US20090079016A1 - Method for forming a dielectric stack - Google Patents
Method for forming a dielectric stack Download PDFInfo
- Publication number
- US20090079016A1 US20090079016A1 US12/272,614 US27261408A US2009079016A1 US 20090079016 A1 US20090079016 A1 US 20090079016A1 US 27261408 A US27261408 A US 27261408A US 2009079016 A1 US2009079016 A1 US 2009079016A1
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- US
- United States
- Prior art keywords
- dielectric
- layer
- dielectric layer
- stack
- hfo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 238000000034 method Methods 0.000 title claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 59
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 55
- 239000010703 silicon Substances 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 21
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 140
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 23
- 238000000231 atomic layer deposition Methods 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- -1 HfOxNy Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- 229910004541 SiN Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 52
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 abstract description 29
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- 238000000151 deposition Methods 0.000 description 31
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 27
- 230000008021 deposition Effects 0.000 description 26
- 229920005591 polysilicon Polymers 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000002243 precursor Substances 0.000 description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 15
- 229910003865 HfCl4 Inorganic materials 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052735 hafnium Inorganic materials 0.000 description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
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- 238000002474 experimental method Methods 0.000 description 6
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- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 238000010406 interfacial reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910002244 LaAlO3 Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
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- 238000010849 ion bombardment Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
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- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229910003227 N2H4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910007264 Si2H6 Inorganic materials 0.000 description 1
- 229910005096 Si3H8 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910020781 SixOy Inorganic materials 0.000 description 1
- CEPICIBPGDWCRU-UHFFFAOYSA-N [Si].[Hf] Chemical compound [Si].[Hf] CEPICIBPGDWCRU-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
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- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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- C23C16/405—Oxides of refractory metals or yttrium
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- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02104—Forming layers
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- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28185—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
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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
- H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
- H01L21/3144—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers on silicon
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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
- H01L21/318—Inorganic layers composed of nitrides
- H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides
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Definitions
- the present invention relates to integrated circuit fabrication processes and in particular to the formation of an integrated circuit comprising a multilayer dielectric stack of high-k material.
- the present invention further relates to such dielectric stack in an integrated circuit and to a MOS transistor having such multilayer dielectric stack.
- a multilayer dielectric stack according to the present invention replaces prior art silicon dioxide as dielectric layer in integrated circuits.
- CMOS gate dielectric material which is amorphous and 100% compatible with polysilicon gate
- nitrogen is a key modifier introduced to improve the resistance against boron diffusion.
- enhanced stability against dopant (boron) diffusion from the polysilicon gate can be achieved through the use of a metal-oxynitride (MO x N y ) or nitridation of metal oxide (U.S. Pat. No. 6,251,761).
- MO x N y metal-oxynitride
- U.S. Pat. No. 6,251,761 describes a gate stack including a gate dielectric with reduced effective electrical thickness. A high-k dielectric is deposited over the silicon substrate.
- remote plasma nitridation of the high-k dielectric layer is performed to convert the upper surface of the high-k dielectric into a nitride layer.
- a conductive layer is formed over the nitride layer to complete the CMOS gate stack.
- Published US patent application No. 2002/0130340 A1 discloses a multilayer dielectric stack, which has alternating layers of high-k material and an interposing material.
- the interposing material can be Al 2 O 3 , AlN, SiN, Si 3 N 4 and SiO 2 .
- the interposing material can be deposited by atomic layer deposition, sputtering or evaporation, resulting in the deposition of the interposing layer on the dielectric layer. Each layer is preferably less tan 50 Angstroms thick. This structure inhibits and prevents the crystallization of the high k-material.
- a method for forming a dielectric stack in an integrated circuit structure comprising the steps of:
- PECVD plasma-enhanced chemical vapor deposition process
- PE ALCVD plasma-enhanced atomic layer chemical vapor deposition
- highly reactive species such as nitrogen ions or radicals and silicon species penetrate into the upper part of the high-k material, thereby promoting intermixing, densification and formation of an intermediate layer.
- the intermediate layer comprises at least the high-k material, silicon and nitrogen.
- Highly reactive species are formed by plasma-enhanced chemical vapor deposition (PECVD) or plasma-enhanced atomic layer chemical vapor deposition (PE ALCVD).
- PECVD plasma-enhanced chemical vapor deposition
- PE ALCVD plasma-enhanced atomic layer chemical vapor deposition
- Highly reactive species can be radicals or ions. Consequently, using PECVD or PE ALCVD, the species formed in the plasma penetrate into the upper part of the underlying high-k dielectric layer.
- the presence of both silicon and nitrogen contributes to the compatibility between the high-k dielectric layer and any other layer such as e.g. the gate electrode.
- a method as recited in any of the previous embodiments wherein the subjecting step results in the formation of a dielectric layer comprising at least silicon and nitrogen and essentially no or no high-k material and in the formation of an intermediate layer disposed between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising at least the high-k material, silicon and nitrogen.
- the dielectric layer is selected from the group consisting of SiN, SiON and Si 3 N 4 .
- a method as recited in any of the previous embodiments wherein the subjecting step results in the formation of an intermediate layer adjacent to the high-k dielectric layer and the dielectric layer, the intermediate layer comprising at least the high-k material, silicon and nitrogen.
- the intermediate layer is on top of the high-k dielectric layer.
- the subjecting step results in essentially no and/or no formation at all of the dielectric layer (in the case of very thin layers).
- a method as recited in any of the previous embodiments is disclosed further comprising subjecting the substrate with the high-k dielectric layer to an oxygen comprising vapor phase reactant.
- the intermediate layer formed comprises oxygen in addition.
- the silicon comprising compound or vapor phase reactant is selected from the group consisting of SiH 4 , Si 2 H 6 , Si 3 H 8 , Si x HyCl z and combinations thereof.
- the nitrogen comprising compound is selected from the group consisting of nitrogen, ammonia, N 2 H 4 , NO, N 2 O, and combinations thereof.
- a method as recited in any of the previous embodiments is disclosed wherein the ratio of silane:nitrogen containing compounds is in the range of 1:1 to 1:10000. Preferably, the ratio is between 1:1 and 1:1000.
- a method as recited in any of the previous embodiments is disclosed further comprising repeating the forming step and the subjecting step between 2 and 100 times, between 2 and 50 times, between 10 and 50 times, between 10 and 30 times and between 2 and 10 times.
- the high-k dielectric layer comprises a high-k material selected from the group consisting of a transition metal or lanthanide oxide and a transition metal or lanthanide oxynitride.
- the high-k material is selected from the group consisting of ZrO 2 , HfO 2 , TiO 2 , Ta 2 O 5 , Al 2 O 3 , HfO x N y , HfN, La x O y , LaAlO 3 , and/or mixtures thereof.
- the forming step comprises subjecting the semiconducting substrate to an atomic layer deposition process.
- the high-k material is selected from the group consisting of HfO 2 , HfO x N y and HfN.
- a method as recited in any of the previous embodiments wherein the subjecting step is performed in a plasma-enhanced chemical vapor deposition (PECVD) chamber at a temperature in the range of 300 to 600 degrees Celsius.
- PECVD plasma-enhanced chemical vapor deposition
- a method as recited in any of the previous embodiments wherein the subjecting step is performed in a plasma-enhanced atomic layer chemical vapor deposition chamber at a temperature in the range of 300 to 600 degrees Celsius.
- the semiconductor substrate with the high-k dielectric layer is subjected to alternating pulses of precursor compounds, the precursor compound being a nitrogen containing vapor phase reactant or a silicon containing vapor phase reactant.
- a method as recited in any of the previous embodiments wherein the subjecting step is performed at a pressure in the range of 10 ⁇ 3 to 100 Torr.
- the pressure can vary, depending on the composition of reactants.
- the pressure is preferably between 0.01 and 100 Torr, while for a silane reactant, the pressure is between 1 and 100 mTorr.
- a method as recited in any of the previous embodiments wherein the subjecting step is performed in a plasma with a plasma density in the range of 10 10 to 10 13 reactive species cm ⁇ 3 .
- the high-k dielectric layer has a thickness in the range of 0.01 nm to 20 nm, 0.05 nm to 20 nm, 0.1 nm to 20 nm, 0.3 nm to 20 nm, 0.5 nm to 20 nm.
- the dielectric layer has a thickness in the range of 0.01 nm to 20 nm, 0.05 nm to 20 nm, 0.1 nm to 20 nm, 0.3 nm to 20 nm, 0.5 nm to 20 nm.
