WO2000065126A1 - Cvd tantalum nitride plug formation from tantalum halide precursors - Google Patents
Cvd tantalum nitride plug formation from tantalum halide precursors Download PDFInfo
- Publication number
- WO2000065126A1 WO2000065126A1 PCT/US2000/011281 US0011281W WO0065126A1 WO 2000065126 A1 WO2000065126 A1 WO 2000065126A1 US 0011281 W US0011281 W US 0011281W WO 0065126 A1 WO0065126 A1 WO 0065126A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tantalum
- precursor
- vapor
- tan
- film
- Prior art date
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 102
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 51
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 title claims abstract description 38
- -1 tantalum halide Chemical class 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 86
- 229910004156 TaNx Inorganic materials 0.000 claims abstract description 82
- 239000010949 copper Substances 0.000 claims abstract description 58
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 45
- 238000000151 deposition Methods 0.000 claims abstract description 41
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 36
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims abstract description 31
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000009832 plasma treatment Methods 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- GCPVYIPZZUPXPB-UHFFFAOYSA-I tantalum(v) bromide Chemical compound Br[Ta](Br)(Br)(Br)Br GCPVYIPZZUPXPB-UHFFFAOYSA-I 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZNRKKSGNBIJSRT-UHFFFAOYSA-L dibromotantalum Chemical compound Br[Ta]Br ZNRKKSGNBIJSRT-UHFFFAOYSA-L 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 24
- 239000012159 carrier gas Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000003028 elevating effect Effects 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 23
- 239000000463 material Substances 0.000 description 18
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 15
- 238000009792 diffusion process Methods 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 238000000864 Auger spectrum Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 241000501105 Aeshnidae Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical class [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000010944 pre-mature reactiony Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MISXNQITXACHNJ-UHFFFAOYSA-I tantalum(5+);pentaiodide Chemical compound [I-].[I-].[I-].[I-].[I-].[Ta+5] MISXNQITXACHNJ-UHFFFAOYSA-I 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H01L21/205—
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
- H01L21/76862—Bombardment with particles, e.g. treatment in noble gas plasmas; UV irradiation
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
Definitions
- This invention relates to the formation of integrated circuits
- integrated circuits provide the pathways for signal transport in an
- An integrated circuit (IC) in a device is composed of a number
- metal “wires” are made between one active transistor in the silicon base of
- the substrate and another active transistor in the silicon base of the substrate are another active transistor in the silicon base of the substrate.
- interconnections collectively known as the metal interconnection of a circuit
- a contact plug As 00/65126
- the contact plug must decrease to allow for the increased number of
- interconnects multilevel metalization structures and higher aspect ratio vias.
- Tne liner must also provi ⁇ e a low eiect ⁇ cal resistance interface
- cnemicai v aoo' ⁇ eoosition (CVD)
- CVD ⁇ eoosition
- r r ⁇ r s to copper.
- Ti reacts with copper to form copper titanium compounds at the
- Ta Sputtered tantalum
- TaN reactive sputtered tantalum nitride
- the deposited Ta and/or TaN have resistance to diffusion of foreign atoms.
- the deposited Ta and/or TaN have resistance to diffusion of foreign atoms.
- the deposited Ta and/or TaN have resistance to diffusion of foreign atoms.
- CVD offers the inherent advantage over PVD of
- TBTDET tertbutyiimidotris(diethylamido)tantalum
- a contact plug makes an electrical connection between doped silicon
- a liner of about 100 A Ta is first deposited using PVD. This Ta layer
- TaN is then deposited on the Ta layer by PVD.
- a seed layer of 1 00 A Cu is then deposited by PVD, and the remainder of the plug is filled with electroplated Cu.
- the TaN layer serves as a metal diffusion barrier to protect the dielectric layer
- TaN also serves as an adhesion layer for the Cu.
- TaN barrier layer may remain at greater than about 200 A for robust performance
- the Ta thickness is still required to be 1 00 A, it follows
- a structure with a diameter of 0J 3 ⁇ m would have a Cu film or "core"
- the size of the via to be filled its relative thickness is about 80% of the via diameter. This is because the deposited film must not only fill the volume of the
- the via is eliminated by depositing more TaN on top of the plug, resulting in a
- thick films be continuous, completely conformal, and seamless.
