. Co., Ltd. | Feeder of oxygen gas containing steam |
US5290609A (en) * | 1991-03-25 | 1994-03-01 | Tokyo Electron Limited | Method of forming dielectric film for semiconductor devices |
US5521126A (en) * | 1993-06-25 | 1996-05-28 | Nec Corporation | Method of fabricating semiconductor devices |
US5807792A (en) * | 1996-12-18 | 1998-09-15 | Siemens Aktiengesellschaft | Uniform distribution of reactants in a device layer |
US5916365A (en) * | 1996-08-16 | 1999-06-29 | Sherman; Arthur | Sequential chemical vapor deposition |
US6013553A (en) * | 1997-07-24 | 2000-01-11 | Texas Instruments Incorporated | Zirconium and/or hafnium oxynitride gate dielectric |
US6020024A (en) * | 1997-08-04 | 2000-02-01 | Motorola, Inc. | Method for forming high dielectric constant metal oxides |
US6025627A (en) * | 1998-05-29 | 2000-02-15 | Micron Technology, Inc. | Alternate method and structure for improved floating gate tunneling devices |
US6060755A (en) * | 1999-07-19 | 2000-05-09 | Sharp Laboratories Of America, Inc. | Aluminum-doped zirconium dielectric film transistor structure and deposition method for same |
US6174809B1 (en) * | 1997-12-31 | 2001-01-16 | Samsung Electronics, Co., Ltd. | Method for forming metal layer using atomic layer deposition |
US6200893B1 (en) * | 1999-03-11 | 2001-03-13 | Genus, Inc | Radical-assisted sequential CVD |
US6203613B1 (en) * | 1999-10-19 | 2001-03-20 | International Business Machines Corporation | Atomic layer deposition with nitrate containing precursors |
US6207487B1 (en) * | 1998-10-13 | 2001-03-27 | Samsung Electronics Co., Ltd. | Method for forming dielectric film of capacitor having different thicknesses partly |
US20010000866A1 (en) * | 1999-03-11 | 2001-05-10 | Ofer Sneh | Apparatus and concept for minimizing parasitic chemical vapor deposition during atomic layer deposition |
US6238734B1 (en) * | 1999-07-08 | 2001-05-29 | Air Products And Chemicals, Inc. | Liquid precursor mixtures for deposition of multicomponent metal containing materials |
US20010009695A1 (en) * | 2000-01-18 | 2001-07-26 | Saanila Ville Antero | Process for growing metalloid thin films |
US6270572B1 (en) * | 1998-08-07 | 2001-08-07 | Samsung Electronics Co., Ltd. | Method for manufacturing thin film using atomic layer deposition |
US20020000598A1 (en) * | 1999-12-08 | 2002-01-03 | Sang-Bom Kang | Semiconductor devices having metal layers as barrier layers on upper or lower electrodes of capacitors |
US20020005556A1 (en) * | 1999-10-06 | 2002-01-17 | Eduard Albert Cartier | Silicate gate dielectric |
US20020008297A1 (en) * | 2000-06-28 | 2002-01-24 | Dae-Gyu Park | Gate structure and method for manufacture thereof |
US6342277B1 (en) * | 1996-08-16 | 2002-01-29 | Licensee For Microelectronics: Asm America, Inc. | Sequential chemical vapor deposition |
US20020014647A1 (en) * | 2000-07-07 | 2002-02-07 | Infineon Technologies Ag | Trench capacitor with isolation collar and corresponding method of production |
US20020015790A1 (en) * | 1999-10-07 | 2002-02-07 | Advanced Technology Materials Inc. | Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same |
US6348420B1 (en) * | 1999-12-23 | 2002-02-19 | Asm America, Inc. | Situ dielectric stacks |
US6348386B1 (en) * | 2001-04-16 | 2002-02-19 | Motorola, Inc. | Method for making a hafnium-based insulating film |
US20020029092A1 (en) * | 1998-09-21 | 2002-03-07 | Baltes Gass | Process tool and process system for processing a workpiece |
US6372598B2 (en) * | 1998-06-16 | 2002-04-16 | Samsung Electronics Co., Ltd. | Method of forming selective metal layer and method of forming capacitor and filling contact hole using the same |
US20020043666A1 (en) * | 2000-07-20 | 2002-04-18 | Parsons Gregory N. | High dielectric constant metal silicates formed by controlled metal-surface reactions |
US20020047151A1 (en) * | 2000-10-19 | 2002-04-25 | Kim Yeong-Kwan | Semiconductor device having thin film formed by atomic layer deposition and method for fabricating the same |
US6391785B1 (en) * | 1999-08-24 | 2002-05-21 | Interuniversitair Microelektronica Centrum (Imec) | Method for bottomless deposition of barrier layers in integrated circuit metallization schemes |
US6391803B1 (en) * | 2001-06-20 | 2002-05-21 | Samsung Electronics Co., Ltd. | Method of forming silicon containing thin films by atomic layer deposition utilizing trisdimethylaminosilane |
US6395650B1 (en) * | 2000-10-23 | 2002-05-28 | International Business Machines Corporation | Methods for forming metal oxide layers with enhanced purity |
US20020064970A1 (en) * | 2000-11-30 | 2002-05-30 | Chartered Semiconductor Manufacturing Inc. | Method to form zirconium oxide and hafnium oxide for high dielectric constant materials |
US6399491B2 (en) * | 2000-04-20 | 2002-06-04 | Samsung Electronics Co., Ltd. | Method of manufacturing a barrier metal layer using atomic layer deposition |
US6399208B1 (en) * | 1999-10-07 | 2002-06-04 | Advanced Technology Materials Inc. | Source reagent composition and method for chemical vapor deposition formation or ZR/HF silicate gate dielectric thin films |