- the thickness is below 1 nm, below 0.5 nm and below 0.3 nm.
- the dielectric layer has a thickness between 0.01 nm and 1 nm, between 0.01 nm and 0.5 nm, between 0.01 nm and 0.1 nm.
- a method as recited in any of the previous embodiments wherein the step of forming a high-k dielectric layer on a semiconductor substrate is performed by an atomic layer deposition process (ALD).
- ALD atomic layer deposition process
- a method as recited in any of the previous embodiments is disclosed further comprising the step of annealing the semiconductor substrate at a temperature between 500 and 1000 degrees Celsius.
- the substrate is annealed at a temperature between 600 and 900 degrees Celsius.
- the step of annealing can be performed after each individual step or can be performed after the formation of the dielectric stack.
- the method as recited in the previous embodiments can further comprise the step of depositing a conductive layer over the dielectric stack.
- the conductive layer can comprise silicon.
- the conductive layer can be polysilicon, polysilicon germanium or a metal.
- the dielectric stack and the electrode layer are patterned to form the desired integrated circuit.
- a dielectric stack in an integrated circuit comprises:
- a device a recited in any of the previous embodiments wherein the dielectric stack further comprises a dielectric layer comprising at least silicon and nitrogen.
- a device as recited in any of the previous embodiments wherein the dielectric stack is characterized by a crystallization temperature, the crystallization temperature of the dielectric stack is higher than the crystallization temperature of the high-k material.
- a dielectric stack as recited in any of the previous embodiments wherein the crystallization temperature is between 800 degrees C. and 1200 degrees C.
- the intermediate layer and the dielectric layer are formed by subjecting the semiconductor substrate with the high-k dielectric layer to a nitrogen comprising vapor phase reactant and a silicon comprising vapor phase reactant in a plasma-enhanced chemical vapor deposition process (PECVD) or plasma-enhanced atomic layer chemical vapor deposition (PE ALCVD) process.
- PECVD plasma-enhanced chemical vapor deposition process
- PE ALCVD plasma-enhanced atomic layer chemical vapor deposition
- the high-k layer is formed by subjecting the semiconductor substrate to an atomic layer deposition process.
- a dielectric stack as recited in any of the previous embodiments wherein a sequence of the high-k dielectric layer, the intermediate layer and the dielectric layer is repeated between 3 and 60 times.
- a dielectric stack is provided wherein between one of the high-k dielectric layers and an adjacent one of the dielectric layers an intermediate layer is disposed, the intermediate layer comprising the dielectric material, silicon and nitrogen.
- the dielectric layer and the intermediate layer further comprise oxygen.
- a dielectric stack as recited in any of the previous embodiments wherein the dielectric layer does essentially not comprise the high-k material.
- the intermediate layer comprises the high-k material, nitrogen and silicon and optionally oxygen.
- the stack as recited in any of the previous embodiments comprises a dielectric layer selected from the group consisting of SiN, SiON, and Si 3 N 4 .
- a dielectric stack as recited in any of the previous embodiments wherein the high-k dielectric layer comprises a compound selected from the group consisting of a transition metal oxide or a transition metal oxynitride.
- the high-k dielectric layer comprises a high-k dielectric material selected from the group consisting of ZrO 2 , HfO 2 , TiO 2 , Ta 2 O 5 , Al 2 O 3 , HfO x N y , HfN and/or mixtures thereof. More preferably, the high-k dielectric material is selected from the group consisting of HfO 2 , HfO x N y and HfN.
- a dielectric stack as recited in any of the previous embodiment wherein the high-k dielectric layer has a thickness between 0.5 nm to 20 nm.
- a dielectric stack as recited in any of the previous embodiment wherein the dielectric layer has a thickness in the range of 0.01 nm to 20 nm, 0.05 nm to 20 nm, 0.1 nm to 20 nm, 0.3 nm to 20 nm, 0.5 nm to 20 nm.
- the thickness is below 1 nm, below 0.5 nm and below 0.3 nm.
- the dielectric layer has a thickness between 0.01 nm and 1 nm, between 0.01 nm and 0.5 nm, between 0.01 nm and 0.1 nm.
- the intermediate layer comprises Hf, nitrogen and silicon and oxygen.
- the dielectric layer of the stack is selected from the group consisting of SiN, SiON and Si 3 N 4 .
- MOS transistor comprises:
- the dielectric stack being interposed between the gate electrode and the upper surface of the channel region, the dielectric stack comprising a high-k dielectric layer comprising at least a high-k material, a dielectric layer comprising at least silicon and nitrogen and an intermediate layer between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising the high-k material, silicon and nitrogen.
- the dielectric stack is characterized by the features as disclosed in the second aspect of the invention.
- FIG. 1 a represents a flow chart of a method of forming a dielectric stack according to a preferred embodiment of the invention.
- FIG. 1 b represents a flow chart of a method of forming a dielectric stack according to another preferred embodiment of the invention.
- FIG. 2 represents a schematic view of a dielectric stack according to an embodiment of the present invention.
- FIG. 3 represents a schematic view of an integrated circuit structure according to an embodiment of the present invention.
- FIG. 4 represents a flow chart of a method of forming an integrated circuit according to a preferred embodiment of the invention.
- FIGS. 5 a - d represent the results of capacitor leakage experiments for devices obtained according to various methods.
- FIGS. 6 a - b represents a TEM picture of dielectric stacks obtained according to various methods.
- FIG. 7 represents a ToF-SIMS depth profile for a preferred embodiment of a device of the present invention.
- FIGS. 8 a - c represents X-Ray diffraction spectra of devices obtained according to various methods.
- the FIG. 9 represents channel electron mobility measurements from n-MOSFET devices obtained according to various methods.
- the FIG. 10 represents the cumulative distribution of gate leakage current for 30 diode/capacitor devices obtained according to different methods.
- a Plasma enhanced CVD or plasma enhanced ALCVD process should be understood as a process wherein at least one chemical compound is subjected to a plasma source, thereby creating highly reactive species such as radicals or ions.
- high-k dielectric layer should be understood as a layer comprising a high-k material.
- a high-k material is a dielectric material having a dielectric constant greater than the dielectric constant of silicon oxide and preferably greater than 10.
- the high-k material can be a high-k material selected from the group consisting of a transition metal oxide or a transition metal oxynitride, a rare earth metal oxide, a rare earth metal oxynitride.
- Transition metals can be Group IV or Group V metals such as e.g. Ti, Zr, Hf, V, Nb, and Ta.
- Rare earth metal can be Lanthanides such as e.g. So, Ce, Pr, Eu. Lanthanides meaning an element from the lanthanide series.
- High-k material can also include lanthanum oxide, neodymium oxide and cerium oxide.
- the metal is Hafnium (Hf).
- the high-k material is selected from the group consisting of ZrO 2 , HfO 2 , TiO 2 , Ta 2 O 5 , Al 2 O 3 , HfO x N y , HfN and/or mixtures thereof.
- the high-k material is LaAlO 3 , ZrO 2 or HfO 2 , more preferably ZrO 2 or HfO 2 , more preferably HfO 2 .
- a method for forming a dielectric stack comprising the steps of:
- PECVD plasma-enhanced chemical vapor deposition process
- PE ALCVD plasma-enhanced atomic layer chemical vapor deposition
- n can be between 2 and 100, between 3 and 70, between 3 and 60, between 3 and 50, between 3 and 40, between 2 and 30, between 2 and 20, between 2 and 10.
- the method can further comprise the step of depositing a gate electrode adjacent to the dielectric layer.
- the gate electrode will be deposited on top of the dielectric layer.
- the gate electrode can be a conducting or semiconducting material such as poly Si or poly SiGe (polysilicon germanium).
- the high-k dielectric layer can be formed by ALD, ALCVD, MOCVD (metalorganic chemical vapor deposition) or sputtering.
- the plasma enhancement effect can be attributed to the enhanced reactivity of nitrogen containing species produced by the plasma, either as ions or as radicals. Energy released from ion bombardment or by radicals help to promote intermixing, densification and incorporation of silicon and nitrogen into the high-k dielectric layer. The presence of both silicon and nitrogen contributes to the compatibility between the high-k dielectric layer and the gate electrode.
- the dielectric layer between the high-k dielectric layer and gate electrode contributes to minimize interfacial reactions between polysilicon and high-k dielectric layer at elevated temperature.