- underlying materials such as low k dielectrics, a deposition rate of more than 1 00
- the invention is directed to a method of filling a via with a TaN plug
- TaN x tantalum halide
- precursor is delivered at a temperature sufficient to vaporize the precursor to
- the vaporization pressure is greater than
- the vapor is combined with a process gas containing nitrogen and
- TaN x is deposited by a thermal chemical vapor deposition (thermal CVD) process.
- the deposition is halted to plasma treat the film, then deposition is resumed.
- plasma treatments are performed at regular intervals in the thermal CVD process
- tantalum fluoride TaF
- tantalum chloride TaCI
- tantalum bromide tantalum bromide
- TaBr tantalum pentafluoride (TaF 5 ), tantalum pentachloride (TaCI 5 )
- the substrate temperature is in the range of
- the present invention is also directed to a method of completely
- a TaN x layer from a TaF 5 or TaCI 5 precursor by elevating the precursor
- the vapor is combined with a process gas containing nitrogen and
- TaN x is deposited in the feature by a thermal chemical vapor deposition (thermal
- CVD chemical vapor deposition
- the invention is further directed to a method of filling a high aspect
- TaBr 5 precursor on a substrate without a carrier gas.
- the temperature of the precursor is elevated sufficient to produce a tantalum vapor.
- the vapor is
- thermal chemical vapor deposition thermal CVD
- deposition is halted to plasma treat the film surface, then deposition is resumed.
- the plasma treatments are performed at regular intervals in the thermal CVD
- the fiims deposited by the method of the invention can completely
- the films are
- the films have a cracking threshold greater than 2000
- A have sufficiently low electrical resistivities, have 1 00% conformality in high
- the films have minimal impurities and are good barriers to copper diffusion.
- films can be deposited at a rate sufficient for throughput considerations. It will be appreciated that it will be deposited at a rate sufficient for throughput considerations. It will be appreciated that it will be deposited at a rate sufficient for throughput considerations. It will be appreciated that it will be deposited at a rate sufficient for throughput considerations. It will be appreciated that it will be deposited at a rate sufficient for throughput considerations. It will be appreciated that it will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited at a rate sufficient for throughput considerations. It will be deposited
- FIG. 1 is a schematic of an apparatus for plasma treated thermal
- FIG. 2 is a graph of vapor pressure versus temperature for tantalum
- FIG. 3 is a schematic representation of a structure fabricated using
- FIG. 4 is a scanning electron micrograph (SEM) image of a plug fill
- FIG. 5 is a SEM image of a plug fill by TaN x deposited by TaF 5 based
- FIG. 6 is a SEM image of a plug fill by TaN x deposited by TaBr 5 based
- FIG. 7 is a SEM image of a plug fill by TaN x deposited by TaBr 5 based
- FIG . 8 is a SEM image of a 1 1 50 A TaF 5 based CVD TaN x film.
- FIG. 9 is a SEM image of a 3700 A TaCI 5 based CVD TaN x film.
- FIG. 1 0 is a SEM image of a 1 350 A TaBr 5 based CVD TaN x film.
- FIG. 1 1 is a SEM image of TaF 5 based CVD Ta/TaN x film deposited
- FIG. 1 2 is a SEM image of TaCI 5 based CVD TaN x film deposited on
- FIG. 1 3 is a SEM image of TaBr 5 based CVD Ta/TaN x film deposited
- FIG . 1 4 is an Auger spectrum of a TaBr 5 based CVD TaN x film
- Refractory transition metals such as tantalum (Ta) and their nitride
- TaN are effective diffusion barriers to copper (Cu) . Their effectiveness is
- Ta and TaN are especially attractive due to
- Tantalum halides provide a convenient inorganic source for Ta and
- the inorganic precursor is a tantalum pentahalide (TaX 5 ) where
- X represents the halides fluorine (F), chlorine (Cl) and bromine (Br).
- tantalum pentafluoride TaF 5
- tantalum pentachloride TaCI 5
- tantalum bromide (TaBr 5 ), with tantalum pentaiodide (Tal 5 ) included for
- TaF 5 , TaCI 5 and TaBr 5 precursor materials are all solids at room
- a preferred method of CVD is
- a chemical vapor deposition (CVD) system 1 0 includes a
- CVD reaction chamber 1 1 and a precursor delivery system 1 2.
