FR2890073A1 - ORGANOMETAL PRECURSORS FOR THE DEPOSIT OF A TANTALUM CARBIDE OR CARBO-NITRIDE FILM AND PROCESS FOR DEPOSITING SUCH FILM - Google Patents
ORGANOMETAL PRECURSORS FOR THE DEPOSIT OF A TANTALUM CARBIDE OR CARBO-NITRIDE FILM AND PROCESS FOR DEPOSITING SUCH FILM Download PDFInfo
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- FR2890073A1 FR2890073A1 FR0552548A FR0552548A FR2890073A1 FR 2890073 A1 FR2890073 A1 FR 2890073A1 FR 0552548 A FR0552548 A FR 0552548A FR 0552548 A FR0552548 A FR 0552548A FR 2890073 A1 FR2890073 A1 FR 2890073A1
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- tantalum
- nitride
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- 239000002243 precursor Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 5
- 238000000151 deposition Methods 0.000 title description 10
- 229910003468 tantalcarbide Inorganic materials 0.000 title description 6
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 title description 5
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 terbutyl Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 claims description 2
- JWJVZCNJVZZHMP-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1.CC(C)(C)C1=CC=CC=C1 JWJVZCNJVZZHMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 description 17
- 229910052715 tantalum Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GZCFDJRQLZSOGV-UHFFFAOYSA-N Cc1ccc(C[Ta](Cc2ccc(C)cc2)(Cc2ccc(C)cc2)(Cc2ccc(C)cc2)Cc2ccc(C)cc2)cc1 Chemical compound Cc1ccc(C[Ta](Cc2ccc(C)cc2)(Cc2ccc(C)cc2)(Cc2ccc(C)cc2)Cc2ccc(C)cc2)cc1 GZCFDJRQLZSOGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910004200 TaSiN Inorganic materials 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- QUWPZPLTANKXAM-UHFFFAOYSA-N niobium(5+) Chemical compound [Nb+5] QUWPZPLTANKXAM-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical class [SiH3]O* 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
-
- 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
- C23C16/36—Carbonitrides
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28088—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a composite, e.g. TiN
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4966—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET the conductor material next to the insulator being a composite material, e.g. organic material, TiN, MoSi2
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
L'invention concerne des précurseurs de films minces de carbure, carbo-nitrure, et /ou carbo-sylylo-nitrure d'un organométallique de formule M [N(SiR<1> R<2> R<3>)2]2R<4>R<5>R<6> avec M = TaR<1>, R<2>, R<3>, R<4>, R<5>, R<6> = CnH2n+1 avec n=1 à 5L'invention concerne plus particulièrement le Ta(CH3)3(N(TMS)2)2.The invention relates to thin film precursors of carbide, carbo-nitride, and / or carbo-sylylo-nitride of an organometallic of formula M [N (SiR <1> R <2> R <3>) 2] 2R <4> R <5> R <6> with M = TaR <1>, R <2>, R <3>, R <4>, R <5>, R <6> = CnH2n + 1 with n = The invention relates more particularly to Ta (CH3) 3 (N (TMS) 2) 2.
Description
La feuille de route de l'industrie des semi-conducteurs prévoit laThe semiconductor industry roadmap provides for the
diminution progressive et régulière des dimensions critiques des gradual and regular decrease in the critical dimensions of
dispositifs semi-conducteurs. Les dimensions de ces dispositifs sont aujourd'hui couramment de l'ordre de 90 nm et les développements actuellement en cours concernent les futures générations 65 nm, 45 nm et 32 nm. semiconductor devices. The dimensions of these devices are now commonly of the order of 90 nm and the developments currently in progress concern the future 65 nm, 45 nm and 32 nm generations.
Dans la génération actuelle, les électrodes de grille des 1 o transistors MOS (Metal Oxide Semiconductor), déposées sur la couche d'oxyde de silicium réalisant le canal de conduction entre drain et source de ce transistor sont réalisées en silicium polycristallin contenant différents dopants permettant un contrôle de leur travail de sortie et une tension de seuil de l'ordre de 1V pour un dispositif CMOS. In the current generation, the gate electrodes of the 1 o MOS (Metal Oxide Semiconductor) transistors, deposited on the silicon oxide layer forming the conduction channel between the drain and the source of this transistor are made of polysilicon containing different dopants allowing a control of their output work and a threshold voltage of the order of 1V for a CMOS device.