- FIG. 1 a illustrates an exemplary sequence for forming a dielectric stack in accordance with a preferred embodiment.
- the sequence is shown for transistor gate dielectric structures between a semiconductor substrate and a gate electrode.
- the semiconductor substrate can be treated for subsequential ALD deposition ( 11 ).
- Such a treatment can comprise water, alcohol or Ozone treatment, intended to create surface —OH groups as known to a person skilled in the art.
- a first high-k dielectric layer is deposited on the semiconductor substrate by ALD ( 12 ).
- a dielectric layer is deposited on the first high-k layer by PECVD ( 13 ).
- the dielectric layer comprises at least Si and N. This can be done in the same tool, but in different reaction chambers. This sequence of two steps can be repeated n times ( 14 ).
- a transistor gate electrode is deposited over the dielectric layer ( 15 ).
- a step of post deposition anneal can be performed before depositing the gate electrode layer to further improve the film integrity, to promote intermixing of individual components in the stack, and to further optimize oxygen-to-nitrogen ratio in the film stack.
- FIG. 1 b illustrates another exemplary sequence for forming a dielectric stack in accordance with a preferred embodiment.
- the sequence is shown for transistor gate dielectric structures between a semiconductor substrate and a gate electrode.
- the semiconductor substrate can be treated for subsequential ALD deposition ( 11 ), as known by a person skilled in the art.
- a first high-k dielectric layer is deposited on the semiconductor substrate by ALD ( 12 ).
- a dielectric layer is deposited on the first high-k layer by PEALCVD ( 13 ).
- This step ( 13 ) comprises subjecting the substrate with the high-k dielectric layer to subsequent pulses of nitrogen comprising vapor phase reactants and silicon comprising vapor phase reactants.
- the dielectric layer comprises at least Si and N. This can be done in the same tool, but in different reaction chambers.
- This sequence of two steps can be repeated n times ( 14 ).
- a transistor gate electrode is deposited over the dielectric layer ( 15 ).
- a step of post deposition anneal can be performed before depositing the gate electrode layer to further improve the film integrity, to promote intermixing of individual components in the stack, and to further optimize oxygen-to-nitrogen ratio in the film stack.
- a dielectric stack for an integrated circuit is disclosed.
- the dielectric stack is part of a transistor gate electrode structure.
- FIG. 2 depicts a cross section of such a structure.
- the dielectric stack ( 24 ) comprises a high-k dielectric layer ( 21 ) comprising at least a high-k material, a dielectric layer ( 23 ) comprising at least silicon and nitrogen and an intermediate layer ( 22 ) between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising the high-k dielectric material, silicon and nitrogen.
- the dielectric stack ( 24 ) can be repeated n times.
- a dielectric layer can be deposited between the substrate and the high-k dielectric layer.
- This layer can have the same characteristics as the dielectric layer discussed above.
- the crystallization temperature of the dielectric stack is higher than the crystallization temperature of the high-k dielectric layer.
- the crystallization temperature is higher than 600 degrees C., higher than 700 degrees C., preferably higher than 800 degrees C. and more preferably higher than 900 degrees C.
- the crystallization temperature is between 800 degrees C. and 1200 degrees C., between 800 degrees C. and 1100 degrees C., and preferably between 900 degrees C. and 1000 degrees C.
- the silicon and nitrogen comprising dielectric layer provides a maximum barrier to prevent interfacial reaction between the high-k dielectric layer and the conductive layer (e.g. polysilicon gate electrode) compared to any dielectric stack consisting of a high-k dielectric layer such as HfO 2 , HfO x N y or HfSiON based single layer dielectric layer.
- FIG. 3 illustrates an integrated circuit (IC) structure.
- the IC ( 38 ) is formed on a semiconductor substrate ( 31 ) above an active region ( 36 ).
- the IC comprises a dielectric stack ( 37 ) that replaces silicon dioxide dielectric layers as known in the prior art.
- the IC has a dielectric stack ( 37 ) being interposed between the gate electrode ( 35 ) and the upper surface of the active region ( 36 ).
- the dielectric stack consists of a high-k dielectric layer ( 32 ) comprising at least a high-k material, a dielectric layer ( 34 ) comprising at least silicon and nitrogen and an intermediate layer ( 33 ) between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising the high-k material, silicon and nitrogen.
- the high-k material is preferably HfO 2 or ZrO 2
- the dielectric layer consists preferably of Si 3 N 4 or Si x O y N z
- the intermediate layer consists preferably of HfSiON produced by the plasma action in the PECVD or PE-ALCVD dielectric layer deposition process.
- This layer is preferably a mixture of the high-k material, silicon and nitrogen.
- This layer is preferably a mixture of the high-k material, silicon and nitrogen.
- the layers 32 , 33 and 34 will repeat.
- the gate electrode ( 35 ) is polysilicon and more preferably polysilicon germanium.
- the thickness of the high-k dielectric layer is between 0.5 nm to 20 nm, between 0.5 nm and 10 nm, between 0.5 nm and 5 nm, between 0.5 nm and 1 nm.
- the thickness of dielectric layer is between 0.5 to 20 nm, between 0.5 nm and 10 nm, between 0.5 nm and 5 nm, between 0.5 nm and 1 nm.
- the thickness of the intermediate layer can be between 0.01 nm 2 nm, between 0.01 nm and 1 nm, between 0.01 nm and 0.5 nm.
- the present invention has the advantage that the incorporation of silicon and nitrogen into the high-k dielectric layer by forming an intermediate layer of metal-silicon oxynitride, leads to improved overall structural integrity and enhanced thermal stability.
- the present invention has further the advantage that the gate oxide thickness can be minimized without sacrificing the yield of the integrate circuits.
- the dielectric stack as provided in this invention leads to excellent equivalent oxide thickness (EOT), while maintaining leakage current reduction benefits from the high-k dielectric layer, which is beneficial since it allows scaling integrated circuits and transistors in particular.
- a method for forming a dielectric stack is formed.
- the dielectric stack comprises alternating layers of HfO 2 , SiN and an intermediate layer comprising Hf, Si and N.
- the method is disclosed in FIG. 4 .
- the method comprises the step of:
- ACVD atomic layer chemical vapor deposition
- n being an integer between 0 and 100.
- PECVD plasma enhanced chemical vapor deposition process
- n is between 2 and 100, between 3 and 70, between 3 and 60, between 3 and 50, between 3 and 40, between 3 and 30, or between 2 and 10; and then
- This method results in the formation of a dielectric stack consisting of alternating layers of HfO 2 , SiN and an intermediate layer comprising Hf, Si and N.
- this dielectric stack will be referred to as the [HfO 2 /SiN]xZ laminate stack.
- Z refers to the number of times that the stack HfO 2 /SiN is repeated.
- Hafnium Dioxide HfO 2
- Hafnium Oxynitride HfO x N y
- ACVD Atomic Layer CVD
- Deposition of 1 st HfO 2 high-k layer is achieved by ALCVD which uses sequential exposure of the starting Si wafer surface to pulses of HfCl 4 and H 2 O precursors in a dedicated ALCVD reactor.
- ALCVD allows for precise HfO 2 thickness control down to (sub)monolayer level by self-limiting surface reactions during the HfCl 4 and H 2 O precursor exposure cycles, respectively.
- deposition of 1 st HfO x N y high-k dielectric is achieved by using sequential exposure of HfCl 4 , H 2 O and/or NH 3 precursors in a dedicated ALCVD reactor.
- the oxygen-to-nitrogen ratio in the ALCVD HfO x N y dielectric can be varied by controlling the H 2 O to NH 3 precursor cycle ratio after the prior HfCl 4 exposure cycle.
- the ALCVD layer produced is pure hafnium nitride, HfN.
- HfO 2 or HfO x N y include tetra-kis-diethylamido hafnium, TDEAH, Hf[N(C 2 H 5 ) 2 ] 4 and ozone (O 3 ).
- HfO 2 or HfO x N y thin dielectric layers are MOCVD or physical (sputter) deposition with suitable precursors or targets.
- an ultra-thin silicon (oxy)nitride cap or intermediate layer can be readily deposited, using a remote N 2 -plasma plus a dilute silane (SiH 4 ) flow in a PECVD reactor that is clustered with the ALCVD reactor. Silicon and nitrogen species are incorporated into the upper part of the underlying high-k dielectric layer in this process.