- reaction chamber a reaction is carried out to convert a precursor gas of, for
- tantalum chloride (TaCI) or other tantalum halide compound, into a film
- TaN tantalum nitride
- film is not limited to any particular stoichiometry (TaN x ).
- TaN x stoichiometry
- TaN x encompasses a tantalum nitride film of any stoichiometry.
- the precursor delivery system 12 includes a source 13 of precursor
- the source 1 3 generates
- a precursor gas for example a tantalum halide vapor, from a tantalum halide
- the compound is one that is in a solid state when at standard
- the precursor source is maintained, preferably by
- the vapor pressure is one that is itself sufficient to deliver the precursor vapor to the reaction chamber, preferably without the use of a
- the metering system 1 5 maintains a flow of the precursor gas vapor
- the reaction chamber 1 1 is a generally conventional CVD reactor and
- a vacuum chamber 20 that is bounded by a vacuum tight chamber
- a substrate support or susceptor 22 on the chamber 20 .
- a substrate support or susceptor 22 on the chamber 20 .
- chamber 20 is maintained at a vacuum appropriate for the performance of a CVD
- reaction chamber 1 1 is in the range of from 0.2 to 5.0 Torr.
- the vacuum is
- the precursor gas source 1 3 includes a sealed evaporator 30 that
- the vessel 31 includes a cylindrical evaporation vessel 31 having a vertically oriented axis 32.
- the vessel 31 is bounded by a cylindrical wall 33 formed of a high temperature
- the wall 33 has a flat circular
- the cover 36 is sealed to a flange ring 37 that is integral to
- seal 38 such as a HELICOFLEX seal, which is formed of a C-shaped nickel tube
- a conventional elastomeric O-ring seal may be used to seal a conventional elastomeric O-ring seal.
- the source 1 3 is preferably an inert gas such as He or Ar.
- precursor material such as tantalum fluoride, chloride or
- the vessel 31 is filled with tantalum halide vapor by
- the halide is supplied as
- TaX mass 40 if a liquid, remains constant regardless of the level of depletion of
- the delivery system 1 2 is not limited to direct delivery of a
- precursor 40 but can be used in the alternative for delivery of precursor 40 along
- Such a gas may be hydrogen (H 2 ) or an inert gas such as helium (He)
- the bottom 35 of the wall 33 is maintained in thermal communication with a
- a lower vapor pressure such as about 1 Torr when a carrier gas is used.
- a vapor pressure can be maintained at the preferred pressure of 5 Torr or above
- the desired temperature is at least about 95 ° C for TaF 5 , the
- desired temperature is at least about 1 45 °C for TaCI 5 , and the desired
- Tal 5 pentaiodide
- a temperature of 1 80 °C is assumed to be
- separately controlled heater 45 that is in thermal contact with the outside of the
- trapped air space 46 which is contained between the chamber wall 33 and a surrounding concentric outer aluminum wall or can 47.
- the can 47 is further
- tantalum or titanium haiide compound tantalum or titanium haiide compound.
- the vapor flow metering system 1 5 includes a delivery tube 50 of
- the tube 50 extends from the precursor gas source 1 3 to which
- temperature of the precursor material 40 for example, to 1 95 °C.
- baffle plate 51 in which is centered a
- circular orifice 52 which preferably has a diameter of approximately 0.089
- gauge 1 56 to gauge 2 57 The pressure drop from gauge 1 56 to gauge 2 57 is regulated by control valve 53. This pressure drop after control valve 53 through orifice 52 and into
- reaction chamber 1 1 is greater than about 10 milliTorr and will be proportional to
- a shut-off valve 54 is provided in the line 50 between the
- Pressure sensors 55-58 are provided in the system 1 0 to provide
- the pressure sensors include
- shut-off valve 54 to monitor the pressure in the evaporation vessel 31 .
- a pressure sensor 56 is connected to the tube 50 between the control valve 53
- pressure sensor 57 is connected to the tube 50 between the baffle 51 and the
- reactor inlet 1 6 to monitor the pressure downstream of the orifice 52.
- pressure sensor 58 is connected to the chamber 20 of the reaction chamber to
- the reaction chamber is achieved by the controller 60 in response to the pressures
- pressure sensors 56 and 57 can be determined from the ratio of the
- the tube 52 is a function of only the pressure monitored by pressure sensor 57.