US20020074588A1 (en) * | 2000-12-20 | 2002-06-20 | Kyu-Mann Lee | Ferroelectric capacitors for integrated circuit memory devices and methods of manufacturing same |
US20020076837A1 (en) * | 2000-11-30 | 2002-06-20 | Juha Hujanen | Thin films for magnetic device |
US20020076831A1 (en) * | 1999-12-28 | 2002-06-20 | Taizo Akimoto | Test piece, analysis method using the test piece, and analysis system used for the method |
US20020081826A1 (en) * | 2000-12-21 | 2002-06-27 | Rotondaro Antonio L. P. | Annealing of high-K dielectric materials |
US20020086111A1 (en) * | 2001-01-03 | 2002-07-04 | Byun Jeong Soo | Method of forming refractory metal nitride layers using chemisorption techniques |
US6416577B1 (en) * | 1997-12-09 | 2002-07-09 | Asm Microchemistry Ltd. | Method for coating inner surfaces of equipment |
US6420279B1 (en) * | 2001-06-28 | 2002-07-16 | Sharp Laboratories Of America, Inc. | Methods of using atomic layer deposition to deposit a high dielectric constant material on a substrate |
US20020093781A1 (en) * | 1999-05-12 | 2002-07-18 | Harald Bachhofer | Capacitor for semiconductor configuration and method for fabricating a dielectric layer therefor |
US20020093046A1 (en) * | 2001-01-16 | 2002-07-18 | Hiroshi Moriya | Semiconductor device and its production process |
US20020098627A1 (en) * | 2000-11-24 | 2002-07-25 | Pomarede Christophe F. | Surface preparation prior to deposition |
US20020106536A1 (en) * | 2001-02-02 | 2002-08-08 | Jongho Lee | Dielectric layer for semiconductor device and method of manufacturing the same |
US20030013320A1 (en) * | 2001-05-31 | 2003-01-16 | Samsung Electronics Co., Ltd. | Method of forming a thin film using atomic layer deposition |
US20030015764A1 (en) * | 2001-06-21 | 2003-01-23 | Ivo Raaijmakers | Trench isolation for integrated circuit |
US20030032281A1 (en) * | 2000-03-07 | 2003-02-13 | Werkhoven Christiaan J. | Graded thin films |
US20030031807A1 (en) * | 1999-10-15 | 2003-02-13 | Kai-Erik Elers | Deposition of transition metal carbides |
US20030049942A1 (en) * | 2001-08-31 | 2003-03-13 | Suvi Haukka | Low temperature gate stack |
US20030049931A1 (en) * | 2001-09-19 | 2003-03-13 | Applied Materials, Inc. | Formation of refractory metal nitrides using chemisorption techniques |
US20030060057A1 (en) * | 2000-02-22 | 2003-03-27 | Ivo Raaijmakers | Method of forming ultrathin oxide layer |
US20030068437A1 (en) * | 1999-09-07 | 2003-04-10 | Genji Nakamura | Method and apparatus for forming insulating film containing silicon oxy-nitride |
US20030072975A1 (en) * | 2001-10-02 | 2003-04-17 | Shero Eric J. | Incorporation of nitrogen into high k dielectric film |
US6552485B2 (en) * | 1998-06-25 | 2003-04-22 | Koninklijke Philips Electronics N.V. | Electron tube comprising a semiconductor cathode |
US20030082301A1 (en) * | 2001-10-26 | 2003-05-01 | Applied Materials, Inc. | Enhanced copper growth with ultrathin barrier layer for high performance interconnects |
US20030082296A1 (en) * | 2001-09-14 | 2003-05-01 | Kai Elers | Metal nitride deposition by ALD with reduction pulse |
US20030089942A1 (en) * | 2001-11-09 | 2003-05-15 | Micron Technology, Inc. | Scalable gate and storage dielectric |
US20030096473A1 (en) * | 2001-11-16 | 2003-05-22 | Taiwan Semiconductor Manufacturing Company | Method for making metal capacitors with low leakage currents for mixed-signal devices |
US20030104710A1 (en) * | 2001-11-30 | 2003-06-05 | Visokay Mark R. | Gate dielectric and method |
US20030109114A1 (en) * | 2001-12-11 | 2003-06-12 | Matsushita Electric Industrial Co., Ltd. | Method for forming insulative film, a semiconductor device and method for manufacturing the same |
US20030106490A1 (en) * | 2001-12-06 | 2003-06-12 | Applied Materials, Inc. | Apparatus and method for fast-cycle atomic layer deposition |
US20030116804A1 (en) * | 2001-12-26 | 2003-06-26 | Visokay Mark Robert | Bilayer deposition to avoid unwanted interfacial reactions during high K gate dielectric processing |
US20030133861A1 (en) * | 2002-01-17 | 2003-07-17 | Bowen Heather Regina | Purification of group IVb metal halides |
US6607973B1 (en) * | 2002-09-16 | 2003-08-19 | Advanced Micro Devices, Inc. | Preparation of high-k nitride silicate layers by cyclic molecular layer deposition |
US6674138B1 (en) * | 2001-12-31 | 2004-01-06 | Advanced Micro Devices, Inc. | Use of high-k dielectric materials in modified ONO structure for semiconductor devices |
US20040005749A1 (en) * | 2002-07-02 | 2004-01-08 | Choi Gil-Heyun | Methods of forming dual gate semiconductor devices having a metal nitride layer |
US20040009675A1 (en) * | 2002-07-15 | 2004-01-15 | Eissa Mona M. | Gate structure and method |
US20040009307A1 (en) * | 2000-06-08 | 2004-01-15 | Won-Yong Koh | Thin film forming method |
US20040007747A1 (en) * | 2002-07-15 | 2004-01-15 | Visokay Mark R. | Gate structure and method |
US20040016973A1 (en) * | 2002-07-26 | 2004-01-29 | Rotondaro Antonio L.P. | Gate dielectric and method |