- a post deposition anneal step is performed to further improve the stack integrity and promote intermixing of material between the components.
- Final optimization of the dielectric stack composition in terms of nitrogen and oxygen content can be made by selecting either an oxidizing, nitridizing or inert ambient along with a suitable annealing temperature.
- Typical inert gas ambient includes N 2 , Ar, He.
- Typical oxidizing ambient gas includes O 2 , NO, N 2 O.
- Typical nitridizing gas ambient without oxygen is NH 3 .
- Capacitor leakage experiments were performed for device structures obtained via the method described above.
- the gate electrode is a conducting polysilicon gate electrode. The results of the experiments are shown in FIGS. 5 and 6 .
- the devices comprising a dielectric stack are achieved according to the following methods:
- FIG. 5 a Sequence of Steps:
- Si substrate with HfO 2 layer subjecting Si substrate with HfO 2 layer to a mixture of silane+MRG (microwave radical generator) N 2 plasma at 600 degrees C. for 15 seconds in a PECVD chamber,
- MRG microwave radical generator
- FIG. 5 b Sequence of Steps:
- Si substrate with HfO 2 layer subjecting Si substrate with HfO 2 layer to silane without N2 plasma at 600 degrees C. for 15 seconds,
- FIG. 5 c Sequence of Steps:
- FIG. 5 d Sequence of Steps:
- 51 in FIG. 5 refers to devices with a 100 by 100 ⁇ m 2 device area
- 52 refers to devices with a 50 by 50 ⁇ m 2 device area
- 53 refers to devices with a 30 by 30 ⁇ m 2 device area.
- Experiment 5 a shows low leakage current capacitor devices with well-behaved area-scaling.
- the effects of (a) silane and nitrogen plasma exposure; (b) silane exposure only; (c) N 2 -plasma exposure only and (d) N 2 post deposition anneal (PDA) on 4 nm HfO 2 are shown.
- a thermal silane exposure without the N 2 -plasma ( FIG. 5 b ) on 4 nm HfO 2 did not achieve the same low leakage current as in FIG. 5 a .
- the plasma enhancement effect can be attributed to the enhanced reactivity of nitrogen-containing species produced by the plasma, either as ions or radicals.
- FIG. 6 a shows a TEM of a dielectric stack.
- the dielectric stack is obtained by the following method:
- Si substrate with HfO 2 layer subjecting Si substrate with HfO 2 layer to a mixture of silane+MRG (microwave radical generator) N 2 plasma at 600 degrees C. for 15 seconds in a PECVD chamber,
- MRG microwave radical generator
- FIG. 6 a 61 refers to the HfO 2 layer, 62 refers to SiN layer and 63 refer to the poly Si gate electrode.
- the dielectric stack was obtained by the method as described for FIG. 5 a .
- FIG. 6 a shows that incorporation of silicon and nitrogen into bulk of the HfO 2 or HfO x N y high-k dielectric layers results in the formation of an intermediate layer of hafnium-silicon oxynitride (HfSiON), leading to improved overall structural integrity and enhanced thermal stability against interface reaction with polysilicon (gate electrode).
- the intermediate layer formation occurs due to the plasma action from the deposition of the silicon oxynitride by plasma enhanced chemical vapor deposition. Relative ratio of Hf, O, Si, and N components can be adjusted by individual layer thickness and deposition parameters.
- FIG. 6 b shows a TEM image of a dielectric stack obtained by the method:
- 61 refers to the HfO 2 layer
- 64 refers to a gray contrast haze layer, and typical for the HfO 2 /polySi interface due to interface reaction
- 63 refers to the poly Si gate electrode.
- the silicon-rich SiN layer 62 of FIG. 6 a between the HfO 2 layer and polisilicon gate electrode, provides an effective barrier to prevent undesired interfacial reaction between HfO 2 and polysilicon (gate electrode) compared to any HfO 2 , HfO x N y or HfSiON based single layer dielectric.
- the dielectric stacks are obtained by the method:
- Si substrate with HfO 2 layer subjecting Si substrate with HfO 2 layer to a mixture of silane+MRG (microwave radical generator) N 2 plasma for 150 seconds in a PECVD chamber at 600 degrees C., resulting in a layer of SiN (thickness approximately 5 nm),
- silane+MRG microwave radical generator
- ToF-SIMS depth profiles show the presence of HfN + secondary ions ( 74 ).
- 71 refers in this figure to Si
- 72 refers to Hf
- 73 refers to SiN 2 , indicating the presence of an intermediate Hf(Si)-oxynitride layer between the HfO 2 layer and the SiN layer.
- FIG. 8 a - c show the x-ray diffraction spectra of the [HfO 2 /SiN]x10 laminate structure with 30 ( FIG. 8 a ), 20 ( FIG. 8 b ) and 15 cycles ( FIG. 8 c ) of HfCl 4 /H 2 O and 0.5 nm SiN (repeated 10 times).
- Diffraction peaks located between 5-10 degrees 2-theta angle represent reflections from the individual laminated [HfO 2 /SiN] layers.
- a second x-ray diffraction peak located between 2-theta angle of 29-31 degrees start to emerge at or above 900° C., indicating the crystallization of the HfO 2 phase-separated from [HfO 2 /SiN] laminate.
- the dielectric stacks were obtained according to the method:
- Si substrate with HfO 2 layer subjecting Si substrate with HfO 2 layer to a mixture of silane+MRG (microwave radical generator) N 2 plasma in a PECVD chamber at 550 degrees C., resulting in a layer of SiN.
- silane+MRG microwave radical generator
- the dielectric stacks are obtained by the method of:
- Si substrate with HfO 2 layer subjecting Si substrate with HfO 2 layer to a mixture of silane+MRG (microwave radical generator) N 2 plasma in a PECVD chamber at 550 degrees C., resulting in a layer of SiN deposition of the poly silicon gate layer (only for condition 92 and 93 ), and optionally
- FIG. 10 show the cumulative distribution of gate leakage current for a sample of 30 diode/capacitor devices.
Abstract
Description
- The present invention relates to integrated circuit fabrication processes and in particular to the formation of an integrated circuit comprising a multilayer dielectric stack of high-k material. The present invention further relates to such dielectric stack in an integrated circuit and to a MOS transistor having such multilayer dielectric stack.
- A multilayer dielectric stack according to the present invention replaces prior art silicon dioxide as dielectric layer in integrated circuits.
- When integrating a high-k dielectric with a gate electrode into a conventional CMOS gate stack, two major process/thermal stability issues need to be addressed and tackled. It is hereby important to
- 1. Reduce reaction(s) at the top interface between the high-k dielectric and the gate electrode such as polysilicon either during polysilicon deposition and/or during subsequent thermal processing and/or to
- 2. Minimize degradation of high-k material integrity due to crystallization, which leads to formation of structural defects such as oxygen vacancies and grain boundaries that interact with gate electrode deposition process leading to pathways of enhanced electrical leakage and/or of dopant/impurity diffusion.
- Based upon knowledge from conventional SiO2-based CMOS gate dielectric material (which is amorphous and 100% compatible with polysilicon gate), it is known that nitrogen is a key modifier introduced to improve the resistance against boron diffusion. Likewise, in high-k dielectric, enhanced stability against dopant (boron) diffusion from the polysilicon gate can be achieved through the use of a metal-oxynitride (MOxNy) or nitridation of metal oxide (U.S. Pat. No. 6,251,761). U.S. Pat. No. 6,251,761 describes a gate stack including a gate dielectric with reduced effective electrical thickness. A high-k dielectric is deposited over the silicon substrate. In a next step, remote plasma nitridation of the high-k dielectric layer is performed to convert the upper surface of the high-k dielectric into a nitride layer. A conductive layer is formed over the nitride layer to complete the CMOS gate stack.
- Published US patent application No. 2002/0130340 A1 discloses a multilayer dielectric stack, which has alternating layers of high-k material and an interposing material. The interposing material can be Al2O3, AlN, SiN, Si3N4 and SiO2. The interposing material can be deposited by atomic layer deposition, sputtering or evaporation, resulting in the deposition of the interposing layer on the dielectric layer. Each layer is preferably less tan 50 Angstroms thick. This structure inhibits and prevents the crystallization of the high k-material.