Dans la génération 65 nm, 45 nm puis 32 nm, il ne sera plus possible d'utiliser de telles électrodes de grilles, car la diminution de l'épaisseur de la grille entraîne la génération de phénomènes d'appauvrissement de la couche de silicium polycristallin. De plus, avec l'introduction de nouveaux matériaux diélectriques remplaçant le diélectrique SiO2, il est apparu que le silicium polycristallin avait une faible stabilité thermodynamique au contact de ces nouveaux diélectriques. Les métaux sont de bons candidats au remplacement du silicium polycristallin, notamment en raison de l'absence de phénomène d'appauvrissement et de la possibilité de diminution de la tension de seuil du transistor. Le choix du métal dépend de sa stabilité thermodynamique sur l'oxyde de grille (qui remplace la silice) et surtout de la valeur du travail d'extraction. Sur un dispositif CMOS, les travaux d'extraction des métaux nMOS (transistor MOS de type n) et pMOS (transistor MOS de type p) déterminent en effet la tension de seuil du dispositif. En outre, les matériaux composant l'électrode (film diélectrique, métal) doivent pouvoir être facilement déposés et gravés complètement. L'article de Lu et al. Intitulé Molybdenum Metal Gate MOS Technology for post-SiO2 Gate Dielectrics et publiés dans IEEE, 2000, IEDM 00-641, 28.2.1-28.2.4: IEEE, 2000, IEDM 00-641, 28.2.1-28.2.4 décrit ces conditions requises pour le choix du matériau optimal comme électrode de grille. In the 65 nm, 45 nm then 32 nm generation, it will no longer be possible to use such grid electrodes, because the decrease in the thickness of the grid leads to the generation of depletion phenomena of the polycrystalline silicon layer. . Moreover, with the introduction of new dielectric materials replacing the SiO2 dielectric, it appeared that polysilicon had poor thermodynamic stability in contact with these new dielectrics. Metals are good candidates for replacing polysilicon, in particular because of the absence of depletion phenomenon and the possibility of reducing the threshold voltage of the transistor. The choice of metal depends on its thermodynamic stability on the gate oxide (which replaces the silica) and above all on the value of the extraction work. On a CMOS device, the work of extracting the metals nMOS (n-type MOS transistor) and pMOS (p-type MOS transistor) in fact determines the threshold voltage of the device. In addition, the materials composing the electrode (dielectric film, metal) must be able to be easily deposited and completely etched. The article by Lu et al. Entitled Molybdenum Metal Gate MOS Technology for post-SiO2 Gate Dielectrics and published in IEEE, 2000, IEDM 00-641, 28.2.1-28.2.4: IEEE, 2000, IEDM 00-641, 28.2.1-28.2.4 describes these conditions required for choosing the optimum material as the gate electrode.
Parmi les composés métalliques envisagés comme électrode de grille, les composés à base de tantale, et en particulier, les carbures de tantale (TaxCy), les carbo-nitrure de tantale (TaxCyNz), les carbo-sylilo-nitrure de tantale (TaxSiyNzCt) sont des candidats prometteurs. Par exemple, Pan et al. dans l'article intitulé A Low-Temperature Metal-Doping Technique for Engineering the Gate Electrode of Replacement Metal Gate CMOS Transistors , IEEE Electron Device Letters, vol 24, n 9, Sept 2003, ont étudié les propriétés de composés à bases de tantale comme électrode pMOS et/ou nMOS parmi lesquels TaN, TaSiN, Ta et TaCN, déposés par voie physique. Among the metal compounds envisaged as gate electrode, compounds based on tantalum, and in particular, tantalum carbides (TaxCy), tantalum carbo-nitride (TaxCyNz), tantalum carbo-sylilo-nitride (TaxSiyNzCt) are promising candidates. For example, Pan et al. in the article entitled A Low-Temperature Metal-Doping Technique for Engineering the Gate Electrode of Replacement Metal Gate CMOS Transistors, IEEE Electron Device Letters, vol 24, n 9, Sept 2003, studied the properties of tantalum-based compounds such as pMOS and / or nMOS electrode among which TaN, TaSiN, Ta and TaCN, deposited by physical route.