US20040018747A1 (en) * | 2002-07-20 | 2004-01-29 | Lee Jung-Hyun | Deposition method of a dielectric layer |
US20040018723A1 (en) * | 2000-06-27 | 2004-01-29 | Applied Materials, Inc. | Formation of boride barrier layers using chemisorption techniques |
US20040023461A1 (en) * | 2002-07-30 | 2004-02-05 | Micron Technology, Inc. | Atomic layer deposited nanolaminates of HfO2/ZrO2 films as gate dielectrics |
US20040023462A1 (en) * | 2002-07-31 | 2004-02-05 | Rotondaro Antonio L.P. | Gate dielectric and method |
US20040029321A1 (en) * | 2002-08-07 | 2004-02-12 | Chartered Semiconductor Manufacturing Ltd. | Method for forming gate insulating layer having multiple dielectric constants and multiple equivalent oxide thicknesses |
US20040028952A1 (en) * | 2002-06-10 | 2004-02-12 | Interuniversitair Microelektronica Centrum (Imec Vzw) | High dielectric constant composition and method of making same |
US20040033698A1 (en) * | 2002-08-17 | 2004-02-19 | Lee Yun-Jung | Method of forming oxide layer using atomic layer deposition method and method of forming capacitor of semiconductor device using the same |
US20040038554A1 (en) * | 2002-08-21 | 2004-02-26 | Ahn Kie Y. | Composite dielectric forming methods and composite dielectrics |
US20040036111A1 (en) * | 2002-03-26 | 2004-02-26 | Matsushita Electric Industrial Co., Ltd. | Semiconductor device and a fabrication method thereof |
US20040043569A1 (en) * | 2002-08-28 | 2004-03-04 | Ahn Kie Y. | Atomic layer deposited HfSiON dielectric films |
US20040043630A1 (en) * | 2002-08-28 | 2004-03-04 | Micron Technology, Inc. | Systems and methods for forming metal oxides using metal organo-amines and metal organo-oxides |
US20040040501A1 (en) * | 2002-08-28 | 2004-03-04 | Micron Technology, Inc. | Systems and methods for forming zirconium and/or hafnium-containing layers |
US20040043149A1 (en) * | 2000-09-28 | 2004-03-04 | Gordon Roy G. | Vapor deposition of metal oxides, silicates and phosphates, and silicon dioxide |
US20040046197A1 (en) * | 2002-05-16 | 2004-03-11 | Cem Basceri | MIS capacitor and method of formation |
US20040048491A1 (en) * | 2002-09-10 | 2004-03-11 | Hyung-Suk Jung | Post thermal treatment methods of forming high dielectric layers in integrated circuit devices |
US20040053484A1 (en) * | 2002-09-16 | 2004-03-18 | Applied Materials, Inc. | Method of fabricating a gate structure of a field effect transistor using a hard mask |
US20040051152A1 (en) * | 2002-09-13 | 2004-03-18 | Semiconductor Technology Academic Research Center | Semiconductor device and method for manufacturing same |
US20040077182A1 (en) * | 2002-10-22 | 2004-04-22 | Lim Jung-Wook | Method for forming introgen-containing oxide thin film using plasma enhanced atomic layer deposition |
US20050006799A1 (en) * | 2002-07-23 | 2005-01-13 | Gregg John N. | Method and apparatus to help promote contact of gas with vaporized material |
Family Cites Families (69)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2207973A (en) * | 1938-03-07 | 1940-07-16 | Nat Automotive Fibres Inc | Feed control for sewing mechanism |
JPH0824191B2 (en) | 1989-03-17 | 1996-03-06 | 富士通株式会社 | Thin film transistor |
US5290509A (en) * | 1990-01-22 | 1994-03-01 | Sanyo Electric Co., Ltd. | Multiphase hydrogen-absorbing alloy electrode for an alkaline storage cell |
JP2637265B2 (en) | 1990-06-28 | 1997-08-06 | 株式会社東芝 | Method of forming silicon nitride film |
US5970384A (en) * | 1994-08-11 | 1999-10-19 | Semiconductor Energy Laboratory Co., Ltd. | Methods of heat treating silicon oxide films by irradiating ultra-violet light |
TWI227531B (en) | 1997-03-05 | 2005-02-01 | Hitachi Ltd | Manufacturing method of semiconductor integrated circuit device |
US6287965B1 (en) | 1997-07-28 | 2001-09-11 | Samsung Electronics Co, Ltd. | Method of forming metal layer using atomic layer deposition and semiconductor device having the metal layer as barrier metal layer or upper or lower electrode of capacitor |
KR100269306B1 (en) | 1997-07-31 | 2000-10-16 | 윤종용 | Integrate circuit device having buffer layer containing metal oxide stabilized by low temperature treatment and fabricating method thereof |
US6149829A (en) | 1998-03-17 | 2000-11-21 | James W. Mitzel | Plasma surface treatment method and resulting device |
JP4214585B2 (en) | 1998-04-24 | 2009-01-28 | 富士ゼロックス株式会社 | Semiconductor device, semiconductor device manufacturing method and manufacturing apparatus |
DE29810954U1 (en) * | 1998-06-18 | 1999-03-25 | Trw Repa Gmbh | Buckle |
US6284652B1 (en) | 1998-07-01 | 2001-09-04 | Advanced Technology Materials, Inc. | Adhesion promotion method for electro-chemical copper metallization in IC applications |
TW419732B (en) | 1998-07-15 | 2001-01-21 | Texas Instruments Inc | A method for gate-stack formation including a high-k dielectric |
US6291283B1 (en) | 1998-11-09 | 2001-09-18 | Texas Instruments Incorporated | Method to form silicates as high dielectric constant materials |