- the controller 60 by interpreting the process conditions.
- the flow rate of precursor gas can be determined by
- the controller 60 through calculation.
- precursor gas is calculated by retrieving flow rate data from lookup or multiplier
- variable orifice control valve 53 the CVD chamber pressure through evacuation
- the solid TaF 5 , TaCI 5 and TaBr 5 precursor As shown in FIG. 1 , the solid TaF 5 , TaCI 5 and TaBr 5 precursor
- TaF 5 , TaCI 5 or TaBr 5 was delivered directly, that is, without the use of a carrier
- reaction chamber 1 1 was heated to a temperature of at least about 1 00° C to
- reaction chamber 1 1 was accomplished by heating the solid tantalum halide
- precursor 40 to a temperature in the range of about 95 ° C-205 °C, the choice
- a sufficient vapor pressure was in the range of
- TaF 5 is a liquid while
- FIG. 2 shows the relationship between the measured vapor pressure
- the desired pressure was greater than about
- TaF 5 , TaCI 5 and TaBr 5 was desirably low enough to be able to deposit
- tantalum in the absence of a carrier gas but yet sufficient to maintain a constant
- substrate 23 was the RF ground.
- the selected TaX 5 vapor was combined with
- process gases in addition to H 2 .
- the thermal CVD is stopped at regular intervals to plasma treat the
- a parallel plate RF -20- discharge is used where the driven electrode is the gas delivery showerhead and
- the wafer stage is the RF ground.
- H 2 was used to plasma treat the film at a flow
- PTTCVD improves the film's morphology from a relatively rough structure to a
- the resistance further decreased to 1 100 ⁇ cm when a 45 A thick
- TaN x film per cycle was subjected to plasma treatment. Similarly, the
- a TaN x film deposited using a TaCI 5 precursor would be
- Plasma treatment times in the range of between 1 0 seconds and
- the microstructure of the TaN x film also changed from a rough to a
- a seamless fiim is one that contains no cracks. The step coverage
- An ideal step coverage is 1 .0 or 1 00%, representing identical thickness
- TaCI 5 based fiims would be expected to exhibit the same
- FIG. 8 is a scanning electron micrograph (SEM) image of a 1 1 50
- FIG. 9 is a SEM image of a
- FIG. 10 is a SEM image
- the TaN x film will be integral, that is, in direct contact with copper, little or no
- TaN x attack or etching of the copper should take place during TaN x deposition.
- FIG. 1 1 shows a TaF 5 based Ta/TaN x film deposited directly on
- FIG. 1 2 shows a TaCI 5 based TaN x film on deposited directly
- FIG. 1 3 shows a TaBr 5 based Ta/TaN x fiim deposited
- FIG. 14 indicates that the thermal TaN x film is nitrogen rich (x > 1 .0),
- bromide concentration was determined to be less than 2 atomic percent.
- One contributing factor may be the nitrogen rich
- an amorphous material defined as having a low fraction of crystalline
- the method is based on the vapor delivery of either TaF 5 , TaCI 5
- step coverage low residual impurity concentrations, sufficiently high
- H 2 RF plasma treatment also significantly improved the microstructure of the
- Ta films may be deposited by PECVD, and TaN films
- thermal CVD chemical vapor deposition
- PECVD plasma treated thermal
- HALIDE PRECURSORS PECVD OF TaN FILMS FROM TANTALUM HALIDE
- Ta/TaN x bilayers may be deposited by CVD as disclosed in the
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Abstract
Description
Claims
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JP2000613856A JP4763894B2 (en) | 1999-04-27 | 2000-04-26 | Formation of CVD tantalum nitride plugs from tantalum halide precursors. |
KR1020017013565A KR100668903B1 (en) | 1999-04-27 | 2000-04-26 | Cvd tantalum nitride plug formation from tantalum halide precursors |
Applications Claiming Priority (2)
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US30064799A | 1999-04-27 | 1999-04-27 | |
US09/300,647 | 1999-04-27 |
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WO2000065126A1 true WO2000065126A1 (en) | 2000-11-02 |