Par ailleurs, les matériaux à base de tantale sont aussi couramment proposés comme barrière de diffusion pour le cuivre. En effet, avec la diminution des dimensions physiques des semi-conducteurs, le métal de contact, l'aluminium, a été remplacé par un métal possédant une résistivité encore plus faible. Le cuivre a été choisi en conséquence, mais sa capacité à se diffuser dans les couches environnantes a conduit à mettre en place des couches dites barrières de diffusion . De telles barrières métalliques en nitrure métallique, en particulier de tantale, sont décrites dans US-A-2003 224600. Furthermore, tantalum-based materials are also commonly proposed as a diffusion barrier for copper. Indeed, with the decrease in the physical dimensions of semiconductors, the contact metal, aluminum, has been replaced by a metal having an even lower resistivity. Copper was chosen accordingly, but its ability to diffuse into the surrounding layers has led to the installation of so-called diffusion barrier layers. Such metal barriers made of metal nitride, in particular tantalum, are described in US-A-2003 224600.
Pour pouvoir réaliser des dépôts par voie chimique en phase vapeur de composés à base de tantale, préférable au dépôt par voie physique, des précurseurs organométalliques sont utilisés. Pour le dépôt par voie chimique en phase vapeur de couches de carbures métalliques, on a constaté qu'un précurseur devrait avoir les propriétés suivantes: - Le précurseur métallique doit être de préférence liquide et de viscosité modérée à température ambiante afin de pouvoir être distribué aisément par les méthodes usuelles (injection liquide ou évaporation avec surface d'échange thermique constante). Il peut également être solide s'il possède une température de fusion proche de la température ambiante - Le précurseur doit être le plus volatile possible; - Le précurseur doit contenir de préférence au moins une liaison Métal-Carbone; - Le précurseur doit être de préférence stable chimiquement à température ambiante; - Le précurseur doit être de préférence réactif avec des gaz 15 réducteurs à des températures inférieures à 500 C, et préférentiellement à des températures de l'ordre de 350 C. In order to be able to carry out chemical vapor deposition of tantalum-based compounds, which is preferable to physical deposition, organometallic precursors are used. For the chemical vapor deposition of layers of metal carbides, it has been found that a precursor should have the following properties: - The metal precursor should preferably be liquid and of moderate viscosity at room temperature in order to be able to be easily distributed. by the usual methods (liquid injection or evaporation with constant heat exchange surface). It can also be solid if it has a melting temperature close to ambient temperature - The precursor must be as volatile as possible; - The precursor should preferably contain at least one Metal-Carbon bond; - The precursor should preferably be chemically stable at room temperature; - The precursor should preferably be reactive with reducing gases at temperatures below 500 ° C., and preferably at temperatures of the order of 350 ° C.
Un certain nombre de précurseurs organométalliques pour des dépôts de composés à base de carbure de tantale ont été proposés dans l'art antérieur: Dans l'article de H. Cai et al., intitulé Synthesis and characterization of tantalum (V) metallaheterocycle TaN(SiMe3)SiMe2CH2 and chloro-mixed-amide (Me2N)3 (Me2N)3 Ta(CI)[N(SiMe3)2]' Gan. J. Chem., 81; 1398-1405 (2003), il a été proposé d'utiliser des composés organométalliques possédant des ligands silylamines ayant une bonne stabilité chimique. A certain number of organometallic precursors for deposits of compounds based on tantalum carbide have been proposed in the prior art: In the article by H. Cai et al., Entitled Synthesis and characterization of tantalum (V) metallaheterocycle TaN ( SiMe3) SiMe2CH2 and chloro-mixed-amide (Me2N) 3 (Me2N) 3 Ta (CI) [N (SiMe3) 2] 'Gan. J. Chem., 81; 1398-1405 (2003), it has been proposed to use organometallic compounds possessing silylamine ligands having good chemical stability.