US6540838B2 (en) | 2000-11-29 | 2003-04-01 | Genus, Inc. | Apparatus and concept for minimizing parasitic chemical vapor deposition during atomic layer deposition |
JP2000349285A (en) * | 1999-06-04 | 2000-12-15 | Hitachi Ltd | Manufacture of semiconductor integrated circuit device and the semiconductor integrated circuit device |
US6124158A (en) | 1999-06-08 | 2000-09-26 | Lucent Technologies Inc. | Method of reducing carbon contamination of a thin dielectric film by using gaseous organic precursors, inert gas, and ozone to react with carbon contaminants |
JP2001011100A (en) | 1999-06-30 | 2001-01-16 | Nec Corp | Substrate for detection of hiv protease and expression vector therefor |
US6503561B1 (en) | 1999-07-08 | 2003-01-07 | Air Products And Chemicals, Inc. | Liquid precursor mixtures for deposition of multicomponent metal containing materials |
US6297539B1 (en) | 1999-07-19 | 2001-10-02 | Sharp Laboratories Of America, Inc. | Doped zirconia, or zirconia-like, dielectric film transistor structure and deposition method for same |
US6299294B1 (en) | 1999-07-29 | 2001-10-09 | Hewlett-Packard Company | High efficiency printhead containing a novel oxynitride-based resistor system |
DE10049257B4 (en) | 1999-10-06 | 2015-05-13 | Samsung Electronics Co., Ltd. | Process for thin film production by means of atomic layer deposition |
FI117942B (en) | 1999-10-14 | 2007-04-30 | Asm Int | Process for making oxide thin films |
TW468212B (en) | 1999-10-25 | 2001-12-11 | Motorola Inc | Method for fabricating a semiconductor structure including a metal oxide interface with silicon |
US6780704B1 (en) | 1999-12-03 | 2004-08-24 | Asm International Nv | Conformal thin films over textured capacitor electrodes |
FI118804B (en) | 1999-12-03 | 2008-03-31 | Asm Int | Process for making oxide films |
KR100358056B1 (en) | 1999-12-27 | 2002-10-25 | 주식회사 하이닉스반도체 | Method of forming a gate dielectric film in a semiconductor device |
KR100348177B1 (en) * | 2000-01-13 | 2002-08-09 | 조동일 | Isolation Method for Single Crystalline Silicon Micro Machining using Deep Trench Dielectric Layer |
KR20010096229A (en) | 2000-04-18 | 2001-11-07 | 황 철 주 | Apparatus and method for forming ultra-thin film of semiconductor device |
US6984591B1 (en) | 2000-04-20 | 2006-01-10 | International Business Machines Corporation | Precursor source mixtures |
JP4868639B2 (en) | 2000-06-12 | 2012-02-01 | 株式会社Adeka | Raw material for chemical vapor deposition and method for producing thin film using the same |
EP1170704A1 (en) | 2000-07-04 | 2002-01-09 | acter AG | Portable access authorization device, GPS receiver and antenna |
US6461909B1 (en) | 2000-08-30 | 2002-10-08 | Micron Technology, Inc. | Process for fabricating RuSixOy-containing adhesion layers |
JP3409290B2 (en) | 2000-09-18 | 2003-05-26 | 株式会社トリケミカル研究所 | Gate oxide film forming material |
JP2002172767A (en) | 2000-09-26 | 2002-06-18 | Canon Inc | Ink jet recorder, its controlling method, and information processor and processing method |
JP4644359B2 (en) | 2000-11-30 | 2011-03-02 | ルネサスエレクトロニクス株式会社 | Deposition method |
KR100385947B1 (en) | 2000-12-06 | 2003-06-02 | 삼성전자주식회사 | Method of forming thin film by atomic layer deposition |
US6713846B1 (en) * | 2001-01-26 | 2004-03-30 | Aviza Technology, Inc. | Multilayer high κ dielectric films |
FI109770B (en) | 2001-03-16 | 2002-10-15 | Asm Microchemistry Oy | Growing transition metal nitride thin films by using compound having hydrocarbon, amino or silyl group bound to nitrogen as nitrogen source material |
US20020142500A1 (en) | 2001-03-27 | 2002-10-03 | Pietro Foglietti | Ultra-thin interface oxidation by ozonated water rinsing for emitter poly structure |
US7005392B2 (en) | 2001-03-30 | 2006-02-28 | Advanced Technology Materials, Inc. | Source reagent compositions for CVD formation of gate dielectric thin films using amide precursors and method of using same |
EP1677361A2 (en) | 2001-04-02 | 2006-07-05 | Matsushita Electric Industrial Co., Ltd. | Semiconductor device and method for manufacture thereof |
JP2002313951A (en) | 2001-04-11 | 2002-10-25 | Hitachi Ltd | Semiconductor integrated circuit device and its manufacturing method |
JP2002314072A (en) | 2001-04-19 | 2002-10-25 | Nec Corp | Semiconductor device with high dielectric thin film and manufacturing method therefor, and film-forming method for dielectric film |
JP2002343790A (en) | 2001-05-21 | 2002-11-29 | Nec Corp | Vapor-phase deposition method of metallic compound thin film and method for manufacturing semiconductor device |
KR100363332B1 (en) | 2001-05-23 | 2002-12-05 | Samsung Electronics Co Ltd | Method for forming semiconductor device having gate all-around type transistor |
US6709989B2 (en) | 2001-06-21 | 2004-03-23 | Motorola, Inc. | Method for fabricating a semiconductor structure including a metal oxide interface with silicon |
US6642131B2 (en) | 2001-06-21 | 2003-11-04 | Matsushita Electric Industrial Co., Ltd. | Method of forming a silicon-containing metal-oxide gate dielectric by depositing a high dielectric constant film on a silicon substrate and diffusing silicon from the substrate into the high dielectric constant film |