- In a first aspect of this invention, a method for forming a dielectric stack in an integrated circuit structure is disclosed comprising the steps of:
- forming a high-k dielectric layer on a semiconductor substrate, and
- subjecting the semiconductor substrate with the high-k dielectric layer to a nitrogen comprising vapor phase reactant and a silicon comprising vapor phase reactant in a plasma-enhanced chemical vapor deposition process (PECVD) or plasma-enhanced atomic layer chemical vapor deposition (PE ALCVD) process.
- With a process according to the present invention, highly reactive species such as nitrogen ions or radicals and silicon species penetrate into the upper part of the high-k material, thereby promoting intermixing, densification and formation of an intermediate layer. The intermediate layer comprises at least the high-k material, silicon and nitrogen. Highly reactive species are formed by plasma-enhanced chemical vapor deposition (PECVD) or plasma-enhanced atomic layer chemical vapor deposition (PE ALCVD). Highly reactive species can be radicals or ions. Consequently, using PECVD or PE ALCVD, the species formed in the plasma penetrate into the upper part of the underlying high-k dielectric layer.
- The presence of both silicon and nitrogen contributes to the compatibility between the high-k dielectric layer and any other layer such as e.g. the gate electrode.
- Compared to prior art methods, the formation of an interfacial layer between the high-k dielectric layer and e.g. the gate electrode layer is avoided, thus leading to improved electrical properties.
- In an embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the subjecting step results in the formation of a dielectric layer comprising at least silicon and nitrogen and essentially no or no high-k material and in the formation of an intermediate layer disposed between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising at least the high-k material, silicon and nitrogen.
- In a preferred embodiment, the dielectric layer is selected from the group consisting of SiN, SiON and Si3N4.
- In another embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the subjecting step results in the formation of an intermediate layer adjacent to the high-k dielectric layer and the dielectric layer, the intermediate layer comprising at least the high-k material, silicon and nitrogen. Preferably, the intermediate layer is on top of the high-k dielectric layer. The subjecting step results in essentially no and/or no formation at all of the dielectric layer (in the case of very thin layers).
- In an embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed further comprising subjecting the substrate with the high-k dielectric layer to an oxygen comprising vapor phase reactant. In this case, the intermediate layer formed comprises oxygen in addition.
- In a preferred embodiment, the silicon comprising compound or vapor phase reactant is selected from the group consisting of SiH4, Si2H6, Si3H8, SixHyClz and combinations thereof. In another preferred embodiment, the nitrogen comprising compound is selected from the group consisting of nitrogen, ammonia, N2H4, NO, N2O, and combinations thereof. In a further embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the ratio of silane:nitrogen containing compounds is in the range of 1:1 to 1:10000. Preferably, the ratio is between 1:1 and 1:1000.
- In an embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed further comprising repeating the forming step and the subjecting step between 2 and 100 times, between 2 and 50 times, between 10 and 50 times, between 10 and 30 times and between 2 and 10 times.
- In an embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the high-k dielectric layer comprises a high-k material selected from the group consisting of a transition metal or lanthanide oxide and a transition metal or lanthanide oxynitride. In a preferred embodiment, the high-k material is selected from the group consisting of ZrO2, HfO2, TiO2, Ta2O5, Al2O3, HfOxNy, HfN, LaxOy, LaAlO3, and/or mixtures thereof.
- In a preferred embodiment of the invention, the forming step comprises subjecting the semiconducting substrate to an atomic layer deposition process.
- In a preferred embodiment, the high-k material is selected from the group consisting of HfO2, HfOxNy and HfN.
- In an embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the subjecting step is performed in a plasma-enhanced chemical vapor deposition (PECVD) chamber at a temperature in the range of 300 to 600 degrees Celsius.
- In a further embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the subjecting step is performed in a plasma-enhanced atomic layer chemical vapor deposition chamber at a temperature in the range of 300 to 600 degrees Celsius. The semiconductor substrate with the high-k dielectric layer is subjected to alternating pulses of precursor compounds, the precursor compound being a nitrogen containing vapor phase reactant or a silicon containing vapor phase reactant.
- In a further embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the subjecting step is performed at a pressure in the range of 10−3 to 100 Torr. The pressure can vary, depending on the composition of reactants. For N2 as reactant, the pressure is preferably between 0.01 and 100 Torr, while for a silane reactant, the pressure is between 1 and 100 mTorr.
- In a further embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the subjecting step is performed in a plasma with a plasma density in the range of 1010 to 1013 reactive species cm−3.
- In another embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the high-k dielectric layer has a thickness in the range of 0.01 nm to 20 nm, 0.05 nm to 20 nm, 0.1 nm to 20 nm, 0.3 nm to 20 nm, 0.5 nm to 20 nm. The dielectric layer has a thickness in the range of 0.01 nm to 20 nm, 0.05 nm to 20 nm, 0.1 nm to 20 nm, 0.3 nm to 20 nm, 0.5 nm to 20 nm. Preferably, the thickness is below 1 nm, below 0.5 nm and below 0.3 nm. According to an embodiment of the first aspect of this invention, the dielectric layer has a thickness between 0.01 nm and 1 nm, between 0.01 nm and 0.5 nm, between 0.01 nm and 0.1 nm.
- In another embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed wherein the step of forming a high-k dielectric layer on a semiconductor substrate is performed by an atomic layer deposition process (ALD). In another embodiment of the first aspect of this invention, a method as recited in any of the previous embodiments is disclosed further comprising the step of annealing the semiconductor substrate at a temperature between 500 and 1000 degrees Celsius. Preferably, the substrate is annealed at a temperature between 600 and 900 degrees Celsius. The step of annealing can be performed after each individual step or can be performed after the formation of the dielectric stack.
- The method as recited in the previous embodiments can further comprise the step of depositing a conductive layer over the dielectric stack. The conductive layer can comprise silicon. The conductive layer can be polysilicon, polysilicon germanium or a metal. In a subsequent step, the dielectric stack and the electrode layer are patterned to form the desired integrated circuit.
- In a second aspect of the invention, a dielectric stack in an integrated circuit is provided. The dielectric stack comprises:
-
- a high-k dielectric layer comprising at least a high-k material; and
- an intermediate layer disposed between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising the high-k material, silicon and nitrogen.
- In a preferred embodiment of the second aspect of this invention, a device a recited in any of the previous embodiments is disclosed wherein the dielectric stack further comprises a dielectric layer comprising at least silicon and nitrogen.
- In an embodiment of the second aspect of this invention, a device as recited in any of the previous embodiments is disclosed wherein the dielectric stack is characterized by a crystallization temperature, the crystallization temperature of the dielectric stack is higher than the crystallization temperature of the high-k material.
- In a preferred embodiment of the second aspect of this invention, a dielectric stack as recited in any of the previous embodiments is disclosed wherein the crystallization temperature is between 800 degrees C. and 1200 degrees C.
- In another embodiment of the second aspect of this invention, the intermediate layer and the dielectric layer are formed by subjecting the semiconductor substrate with the high-k dielectric layer to a nitrogen comprising vapor phase reactant and a silicon comprising vapor phase reactant in a plasma-enhanced chemical vapor deposition process (PECVD) or plasma-enhanced atomic layer chemical vapor deposition (PE ALCVD) process.
- In another embodiment of the second aspect of this invention, the high-k layer is formed by subjecting the semiconductor substrate to an atomic layer deposition process.
- In another embodiment of the second aspect of this invention, a dielectric stack as recited in any of the previous embodiments is disclosed wherein a sequence of the high-k dielectric layer, the intermediate layer and the dielectric layer is repeated between 3 and 60 times. In a preferred embodiment, a dielectric stack is provided wherein between one of the high-k dielectric layers and an adjacent one of the dielectric layers an intermediate layer is disposed, the intermediate layer comprising the dielectric material, silicon and nitrogen.
- In another embodiment, the dielectric layer and the intermediate layer further comprise oxygen.
- In another embodiment of the second aspect of this invention, a dielectric stack as recited in any of the previous embodiments is disclosed wherein the dielectric layer does essentially not comprise the high-k material. In a preferred embodiment, the intermediate layer comprises the high-k material, nitrogen and silicon and optionally oxygen.
- In another embodiment, the stack as recited in any of the previous embodiments comprises a dielectric layer selected from the group consisting of SiN, SiON, and Si3N4.