US-A-200040014163 décrit des complexes siloxy ou silyl-amino comme précurseurs de silicates métalliques On sait également que les complexes traditionnellement utilisés comme précurseurs de films de tantale nitrurés possèdent en général uniquement l'élément azote en première sphère de coordination. Leur utilisation pour former des films de tantale carbonés conduit généralement à des films de type TaCN, le matériau étant sous forme de solution solide de TaC et de TaN (voir, par exemple, l'article intitulé Low Temperature Deposition of TaCN films using PDEATa , publié par G.-C. Jun et al., MRS Symp., 1996, vol 427, 349-354) Utilisés avec des réactifs carbonés, et même s'ils permettent des températures de dépôt relativement basses, ils incorporent nécessairement beaucoup d'azote (voir par exemple l'intitulé Chemical vapor deposition growth and properties of TaCXNy. de E.R. Engbrecht et al. (Thin Solid Films (2002), 418(2),145-150). Cependant, la concentration en azote reste très importante dans le film obtenu. US-A-200040014163 describes siloxy or silyl-amino complexes as precursors of metal silicates. It is also known that the complexes traditionally used as precursors of nitrided tantalum films generally have only the nitrogen element in the first coordination sphere. Their use to form carbonaceous tantalum films generally leads to TaCN type films, the material being in the form of a solid solution of TaC and TaN (see, for example, the article entitled Low Temperature Deposition of TaCN films using PDEATa, published by G.-C. Jun et al., MRS Symp., 1996, vol 427, 349-354) Used with carbonaceous reagents, and even if they allow relatively low deposition temperatures, they necessarily incorporate a lot of nitrogen (see for example the title Chemical vapor deposition growth and properties of TaCXNy. by ER Engbrecht et al. (Thin Solid Films (2002), 418 (2), 145-150). However, the nitrogen concentration remains very high in the movie got.
Les complexes alkyls homoleptiques de tantale (V) de faible poids moléculaire ont été décrits dans l'article de Schrock et al., intitulé multiple metal carbon bonds 7.1 preparation and Characterization of Ta (n5C5H5)2(CH2)(CH3), a study of its Decomposition, and Some Simple Reactions , Journal of Organomet. Chemistry, 1976, 122(2), 209-25. Low molecular weight alkyl homoleptic tantalum (V) complexes have been described in the article by Schrock et al., Entitled multiple metal carbon bonds 7.1 preparation and Characterization of Ta (n5C5H5) 2 (CH2) (CH3), a study of its Decomposition, and Some Simple Reactions, Journal of Organomet. Chemistry, 1976, 122 (2), 209-25.
Cependant, des molécules de type Ta(Me)5 sont particulièrement instables. L'article de Rothwell et al., intitulé Crystal and molecular structure of penta(4-methylbenzyl)tantalum, [Ta(CH2C6H4Me-4)5] publié dans Polyhedron, 1993, 12(14), 1779-83), décrit le Ta (4-méthylbenzène)5 qui est une molécule plus stable mais son poids moléculaire trop élevé rend son utilisation impropre à la réalisation de films minces par dépôt en phase vapeur. However, Ta (Me) 5 type molecules are particularly unstable. The article by Rothwell et al., Entitled Crystal and molecular structure of penta (4-methylbenzyl) tantalum, [Ta (CH2C6H4Me-4) 5] published in Polyhedron, 1993, 12 (14), 1779-83), describes the Ta (4-methylbenzene) 5 which is a more stable molecule but its excessively high molecular weight makes its use unsuitable for producing thin films by vapor deposition.