US6514808B1 (en) * | 2001-11-30 | 2003-02-04 | Motorola, Inc. | Transistor having a high K dielectric and short gate length and method therefor |
US20030111678A1 (en) | 2001-12-14 | 2003-06-19 | Luigi Colombo | CVD deposition of M-SION gate dielectrics |
US6790755B2 (en) | 2001-12-27 | 2004-09-14 | Advanced Micro Devices, Inc. | Preparation of stack high-K gate dielectrics with nitrided layer |
US6452229B1 (en) | 2002-02-21 | 2002-09-17 | Advanced Micro Devices, Inc. | Ultra-thin fully depleted SOI device with T-shaped gate and method of fabrication |
US7323422B2 (en) | 2002-03-05 | 2008-01-29 | Asm International N.V. | Dielectric layers and methods of forming the same |
US6753618B2 (en) | 2002-03-11 | 2004-06-22 | Micron Technology, Inc. | MIM capacitor with metal nitride electrode materials and method of formation |
US6825134B2 (en) | 2002-03-26 | 2004-11-30 | Applied Materials, Inc. | Deposition of film layers by alternately pulsing a precursor and high frequency power in a continuous gas flow |
JP3937892B2 (en) | 2002-04-01 | 2007-06-27 | 日本電気株式会社 | Thin film forming method and semiconductor device manufacturing method |
US6846516B2 (en) | 2002-04-08 | 2005-01-25 | Applied Materials, Inc. | Multiple precursor cyclical deposition system |
US6869838B2 (en) | 2002-04-09 | 2005-03-22 | Applied Materials, Inc. | Deposition of passivation layers for active matrix liquid crystal display (AMLCD) applications |
US20030235961A1 (en) | 2002-04-17 | 2003-12-25 | Applied Materials, Inc. | Cyclical sequential deposition of multicomponent films |
KR100505043B1 (en) | 2002-05-25 | 2005-07-29 | 삼성전자주식회사 | Method for forming a capacitor |
US7135421B2 (en) | 2002-06-05 | 2006-11-14 | Micron Technology, Inc. | Atomic layer-deposited hafnium aluminum oxide |
US7067439B2 (en) | 2002-06-14 | 2006-06-27 | Applied Materials, Inc. | ALD metal oxide deposition process using direct oxidation |
US20030232501A1 (en) | 2002-06-14 | 2003-12-18 | Kher Shreyas S. | Surface pre-treatment for enhancement of nucleation of high dielectric constant materials |
US6858547B2 (en) | 2002-06-14 | 2005-02-22 | Applied Materials, Inc. | System and method for forming a gate dielectric |
US7081409B2 (en) | 2002-07-17 | 2006-07-25 | Samsung Electronics Co., Ltd. | Methods of producing integrated circuit devices utilizing tantalum amine derivatives |
JP2004103208A (en) * | 2002-07-18 | 2004-04-02 | Nec Corp | Information recording medium, method for indicator generation, manufacturing method, recording condition adjusting method, and recording method for the same medium, and information recorder |
US6919263B2 (en) * | 2002-11-08 | 2005-07-19 | Lsi Logic Corporation | High-K dielectric gate material uniquely formed |
DE10319540A1 (en) | 2003-04-30 | 2004-11-25 | Infineon Technologies Ag | Process for ALD coating of substrates and a device suitable for carrying out the process |
US7088009B2 (en) * | 2003-08-20 | 2006-08-08 | Freescale Semiconductor, Inc. | Wirebonded assemblage method and apparatus |
-
2002
- 2002-11-21 US US10/302,752 patent/US20030232501A1/en not_active Abandoned
-
2006
- 2006-07-06 US US11/456,062 patent/US20060264067A1/en not_active Abandoned
-
2010
- 2010-06-04 US US12/794,047 patent/US8071167B2/en not_active Expired - Fee Related
Patent Citations (99)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4693208A (en) * | 1985-07-15 | 1987-09-15 | Dainippon Screen Mfg. Co., Ltd. | Feeder of oxygen gas containing steam |
US5290609A (en) * | 1991-03-25 | 1994-03-01 | Tokyo Electron Limited | Method of forming dielectric film for semiconductor devices |
US5521126A (en) * | 1993-06-25 | 1996-05-28 | Nec Corporation | Method of fabricating semiconductor devices |
US5916365A (en) * | 1996-08-16 | 1999-06-29 | Sherman; Arthur | Sequential chemical vapor deposition |
US6342277B1 (en) * | 1996-08-16 | 2002-01-29 | Licensee For Microelectronics: Asm America, Inc. | Sequential chemical vapor deposition |
US20020031618A1 (en) * | 1996-08-16 | 2002-03-14 | Arthur Sherman | Sequential chemical vapor deposition |
US5807792A (en) * | 1996-12-18 | 1998-09-15 | Siemens Aktiengesellschaft | Uniform distribution of reactants in a device layer |
US6013553A (en) * | 1997-07-24 | 2000-01-11 | Texas Instruments Incorporated | Zirconium and/or hafnium oxynitride gate dielectric |
US6020243A (en) * | 1997-07-24 | 2000-02-01 | Texas Instruments Incorporated | Zirconium and/or hafnium silicon-oxynitride gate dielectric |
US6020024A (en) * | 1997-08-04 | 2000-02-01 | Motorola, Inc. | Method for forming high dielectric constant metal oxides |
US6416577B1 (en) * | 1997-12-09 | 2002-07-09 | Asm Microchemistry Ltd. | Method for coating inner surfaces of equipment |
US6174809B1 (en) * | 1997-12-31 | 2001-01-16 | Samsung Electronics, Co., Ltd. | Method for forming metal layer using atomic layer deposition |
US6025627A (en) * | 1998-05-29 | 2000-02-15 | Micron Technology, Inc. | Alternate method and structure for improved floating gate tunneling devices |