In another embodiment of the second aspect of this invention, a dielectric stack as recited in any of the previous embodiments is disclosed wherein the high-k dielectric layer comprises a compound selected from the group consisting of a transition metal oxide or a transition metal oxynitride. In a preferred embodiment, the high-k dielectric layer comprises a high-k dielectric material selected from the group consisting of ZrO2, HfO2, TiO2, Ta2O5, Al2O3, HfOxNy, HfN and/or mixtures thereof. More preferably, the high-k dielectric material is selected from the group consisting of HfO2, HfOxNy and HfN. - In a further embodiment of the second aspect of this invention, a dielectric stack as recited in any of the previous embodiment is disclosed wherein the high-k dielectric layer has a thickness between 0.5 nm to 20 nm.
- In a further embodiment of the second aspect of this invention, a dielectric stack as recited in any of the previous embodiment is disclosed wherein the dielectric layer has a thickness in the range of 0.01 nm to 20 nm, 0.05 nm to 20 nm, 0.1 nm to 20 nm, 0.3 nm to 20 nm, 0.5 nm to 20 nm. Preferably, the thickness is below 1 nm, below 0.5 nm and below 0.3 nm. According to an embodiment of the second aspect of this invention, the dielectric layer has a thickness between 0.01 nm and 1 nm, between 0.01 nm and 0.5 nm, between 0.01 nm and 0.1 nm.
- In an embodiment of the invention, the intermediate layer comprises Hf, nitrogen and silicon and oxygen.
- Preferably the dielectric layer of the stack is selected from the group consisting of SiN, SiON and Si3N4.
- In a third aspect of this invention, a MOS transistor is disclosed. The MOS transistor comprises:
- a gate electrode;
- a channel region having an upper surface underlying the gate electrode; and
- a dielectric stack being interposed between the gate electrode and the upper surface of the channel region, the dielectric stack comprising a high-k dielectric layer comprising at least a high-k material, a dielectric layer comprising at least silicon and nitrogen and an intermediate layer between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising the high-k material, silicon and nitrogen.
- The dielectric stack is characterized by the features as disclosed in the second aspect of the invention.
- The
FIG. 1 a represents a flow chart of a method of forming a dielectric stack according to a preferred embodiment of the invention. - The
FIG. 1 b represents a flow chart of a method of forming a dielectric stack according to another preferred embodiment of the invention. - The
FIG. 2 represents a schematic view of a dielectric stack according to an embodiment of the present invention. - The
FIG. 3 represents a schematic view of an integrated circuit structure according to an embodiment of the present invention. - The
FIG. 4 represents a flow chart of a method of forming an integrated circuit according to a preferred embodiment of the invention. - The
FIGS. 5 a-d represent the results of capacitor leakage experiments for devices obtained according to various methods. - The
FIGS. 6 a-b represents a TEM picture of dielectric stacks obtained according to various methods. - The
FIG. 7 represents a ToF-SIMS depth profile for a preferred embodiment of a device of the present invention. - The
FIGS. 8 a-c represents X-Ray diffraction spectra of devices obtained according to various methods. - The
FIG. 9 represents channel electron mobility measurements from n-MOSFET devices obtained according to various methods. - The
FIG. 10 represents the cumulative distribution of gate leakage current for 30 diode/capacitor devices obtained according to different methods. - In relation to the appended drawings the present invention is described in details in the sequel. It is apparent however that a person skilled in the art can imagine several other equivalent embodiments or other ways of executing the present invention.
- While the invention is described in conjunction with a MOS transistor, it will be apparent to those ordinary skilled in the art that the benefits of this invention can be applied to other transistor structures and other structures such as memory cell capacitors. In particular, one ordinary skilled in the art can imagine other situations where similar electrical and physical properties at an interface are desired.
- For the purpose of this invention, a Plasma enhanced CVD or plasma enhanced ALCVD process should be understood as a process wherein at least one chemical compound is subjected to a plasma source, thereby creating highly reactive species such as radicals or ions.
- The term high-k dielectric layer should be understood as a layer comprising a high-k material. A high-k material is a dielectric material having a dielectric constant greater than the dielectric constant of silicon oxide and preferably greater than 10.
- The high-k material can be a high-k material selected from the group consisting of a transition metal oxide or a transition metal oxynitride, a rare earth metal oxide, a rare earth metal oxynitride. Transition metals can be Group IV or Group V metals such as e.g. Ti, Zr, Hf, V, Nb, and Ta. Rare earth metal can be Lanthanides such as e.g. So, Ce, Pr, Eu. Lanthanides meaning an element from the lanthanide series. High-k material can also include lanthanum oxide, neodymium oxide and cerium oxide. Preferably, the metal is Hafnium (Hf). Preferably, the high-k material is selected from the group consisting of ZrO2, HfO2, TiO2, Ta2O5, Al2O3, HfOxNy, HfN and/or mixtures thereof. Preferably, the high-k material is LaAlO3, ZrO2 or HfO2, more preferably ZrO2 or HfO2, more preferably HfO2.
- In a first aspect of this invention, a method for forming a dielectric stack is provided, the method comprising the steps of:
- forming a high-k dielectric layer on a semiconductor substrate, and
- subjecting the semiconductor substrate to nitrogen comprising vapor phase reactants and silicon comprising vapor phase reactants in a plasma-enhanced chemical vapor deposition process (PECVD) or plasma-enhanced atomic layer chemical vapor deposition (PE ALCVD) process.
- Preferably, the forming step and the subjecting step are repeated n times, such that a laminate structure is formed. n can be between 2 and 100, between 3 and 70, between 3 and 60, between 3 and 50, between 3 and 40, between 2 and 30, between 2 and 20, between 2 and 10.
- The method can further comprise the step of depositing a gate electrode adjacent to the dielectric layer. Preferably, the gate electrode will be deposited on top of the dielectric layer. The gate electrode can be a conducting or semiconducting material such as poly Si or poly SiGe (polysilicon germanium).
- The high-k dielectric layer can be formed by ALD, ALCVD, MOCVD (metalorganic chemical vapor deposition) or sputtering.
- The plasma enhancement effect can be attributed to the enhanced reactivity of nitrogen containing species produced by the plasma, either as ions or as radicals. Energy released from ion bombardment or by radicals help to promote intermixing, densification and incorporation of silicon and nitrogen into the high-k dielectric layer. The presence of both silicon and nitrogen contributes to the compatibility between the high-k dielectric layer and the gate electrode.
- The dielectric layer between the high-k dielectric layer and gate electrode contributes to minimize interfacial reactions between polysilicon and high-k dielectric layer at elevated temperature.
-
FIG. 1 a illustrates an exemplary sequence for forming a dielectric stack in accordance with a preferred embodiment. The sequence is shown for transistor gate dielectric structures between a semiconductor substrate and a gate electrode. Initially, the semiconductor substrate can be treated for subsequential ALD deposition (11). Such a treatment can comprise water, alcohol or Ozone treatment, intended to create surface —OH groups as known to a person skilled in the art. Subsequently, a first high-k dielectric layer is deposited on the semiconductor substrate by ALD (12). A dielectric layer is deposited on the first high-k layer by PECVD (13). The dielectric layer comprises at least Si and N. This can be done in the same tool, but in different reaction chambers. This sequence of two steps can be repeated n times (14). Subsequently, a transistor gate electrode is deposited over the dielectric layer (15). - Optionally, a step of post deposition anneal can be performed before depositing the gate electrode layer to further improve the film integrity, to promote intermixing of individual components in the stack, and to further optimize oxygen-to-nitrogen ratio in the film stack.
-
FIG. 1 b illustrates another exemplary sequence for forming a dielectric stack in accordance with a preferred embodiment. The sequence is shown for transistor gate dielectric structures between a semiconductor substrate and a gate electrode. Initially, the semiconductor substrate can be treated for subsequential ALD deposition (11), as known by a person skilled in the art. Subsequently, a first high-k dielectric layer is deposited on the semiconductor substrate by ALD (12). A dielectric layer is deposited on the first high-k layer by PEALCVD (13). This step (13) comprises subjecting the substrate with the high-k dielectric layer to subsequent pulses of nitrogen comprising vapor phase reactants and silicon comprising vapor phase reactants. The dielectric layer comprises at least Si and N. This can be done in the same tool, but in different reaction chambers. This sequence of two steps can be repeated n times (14). Subsequently, a transistor gate electrode is deposited over the dielectric layer (15). - Optionally, a step of post deposition anneal can be performed before depositing the gate electrode layer to further improve the film integrity, to promote intermixing of individual components in the stack, and to further optimize oxygen-to-nitrogen ratio in the film stack.