II est connu du document de Schrock (R.R. Schrock., Acc. Chem. Res, 1979, 12, 98-104) la synthèse de la molécule suivante: Ta(CHCMe3)(CH2CMe3)3. Cette molécule a été testée pour des dépôts de tantale par le procédé dit MOCVD (Y.H. Chang et al., J. Mater. Chem., 2890073 5 2003, 13, 365-369) : elle conduit à des films minces, mais possède l'inconvénient d'être un solide à température ambiante et d'avoir une faible volatilité, conduisant à des températures de dépôts élevées (450-550 C). II est connu de Chiu et al. (223rd ACS, 2002) le tBuCH=Ta(CH2tBu)3 qui peut être utilisé pour le dépôt de carbure de tantale (223rd ACS, 2002). It is known from the document by Schrock (R.R. Schrock., Acc. Chem. Res, 1979, 12, 98-104) the synthesis of the following molecule: Ta (CHCMe3) (CH2CMe3) 3. This molecule has been tested for tantalum deposits by the so-called MOCVD method (YH Chang et al., J. Mater. Chem., 2890073 5 2003, 13, 365-369): it leads to thin films, but has l 'disadvantage of being a solid at room temperature and of having low volatility, leading to high deposition temperatures (450-550 C). It is known from Chiu et al. (223rd ACS, 2002) tBuCH = Ta (CH2tBu) 3 which can be used for the deposition of tantalum carbide (223rd ACS, 2002).
Il est décrit dans l'article de Schrock et al., JAGS, 1978, 100, 8, 23892399, intitulé Multiple Metal-Carbon Bonds. 7. Preparation and Characterization of Ta(n5-05H5)2(CH2)(CH3), a Study of Its Decomposition, and some Simple Reactions la molécule suivante: Ta(Cp)2(CH2)(CH3), de plus bas poids moléculaire. Cependant, cette molécule n'est pas stable et se décompose. La molécule TaCp2H3 a également été identifiée comme possible précurseur de film mince de tantale, et est mentionnée dans US-A20040142555, mais se décompose et polymérise peu après sa fusion à 190 C. Des dérivés ont été synthétisés, tels que Cp2TaR.R'NC (Teuben et al. Journal of Organomet. Chemistry, 1980, 192(1), 75-81), Ta(iPrCp)2H3 (Green et al., Journal of Organomet. Chemistry, 1980, 193(3), 339-44), Cp2TaH(alkane) (Yasuda et al., Organometallics, 1991, 10(12), 4058-66), mais sont en général solides et doivent être délivrés en solution (voir par exemple, US-A-20040142555, US-B-6379748, US-B-6015917, WO9937655 ou WO2004065650). It is described in the article by Schrock et al., JAGS, 1978, 100, 8, 23892399, entitled Multiple Metal-Carbon Bonds. 7. Preparation and Characterization of Ta (n5-05H5) 2 (CH2) (CH3), a Study of Its Decomposition, and some Simple Reactions the following molecule: Ta (Cp) 2 (CH2) (CH3), lower weight molecular. However, this molecule is not stable and breaks down. The TaCp2H3 molecule has also been identified as a possible thin film precursor of tantalum, and is mentioned in US-A20040142555, but decomposes and polymerizes shortly after its fusion at 190 C. Derivatives have been synthesized, such as Cp2TaR.R'NC (Teuben et al. Journal of Organomet. Chemistry, 1980, 192 (1), 75-81), Ta (iPrCp) 2H3 (Green et al., Journal of Organomet. Chemistry, 1980, 193 (3), 339-44 ), Cp2TaH (alkane) (Yasuda et al., Organometallics, 1991, 10 (12), 4058-66), but are generally solid and must be delivered in solution (see for example, US-A-20040142555, US- B-6379748, US-B-6015917, WO9937655 or WO2004065650).