US6372598B2 (en) * | 1998-06-16 | 2002-04-16 | Samsung Electronics Co., Ltd. | Method of forming selective metal layer and method of forming capacitor and filling contact hole using the same |
US6552485B2 (en) * | 1998-06-25 | 2003-04-22 | Koninklijke Philips Electronics N.V. | Electron tube comprising a semiconductor cathode |
US6270572B1 (en) * | 1998-08-07 | 2001-08-07 | Samsung Electronics Co., Ltd. | Method for manufacturing thin film using atomic layer deposition |
US20020029092A1 (en) * | 1998-09-21 | 2002-03-07 | Baltes Gass | Process tool and process system for processing a workpiece |
US6207487B1 (en) * | 1998-10-13 | 2001-03-27 | Samsung Electronics Co., Ltd. | Method for forming dielectric film of capacitor having different thicknesses partly |
US20010000866A1 (en) * | 1999-03-11 | 2001-05-10 | Ofer Sneh | Apparatus and concept for minimizing parasitic chemical vapor deposition during atomic layer deposition |
US20010002280A1 (en) * | 1999-03-11 | 2001-05-31 | Ofer Sneh | Radical-assisted sequential CVD |
US6200893B1 (en) * | 1999-03-11 | 2001-03-13 | Genus, Inc | Radical-assisted sequential CVD |
US20020093781A1 (en) * | 1999-05-12 | 2002-07-18 | Harald Bachhofer | Capacitor for semiconductor configuration and method for fabricating a dielectric layer therefor |
US6238734B1 (en) * | 1999-07-08 | 2001-05-29 | Air Products And Chemicals, Inc. | Liquid precursor mixtures for deposition of multicomponent metal containing materials |
US6060755A (en) * | 1999-07-19 | 2000-05-09 | Sharp Laboratories Of America, Inc. | Aluminum-doped zirconium dielectric film transistor structure and deposition method for same |
US6391785B1 (en) * | 1999-08-24 | 2002-05-21 | Interuniversitair Microelektronica Centrum (Imec) | Method for bottomless deposition of barrier layers in integrated circuit metallization schemes |
US20030068437A1 (en) * | 1999-09-07 | 2003-04-10 | Genji Nakamura | Method and apparatus for forming insulating film containing silicon oxy-nitride |
US20020005556A1 (en) * | 1999-10-06 | 2002-01-17 | Eduard Albert Cartier | Silicate gate dielectric |
US6399208B1 (en) * | 1999-10-07 | 2002-06-04 | Advanced Technology Materials Inc. | Source reagent composition and method for chemical vapor deposition formation or ZR/HF silicate gate dielectric thin films |
US20020015790A1 (en) * | 1999-10-07 | 2002-02-07 | Advanced Technology Materials Inc. | Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same |
US20030031807A1 (en) * | 1999-10-15 | 2003-02-13 | Kai-Erik Elers | Deposition of transition metal carbides |
US6203613B1 (en) * | 1999-10-19 | 2001-03-20 | International Business Machines Corporation | Atomic layer deposition with nitrate containing precursors |
US20020000598A1 (en) * | 1999-12-08 | 2002-01-03 | Sang-Bom Kang | Semiconductor devices having metal layers as barrier layers on upper or lower electrodes of capacitors |
US6348420B1 (en) * | 1999-12-23 | 2002-02-19 | Asm America, Inc. | Situ dielectric stacks |
US20020076831A1 (en) * | 1999-12-28 | 2002-06-20 | Taizo Akimoto | Test piece, analysis method using the test piece, and analysis system used for the method |
US6599572B2 (en) * | 2000-01-18 | 2003-07-29 | Asm Microchemistry Oy | Process for growing metalloid thin films utilizing boron-containing reducing agents |
US20010009695A1 (en) * | 2000-01-18 | 2001-07-26 | Saanila Ville Antero | Process for growing metalloid thin films |
US20030060057A1 (en) * | 2000-02-22 | 2003-03-27 | Ivo Raaijmakers | Method of forming ultrathin oxide layer |
US6534395B2 (en) * | 2000-03-07 | 2003-03-18 | Asm Microchemistry Oy | Method of forming graded thin films using alternating pulses of vapor phase reactants |
US20030032281A1 (en) * | 2000-03-07 | 2003-02-13 | Werkhoven Christiaan J. | Graded thin films |
US20030129826A1 (en) * | 2000-03-07 | 2003-07-10 | Werkhoven Christiaan J. | Graded thin films |
US6399491B2 (en) * | 2000-04-20 | 2002-06-04 | Samsung Electronics Co., Ltd. | Method of manufacturing a barrier metal layer using atomic layer deposition |
US20020081844A1 (en) * | 2000-04-20 | 2002-06-27 | In-Sang Jeon | Method of manufacturing a barrier metal layer using atomic layer deposition |
US20040009307A1 (en) * | 2000-06-08 | 2004-01-15 | Won-Yong Koh | Thin film forming method |
US20040018723A1 (en) * | 2000-06-27 | 2004-01-29 | Applied Materials, Inc. | Formation of boride barrier layers using chemisorption techniques |
US20020008297A1 (en) * | 2000-06-28 | 2002-01-24 | Dae-Gyu Park | Gate structure and method for manufacture thereof |
US20020014647A1 (en) * | 2000-07-07 | 2002-02-07 | Infineon Technologies Ag | Trench capacitor with isolation collar and corresponding method of production |
US20020043666A1 (en) * | 2000-07-20 | 2002-04-18 | Parsons Gregory N. | High dielectric constant metal silicates formed by controlled metal-surface reactions |
US20040043149A1 (en) * | 2000-09-28 | 2004-03-04 | Gordon Roy G. | Vapor deposition of metal oxides, silicates and phosphates, and silicon dioxide |