- In a second aspect of this invention a dielectric stack for an integrated circuit is disclosed. In an embodiment, the dielectric stack is part of a transistor gate electrode structure.
FIG. 2 depicts a cross section of such a structure. The dielectric stack (24) comprises a high-k dielectric layer (21) comprising at least a high-k material, a dielectric layer (23) comprising at least silicon and nitrogen and an intermediate layer (22) between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising the high-k dielectric material, silicon and nitrogen. The dielectric stack (24) can be repeated n times. - Optionally, a dielectric layer can be deposited between the substrate and the high-k dielectric layer. This layer can have the same characteristics as the dielectric layer discussed above.
- The crystallization temperature of the dielectric stack is higher than the crystallization temperature of the high-k dielectric layer. The crystallization temperature is higher than 600 degrees C., higher than 700 degrees C., preferably higher than 800 degrees C. and more preferably higher than 900 degrees C. The crystallization temperature is between 800 degrees C. and 1200 degrees C., between 800 degrees C. and 1100 degrees C., and preferably between 900 degrees C. and 1000 degrees C.
- The silicon and nitrogen comprising dielectric layer provides a maximum barrier to prevent interfacial reaction between the high-k dielectric layer and the conductive layer (e.g. polysilicon gate electrode) compared to any dielectric stack consisting of a high-k dielectric layer such as HfO2, HfOxNy or HfSiON based single layer dielectric layer.
-
FIG. 3 illustrates an integrated circuit (IC) structure. The IC (38) is formed on a semiconductor substrate (31) above an active region (36). The IC comprises a dielectric stack (37) that replaces silicon dioxide dielectric layers as known in the prior art. The IC has a dielectric stack (37) being interposed between the gate electrode (35) and the upper surface of the active region (36). The dielectric stack consists of a high-k dielectric layer (32) comprising at least a high-k material, a dielectric layer (34) comprising at least silicon and nitrogen and an intermediate layer (33) between the high-k dielectric layer and the dielectric layer, the intermediate layer comprising the high-k material, silicon and nitrogen. - The high-k material is preferably HfO2 or ZrO2, while the dielectric layer consists preferably of Si3N4 or SixOyNz. The intermediate layer consists preferably of HfSiON produced by the plasma action in the PECVD or PE-ALCVD dielectric layer deposition process. This layer is preferably a mixture of the high-k material, silicon and nitrogen. This layer is preferably a mixture of the high-k material, silicon and nitrogen.
- In a preferred embodiment, the
layers - In a preferred embodiment, the gate electrode (35) is polysilicon and more preferably polysilicon germanium.
- The thickness of the high-k dielectric layer is between 0.5 nm to 20 nm, between 0.5 nm and 10 nm, between 0.5 nm and 5 nm, between 0.5 nm and 1 nm. The thickness of dielectric layer is between 0.5 to 20 nm, between 0.5 nm and 10 nm, between 0.5 nm and 5 nm, between 0.5 nm and 1 nm. The thickness of the intermediate layer can be between 0.01
nm 2 nm, between 0.01 nm and 1 nm, between 0.01 nm and 0.5 nm. - The present invention has the advantage that the incorporation of silicon and nitrogen into the high-k dielectric layer by forming an intermediate layer of metal-silicon oxynitride, leads to improved overall structural integrity and enhanced thermal stability.
- The present invention has further the advantage that the gate oxide thickness can be minimized without sacrificing the yield of the integrate circuits. The dielectric stack as provided in this invention leads to excellent equivalent oxide thickness (EOT), while maintaining leakage current reduction benefits from the high-k dielectric layer, which is beneficial since it allows scaling integrated circuits and transistors in particular.
- In a preferred embodiment, a method for forming a dielectric stack is formed. The dielectric stack comprises alternating layers of HfO2, SiN and an intermediate layer comprising Hf, Si and N. The method is disclosed in
FIG. 4 . The method comprises the step of: - preparing a silicon surface for ALD (41);
- forming a layer of HfO2 by atomic layer chemical vapor deposition (ALCVD) on the silicon substrate (42);
- subjecting the silicon substrate with the HfO2 layer to a nitrogen containing species and a silicon containing species in a plasma enhanced chemical vapor deposition process (PECVD) (43), repeating step (42) and (43) n times, n being an integer between 0 and 100. Preferably, n is between 2 and 100, between 3 and 70, between 3 and 60, between 3 and 50, between 3 and 40, between 3 and 30, or between 2 and 10; and then
- depositing a poly Si gate electrode layer (45).
- This method results in the formation of a dielectric stack consisting of alternating layers of HfO2, SiN and an intermediate layer comprising Hf, Si and N. For the purpose of this invention, this dielectric stack will be referred to as the [HfO2/SiN]xZ laminate stack. Z refers to the number of times that the stack HfO2/SiN is repeated. This dielectric stack results in advantages obtained by 1) incorporation of silicon and nitrogen into the high-k material; 2) formation of an intermediate layer containing HfSiON. Consequently, high-k/polysilicon interface reaction is prevented and concurrently the thermal stability of the high-k material against crystallization is improved.
- Deposition of 1st HfO2 high-k layer is achieved by ALCVD which uses sequential exposure of the starting Si wafer surface to pulses of HfCl4 and H2O precursors in a dedicated ALCVD reactor. ALCVD allows for precise HfO2 thickness control down to (sub)monolayer level by self-limiting surface reactions during the HfCl4 and H2O precursor exposure cycles, respectively.
- Alternatively, deposition of 1st HfOxNy high-k dielectric is achieved by using sequential exposure of HfCl4, H2O and/or NH3 precursors in a dedicated ALCVD reactor. The oxygen-to-nitrogen ratio in the ALCVD HfOxNy dielectric can be varied by controlling the H2O to NH3 precursor cycle ratio after the prior HfCl4 exposure cycle. In the case of using NH3 precursor only, the ALCVD layer produced is pure hafnium nitride, HfN. Other precursors that can be used for producing HfO2 or HfOxNy include tetra-kis-diethylamido hafnium, TDEAH, Hf[N(C2H5)2]4 and ozone (O3).
- Alternative methods to produce HfO2 or HfOxNy thin dielectric layers are MOCVD or physical (sputter) deposition with suitable precursors or targets.
- Following the formation of HfO2 high-k dielectric, an ultra-thin silicon (oxy)nitride cap or intermediate layer can be readily deposited, using a remote N2-plasma plus a dilute silane (SiH4) flow in a PECVD reactor that is clustered with the ALCVD reactor. Silicon and nitrogen species are incorporated into the upper part of the underlying high-k dielectric layer in this process.
- The above CVD processes are repeated twice to complete the fabrication of the stack.
- A post deposition anneal step is performed to further improve the stack integrity and promote intermixing of material between the components. Final optimization of the dielectric stack composition in terms of nitrogen and oxygen content can be made by selecting either an oxidizing, nitridizing or inert ambient along with a suitable annealing temperature. Typical inert gas ambient includes N2, Ar, He. Typical oxidizing ambient gas includes O2, NO, N2O. Typical nitridizing gas ambient without oxygen is NH3.
- Capacitor leakage experiments were performed for device structures obtained via the method described above. The gate electrode is a conducting polysilicon gate electrode. The results of the experiments are shown in
FIGS. 5 and 6 . - The devices comprising a dielectric stack are achieved according to the following methods:
-
FIG. 5 a—Sequence of Steps: - treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of 80 cycles, resulting in a layer of HfO2 of approximate thickness of 4 nm,
- subjecting Si substrate with HfO2 layer to a mixture of silane+MRG (microwave radical generator) N2 plasma at 600 degrees C. for 15 seconds in a PECVD chamber,
- deposition of the poly silicon gate layer, and
- post gate electrode anneal at 1000 degrees C.
-
FIG. 5 b—Sequence of Steps: - treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of 80 cycles, resulting in a layer of HfO2 of approximate thickness of 4 nm,
- subjecting Si substrate with HfO2 layer to silane without N2 plasma at 600 degrees C. for 15 seconds,
- deposition of the poly silicon gate layer, and
- post gate electrode anneal at 1000 degrees C.
-
FIG. 5 c—Sequence of Steps: - treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of 80 cycles, resulting in a layer of HfO2 of approximate thickness of 4 nm,
- subjecting Si substrate with HfO2 layer to MRG N2 plasma in a PECVD chamber at 600 degrees C. for 15 seconds,
- deposition of the poly silicon gate layer, and
- post gate electrode anneal at 1000 degrees C.