WO2000065126A9 WO2000065126A9 (en) | 2002-03-14 |
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PCT/US2000/011281 WO2000065126A1 (en) | 1999-04-27 | 2000-04-26 | Cvd tantalum nitride plug formation from tantalum halide precursors |
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JP (1) | JP4763894B2 (en) |
KR (1) | KR100668903B1 (en) |
TW (1) | TW593733B (en) |
WO (1) | WO2000065126A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003203878A (en) * | 2001-10-24 | 2003-07-18 | Tokyo Electron Ltd | Method for improving adhesion and durability of cvd tantalum and tantalum nitride modulated film by plasma treatment |
KR100449782B1 (en) * | 2001-07-19 | 2004-09-22 | 삼성전자주식회사 | Method of depositing an atomic layer, and method of depositing a thin layer and a metal layer using the same |
US7094680B2 (en) * | 2001-02-02 | 2006-08-22 | Applied Materials, Inc. | Formation of a tantalum-nitride layer |
Citations (2)
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EP0818560A2 (en) * | 1996-07-09 | 1998-01-14 | Applied Materials, Inc. | Construction of a film on a semiconductor wafer |
EP0869544A2 (en) * | 1997-03-31 | 1998-10-07 | Motorola, Inc. | Method for depositing a diffusion barrier |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06349774A (en) * | 1993-06-08 | 1994-12-22 | Sony Corp | Method of forming buried plug |
JP3027946B2 (en) * | 1997-01-24 | 2000-04-04 | 日本電気株式会社 | Semiconductor device and manufacturing method thereof |
TW380308B (en) * | 1997-07-03 | 2000-01-21 | Motorola Inc | Semiconductor device and a process for forming the device |
JP3129251B2 (en) * | 1997-09-19 | 2001-01-29 | 日本電気株式会社 | Contact plug formation method |
-
2000
- 2000-04-26 TW TW089107862A patent/TW593733B/en not_active IP Right Cessation
- 2000-04-26 WO PCT/US2000/011281 patent/WO2000065126A1/en active IP Right Grant
- 2000-04-26 JP JP2000613856A patent/JP4763894B2/en not_active Expired - Fee Related
- 2000-04-26 KR KR1020017013565A patent/KR100668903B1/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0818560A2 (en) * | 1996-07-09 | 1998-01-14 | Applied Materials, Inc. | Construction of a film on a semiconductor wafer |
EP0869544A2 (en) * | 1997-03-31 | 1998-10-07 | Motorola, Inc. | Method for depositing a diffusion barrier |
Non-Patent Citations (2)
Title |
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HIROSHI FUNAKUBO ET AL: "PREPARATION OF TANX-TIN FILMS BY CVD", JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, INTERNATIONAL EDITION,JP,FUJI TECHNOLOGY PRESS, TOKYO, vol. 98, no. 2, 1 February 1990 (1990-02-01), pages 173 - 178, XP000162310, ISSN: 0912-9200 * |
KALOYEROS A E ET AL: "Tantalum nitride films grown by inorganic low temperature thermal chemical vapor deposition-diffusion barrier properties in copper metallization", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, JAN. 1999, ELECTROCHEM. SOC, USA, vol. 146, no. 1, pages 170 - 176, XP002145088, ISSN: 0013-4651 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7094680B2 (en) * | 2001-02-02 | 2006-08-22 | Applied Materials, Inc. | Formation of a tantalum-nitride layer |
KR100449782B1 (en) * | 2001-07-19 | 2004-09-22 | 삼성전자주식회사 | Method of depositing an atomic layer, and method of depositing a thin layer and a metal layer using the same |
JP2003203878A (en) * | 2001-10-24 | 2003-07-18 | Tokyo Electron Ltd | Method for improving adhesion and durability of cvd tantalum and tantalum nitride modulated film by plasma treatment |
JP4544817B2 (en) * | 2001-10-24 | 2010-09-15 | 東京エレクトロン株式会社 | Method for improving adhesion and durability of CVD tantalum and tantalum nitride controlled films by plasma treatment |
Also Published As
Publication number | Publication date |
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TW593733B (en) | 2004-06-21 |
JP2002543580A (en) | 2002-12-17 |
WO2000065126A9 (en) | 2002-03-14 |
KR100668903B1 (en) | 2007-01-12 |
JP4763894B2 (en) | 2011-08-31 |
KR20020010612A (en) | 2002-02-04 |
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