US20020047151A1 (en) * | 2000-10-19 | 2002-04-25 | Kim Yeong-Kwan | Semiconductor device having thin film formed by atomic layer deposition and method for fabricating the same |
US6395650B1 (en) * | 2000-10-23 | 2002-05-28 | International Business Machines Corporation | Methods for forming metal oxide layers with enhanced purity |
US20020098627A1 (en) * | 2000-11-24 | 2002-07-25 | Pomarede Christophe F. | Surface preparation prior to deposition |
US20020076837A1 (en) * | 2000-11-30 | 2002-06-20 | Juha Hujanen | Thin films for magnetic device |
US20020064970A1 (en) * | 2000-11-30 | 2002-05-30 | Chartered Semiconductor Manufacturing Inc. | Method to form zirconium oxide and hafnium oxide for high dielectric constant materials |
US20020074588A1 (en) * | 2000-12-20 | 2002-06-20 | Kyu-Mann Lee | Ferroelectric capacitors for integrated circuit memory devices and methods of manufacturing same |
US20020081826A1 (en) * | 2000-12-21 | 2002-06-27 | Rotondaro Antonio L. P. | Annealing of high-K dielectric materials |
US20020086111A1 (en) * | 2001-01-03 | 2002-07-04 | Byun Jeong Soo | Method of forming refractory metal nitride layers using chemisorption techniques |
US20020093046A1 (en) * | 2001-01-16 | 2002-07-18 | Hiroshi Moriya | Semiconductor device and its production process |
US20020106536A1 (en) * | 2001-02-02 | 2002-08-08 | Jongho Lee | Dielectric layer for semiconductor device and method of manufacturing the same |
US6348386B1 (en) * | 2001-04-16 | 2002-02-19 | Motorola, Inc. | Method for making a hafnium-based insulating film |
US20030013320A1 (en) * | 2001-05-31 | 2003-01-16 | Samsung Electronics Co., Ltd. | Method of forming a thin film using atomic layer deposition |
US6391803B1 (en) * | 2001-06-20 | 2002-05-21 | Samsung Electronics Co., Ltd. | Method of forming silicon containing thin films by atomic layer deposition utilizing trisdimethylaminosilane |
US20030015764A1 (en) * | 2001-06-21 | 2003-01-23 | Ivo Raaijmakers | Trench isolation for integrated circuit |
US6420279B1 (en) * | 2001-06-28 | 2002-07-16 | Sharp Laboratories Of America, Inc. | Methods of using atomic layer deposition to deposit a high dielectric constant material on a substrate |
US20030049942A1 (en) * | 2001-08-31 | 2003-03-13 | Suvi Haukka | Low temperature gate stack |
US20030082296A1 (en) * | 2001-09-14 | 2003-05-01 | Kai Elers | Metal nitride deposition by ALD with reduction pulse |
US20030049931A1 (en) * | 2001-09-19 | 2003-03-13 | Applied Materials, Inc. | Formation of refractory metal nitrides using chemisorption techniques |
US20030072975A1 (en) * | 2001-10-02 | 2003-04-17 | Shero Eric J. | Incorporation of nitrogen into high k dielectric film |
US20030082301A1 (en) * | 2001-10-26 | 2003-05-01 | Applied Materials, Inc. | Enhanced copper growth with ultrathin barrier layer for high performance interconnects |
US20030089942A1 (en) * | 2001-11-09 | 2003-05-15 | Micron Technology, Inc. | Scalable gate and storage dielectric |
US20030160277A1 (en) * | 2001-11-09 | 2003-08-28 | Micron Technology, Inc. | Scalable gate and storage dielectric |
US20030096473A1 (en) * | 2001-11-16 | 2003-05-22 | Taiwan Semiconductor Manufacturing Company | Method for making metal capacitors with low leakage currents for mixed-signal devices |
US20030104710A1 (en) * | 2001-11-30 | 2003-06-05 | Visokay Mark R. | Gate dielectric and method |
US20030106490A1 (en) * | 2001-12-06 | 2003-06-12 | Applied Materials, Inc. | Apparatus and method for fast-cycle atomic layer deposition |
US20030109114A1 (en) * | 2001-12-11 | 2003-06-12 | Matsushita Electric Industrial Co., Ltd. | Method for forming insulative film, a semiconductor device and method for manufacturing the same |
US20030116804A1 (en) * | 2001-12-26 | 2003-06-26 | Visokay Mark Robert | Bilayer deposition to avoid unwanted interfacial reactions during high K gate dielectric processing |
US6674138B1 (en) * | 2001-12-31 | 2004-01-06 | Advanced Micro Devices, Inc. | Use of high-k dielectric materials in modified ONO structure for semiconductor devices |
US20030133861A1 (en) * | 2002-01-17 | 2003-07-17 | Bowen Heather Regina | Purification of group IVb metal halides |
US20040036111A1 (en) * | 2002-03-26 | 2004-02-26 | Matsushita Electric Industrial Co., Ltd. | Semiconductor device and a fabrication method thereof |
US20040046197A1 (en) * | 2002-05-16 | 2004-03-11 | Cem Basceri | MIS capacitor and method of formation |
US20040028952A1 (en) * | 2002-06-10 | 2004-02-12 | Interuniversitair Microelektronica Centrum (Imec Vzw) | High dielectric constant composition and method of making same |
US20040005749A1 (en) * | 2002-07-02 | 2004-01-08 | Choi Gil-Heyun | Methods of forming dual gate semiconductor devices having a metal nitride layer |
US20040009675A1 (en) * | 2002-07-15 | 2004-01-15 | Eissa Mona M. | Gate structure and method |
US20040007747A1 (en) * | 2002-07-15 | 2004-01-15 | Visokay Mark R. | Gate structure and method |