-
FIG. 5 d—Sequence of Steps: - treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of 80 cycles, resulting in a layer of HfO2 of approximate thickness of 4 nm,
-
- subjecting Si substrate with HfO2 layer to N2
- post deposition anneal (PDA) treatment at 600 degrees C. for 15 seconds,
- deposition of the poly silicon gate layer, and
- post gate electrode anneal at 1000 degrees C.
- 51 in
FIG. 5 refers to devices with a 100 by 100 μm2 device area, 52 refers to devices with a 50 by 50 μm2 device area, 53 refers to devices with a 30 by 30 μm2 device area. - Experiment 5 a shows low leakage current capacitor devices with well-behaved area-scaling. In the next set of comparison experiments, the effects of (a) silane and nitrogen plasma exposure; (b) silane exposure only; (c) N2-plasma exposure only and (d) N2 post deposition anneal (PDA) on 4 nm HfO2 are shown. A thermal silane exposure without the N2-plasma (
FIG. 5 b) on 4 nm HfO2 did not achieve the same low leakage current as inFIG. 5 a. The plasma enhancement effect can be attributed to the enhanced reactivity of nitrogen-containing species produced by the plasma, either as ions or radicals. Energy released from ion bombardment or by radicals help to promote intermixing, densification and silicon/nitrogen incorporation into the HfO2 high-k dielectric. The presence of both silicon and nitrogen contributes to ensure polysilicon compatibility of the 4 nm HfO2 dielectric as a N2-plasma treatment alone (FIG. 5 c) or a N2 post deposition anneal treatment (FIG. 5 d) did not achieve the same low leakage current as the plasma CVD SiN—HfO2 control (FIG. 5 a). Thus, the incorporation of silicon and nitrogen into the HfO2 from the N2-plasma/silane plasma by plasma enhanced CVD process deposition process contributes to a dielectric stack with desired chemical composition and structural/electrical integrity. - The effect of reduced interface reaction between polysilicon gate and high-k material is demonstrated in the cross-sectional TEM images shown in
FIG. 6 .FIG. 6 a shows a TEM of a dielectric stack. The dielectric stack is obtained by the following method: - treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of 80 cycles, resulting in a layer of HfO2 of approximate thickness of 4 nm,
- subjecting Si substrate with HfO2 layer to a mixture of silane+MRG (microwave radical generator) N2 plasma at 600 degrees C. for 15 seconds in a PECVD chamber,
- deposition of the poly silicon gate layer, and
- post gate electrode anneal at 1000 degrees C.
- In
FIG. 6 a, 61 refers to the HfO2 layer, 62 refers to SiN layer and 63 refer to the poly Si gate electrode. The dielectric stack was obtained by the method as described forFIG. 5 a.FIG. 6 a shows that incorporation of silicon and nitrogen into bulk of the HfO2 or HfOxNy high-k dielectric layers results in the formation of an intermediate layer of hafnium-silicon oxynitride (HfSiON), leading to improved overall structural integrity and enhanced thermal stability against interface reaction with polysilicon (gate electrode). The intermediate layer formation occurs due to the plasma action from the deposition of the silicon oxynitride by plasma enhanced chemical vapor deposition. Relative ratio of Hf, O, Si, and N components can be adjusted by individual layer thickness and deposition parameters. -
FIG. 6 b shows a TEM image of a dielectric stack obtained by the method: - treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of 80 cycles, resulting in a layer of HfO2 of approximate thickness of 4 nm,
- deposition of the poly silicon gate layer, and
- post gate electrode anneal at 1000 degrees C.
- In
FIG. 6 b, 61 refer to the HfO2 layer, 64 refer to a gray contrast haze layer, and typical for the HfO2/polySi interface due to interface reaction and 63 refers to the poly Si gate electrode. - The silicon-
rich SiN layer 62 ofFIG. 6 a, between the HfO2 layer and polisilicon gate electrode, provides an effective barrier to prevent undesired interfacial reaction between HfO2 and polysilicon (gate electrode) compared to any HfO2, HfOxNy or HfSiON based single layer dielectric. - An example of the intermixing of the high-k layer with silicon and nitrogen is described in the ToF SIMS depth profiles shown in
FIG. 7 . - The dielectric stacks are obtained by the method:
- treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of 80 cycles, resulting in a layer of HfO2 of approximate thickness of 4 nm,
- subjecting Si substrate with HfO2 layer to a mixture of silane+MRG (microwave radical generator) N2 plasma for 150 seconds in a PECVD chamber at 600 degrees C., resulting in a layer of SiN (thickness approximately 5 nm),
- deposition of the poly silicon gate layer, and
- post gate electrode anneal at 1000 degrees C.
- ToF-SIMS depth profiles show the presence of HfN+ secondary ions (74). 71 refers in this figure to Si, 72 refers to Hf and 73 refers to SiN2, indicating the presence of an intermediate Hf(Si)-oxynitride layer between the HfO2 layer and the SiN layer.
- Experimental results on crystallization temperature of the dielectric stack are shown in
FIG. 8 . - Binary oxides such as ZrO2 and HfO2 have a crystallization onset temperature between 450-550 degrees C. The [HfO2/SiN] laminate approach significantly increases the crystallization onset temperature to 900-1000 degrees C.
FIG. 8 a-c show the x-ray diffraction spectra of the [HfO2/SiN]x10 laminate structure with 30 (FIG. 8 a), 20 (FIG. 8 b) and 15 cycles (FIG. 8 c) of HfCl4/H2O and 0.5 nm SiN (repeated 10 times). Diffraction peaks located between 5-10 degrees 2-theta angle represent reflections from the individual laminated [HfO2/SiN] layers. As a function of increasing annealing temperature, a second x-ray diffraction peak located between 2-theta angle of 29-31 degrees start to emerge at or above 900° C., indicating the crystallization of the HfO2 phase-separated from [HfO2/SiN] laminate. - The dielectric stacks were obtained according to the method:
- treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- performing 10 times the sequence of steps:
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, repeat this up to a total of y cycles, resulting in layer of HfO2, and
- subjecting Si substrate with HfO2 layer to a mixture of silane+MRG (microwave radical generator) N2 plasma in a PECVD chamber at 550 degrees C., resulting in a layer of SiN.
- Hereby, y=30 (
FIG. 8 a), y=20 (FIG. 8 b), y=15 (FIG. 8 c). -
FIG. 9 shows channel electron mobility measurements from nMOSFET devices fabricated with HfO2 (91), HfO2/SiN (92), and [HfO2/SiN]x2 (z=2) laminate (93) as dielectric stack. It can be seen that the [HfO2/SiN]x2 laminate (93) and the HfO2/SiN (92) has a higher peak and overall mobility compared to the HfO2 reference (91). - The dielectric stacks are obtained by the method of:
- treating Si substrate to a mixture of O3 and DI water to obtain an —OH terminated surface,
- subjecting Si substrate subsequently to HfCl4 and H2O precursors (one cycle) in ALD chamber, (up to a total of 80 cycles for
condition 91, 60 cycles forcondition - subjecting Si substrate with HfO2 layer to a mixture of silane+MRG (microwave radical generator) N2 plasma in a PECVD chamber at 550 degrees C., resulting in a layer of SiN deposition of the poly silicon gate layer (only for
condition 92 and 93), and optionally - repeating both subjecting steps once (only for condition 93).
-
FIG. 10 show the cumulative distribution of gate leakage current for a sample of 30 diode/capacitor devices. The devices are obtained according to method described above (conditions FIG. 9 ). Both the HfO2/SiN and [HfO2/SiN]x2 (z=2) devices give near 100% yield whereas about 30% HfO2 devices fail the leakage distribution trend.
Claims (15)
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US11/138,746 US7465626B2 (en) | 2002-12-09 | 2005-05-25 | Method for forming a high-k dielectric stack |
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AU2003289764A1 (en) | 2004-06-30 |
JP2006511934A (en) | 2006-04-06 |
JP4647311B2 (en) | 2011-03-09 |
EP1570525A1 (en) | 2005-09-07 |
JP2010245548A (en) | 2010-10-28 |
AU2003289764A8 (en) | 2004-06-30 |
EP1570525B1 (en) | 2015-12-02 |
US20050269651A1 (en) | 2005-12-08 |
US7465626B2 (en) | 2008-12-16 |
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JP5214667B2 (en) | 2013-06-19 |
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