US20040018747A1 (en) * | 2002-07-20 | 2004-01-29 | Lee Jung-Hyun | Deposition method of a dielectric layer |
US20050006799A1 (en) * | 2002-07-23 | 2005-01-13 | Gregg John N. | Method and apparatus to help promote contact of gas with vaporized material |
US20040016973A1 (en) * | 2002-07-26 | 2004-01-29 | Rotondaro Antonio L.P. | Gate dielectric and method |
US20040023461A1 (en) * | 2002-07-30 | 2004-02-05 | Micron Technology, Inc. | Atomic layer deposited nanolaminates of HfO2/ZrO2 films as gate dielectrics |
US20040023462A1 (en) * | 2002-07-31 | 2004-02-05 | Rotondaro Antonio L.P. | Gate dielectric and method |
US20040029321A1 (en) * | 2002-08-07 | 2004-02-12 | Chartered Semiconductor Manufacturing Ltd. | Method for forming gate insulating layer having multiple dielectric constants and multiple equivalent oxide thicknesses |
US20040033698A1 (en) * | 2002-08-17 | 2004-02-19 | Lee Yun-Jung | Method of forming oxide layer using atomic layer deposition method and method of forming capacitor of semiconductor device using the same |
US20040038554A1 (en) * | 2002-08-21 | 2004-02-26 | Ahn Kie Y. | Composite dielectric forming methods and composite dielectrics |
US20040043569A1 (en) * | 2002-08-28 | 2004-03-04 | Ahn Kie Y. | Atomic layer deposited HfSiON dielectric films |
US20040040501A1 (en) * | 2002-08-28 | 2004-03-04 | Micron Technology, Inc. | Systems and methods for forming zirconium and/or hafnium-containing layers |
US20040043630A1 (en) * | 2002-08-28 | 2004-03-04 | Micron Technology, Inc. | Systems and methods for forming metal oxides using metal organo-amines and metal organo-oxides |
US20040048491A1 (en) * | 2002-09-10 | 2004-03-11 | Hyung-Suk Jung | Post thermal treatment methods of forming high dielectric layers in integrated circuit devices |
US20040051152A1 (en) * | 2002-09-13 | 2004-03-18 | Semiconductor Technology Academic Research Center | Semiconductor device and method for manufacturing same |
US20040053484A1 (en) * | 2002-09-16 | 2004-03-18 | Applied Materials, Inc. | Method of fabricating a gate structure of a field effect transistor using a hard mask |
US6607973B1 (en) * | 2002-09-16 | 2003-08-19 | Advanced Micro Devices, Inc. | Preparation of high-k nitride silicate layers by cyclic molecular layer deposition |
US20040077182A1 (en) * | 2002-10-22 | 2004-04-22 | Lim Jung-Wook | Method for forming introgen-containing oxide thin film using plasma enhanced atomic layer deposition |
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US20030232511A1 (en) * | 2002-06-14 | 2003-12-18 | Applied Materials, Inc. | ALD metal oxide deposition process using direct oxidation |
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US8343279B2 (en) | 2004-05-12 | 2013-01-01 | Applied Materials, Inc. | Apparatuses for atomic layer deposition |
US8282992B2 (en) | 2004-05-12 | 2012-10-09 | Applied Materials, Inc. | Methods for atomic layer deposition of hafnium-containing high-K dielectric materials |
US7794544B2 (en) | 2004-05-12 | 2010-09-14 | Applied Materials, Inc. | Control of gas flow and delivery to suppress the formation of particles in an MOCVD/ALD system |
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US8323754B2 (en) | 2004-05-21 | 2012-12-04 | Applied Materials, Inc. | Stabilization of high-k dielectric materials |
WO2006012338A3 (en) * | 2004-06-30 | 2006-10-19 | Intel Corp | Forming high-k dielectric layers on smooth substrates |
US20060001071A1 (en) * | 2004-06-30 | 2006-01-05 | Brask Justin K | Forming high-k dielectric layers on smooth substrates |
US7323423B2 (en) | 2004-06-30 | 2008-01-29 | Intel Corporation | Forming high-k dielectric layers on smooth substrates |
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US20070196011A1 (en) * | 2004-11-22 | 2007-08-23 | Cox Damon K | Integrated vacuum metrology for cluster tool |
US20060156979A1 (en) * | 2004-11-22 | 2006-07-20 | Applied Materials, Inc. | Substrate processing apparatus using a batch processing chamber |
US7423311B2 (en) | 2005-02-15 | 2008-09-09 | Micron Technology, Inc. | Atomic layer deposition of Zr3N4/ZrO2 films as gate dielectrics |
US7960803B2 (en) | 2005-02-23 | 2011-06-14 | Micron Technology, Inc. | Electronic device having a hafnium nitride and hafnium oxide film |
US7498247B2 (en) * | 2005-02-23 | 2009-03-03 | Micron Technology, Inc. | Atomic layer deposition of Hf3N4/HfO2 films as gate dielectrics |
US7754620B2 (en) * | 2005-03-30 | 2010-07-13 | Tokyo Electron Limited | Film formation method and recording medium |
US20060223338A1 (en) * | 2005-03-30 | 2006-10-05 | Tokyo Electron Limited | Film formation method and recording medium |
US8361910B2 (en) * | 2005-08-26 | 2013-01-29 | Applied Materials, Inc. | Pretreatment processes within a batch ALD reactor |
US20110263137A1 (en) * | 2005-08-26 | 2011-10-27 | Maitreyee Mahajani | Pretreatment processes within a batch ald reactor |
US7972978B2 (en) | 2005-08-26 | 2011-07-05 | Applied Materials, Inc. | Pretreatment processes within a batch ALD reactor |
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