US-A-20040142555 décrit le Ta(CpTMS)2H3 comme étant plus stable que le TaCp2H3 et ne se décomposant pas avant sa fusion à 90 C. Toutefois sa température de fusion reste relativement élevée ce qui rend plus difficile sa mise en oeuvre. De plus, on a mis en évidence que les liaisons Ta-H doivent préférentiellementétre évitées. Des molécules ne comportant qu'un seul ligand de type Cp ont également été synthétisées, par exemple Cp'Ta(CH2SiMe3)2(CHSiMe3) (voir l'article de De Castro et al., intitulé Monocyclopentadienyl alkyl alkylidene niobium(V) and tantalum(V) complexes. X-ray crystal structure of Ta(n5- Cp')(CH2SiMe3) 2(CHSiMe3) Polyhedron (1992), 11(9), 1023-7). Ces molécules ont toutefois un poids moléculaire trop élevé pour être utilisables dans des procédés de dépôt en phase vapeur. Le TaCpMeH3, solide, est par exemple décrit dans US-A-2005009325. US-A-20040142555 describes Ta (CpTMS) 2H3 as being more stable than TaCp2H3 and not decomposing before it melts at 90 ° C. However, its melting point remains relatively high, which makes it more difficult to use. In addition, it has been demonstrated that Ta-H bonds should preferably be avoided. Molecules comprising only one ligand of Cp type have also been synthesized, for example Cp'Ta (CH2SiMe3) 2 (CHSiMe3) (see the article by De Castro et al., Entitled Monocyclopentadienyl alkyl alkylidene niobium (V) and tantalum (V) complexes X-ray crystal structure of Ta (n5-Cp ') (CH2SiMe3) 2 (CHSiMe3) Polyhedron (1992), 11 (9), 1023-7). These molecules, however, have too high a molecular weight to be used in vapor deposition processes. TaCpMeH3, solid, is for example described in US-A-2005009325.
Des molécules de type carbonyls ont été proposées, comme le Ta(CO)4Cp et le TMSCpTa(CO)4 (voir US-B-6491978), mais ces molécules sont solides et présentes des inconvénients en termes de mise en oeuvre liés à leurs sousproduits toxiques de réaction avec l'air. Carbonyl-type molecules have been proposed, such as Ta (CO) 4Cp and TMSCpTa (CO) 4 (see US-B-6491978), but these molecules are solid and have drawbacks in terms of use linked to their use. toxic byproducts of reaction with air.
Il a été suggéré d'utiliser des molécules ne contenant pas uniquement des liaisons directes Métal-Carbone mais d'utiliser, par exemple, des molécules ayant le type de liaisons suivantes: Liaisons Ta-N: Cp*(DippN=) TaRR', Ta(NMe2)4R, Ta(NMe2)3Me3, Liaisons Ta-Si: Ta(CH2CMe3)2(CHCMe3) (SiR3) - Liaisons Ta-O: TaMe3(OR)2, Cependant: Les familles de type Cp*(DippN=)TaRR' (décrit par T. Don Tilley et al., Organometallics, vol 21, n 15, 2002, 3108-3122) sont généralement des solides à haute température de fusion, de haut poids moléculaire, donc de très faible volatilité. It has been suggested to use molecules not only containing direct Metal-Carbon bonds but to use, for example, molecules having the following type of bonds: Ta-N bonds: Cp * (DippN =) TaRR ', Ta (NMe2) 4R, Ta (NMe2) 3Me3, Ta-Si bonds: Ta (CH2CMe3) 2 (CHCMe3) (SiR3) - Ta-O bonds: TaMe3 (OR) 2, However: Cp * type families (DippN =) TaRR '(described by T. Don Tilley et al., Organometallics, vol 21, no 15, 2002, 3108-3122) are generally solids with a high melting temperature, of high molecular weight, and therefore of very low volatility.
Les familles de type Ta(NMe2)4R sont soit des produits solides soit des liquides visqueux, rendant leur mise en oeuvre difficile (voir l'article de Chisholm et al., JACS, 1982, 104, 4879-4884). Par exemple, Ta(NMe2) 2Me3 se décompose lors de sa fusion (voir l'article de Wilkinson et al., J.C.S. Dalton, 1976, 807-811). The Ta (NMe2) 4R type families are either solid products or viscous liquids, making them difficult to use (see the article by Chisholm et al., JACS, 1982, 104, 4879-4884). For example, Ta (NMe2) 2Me3 decomposes upon fusion (see the article by Wilkinson et al., J.C.S. Dalton, 1976, 807-811).
Les familles de type Ta(CH2CMe3)2(CHCMe3)(SiR3) (décrites par Z. Xue et al., JACS, 1994, 116(5), 2169-70; Chem. Commun. (Cambridge), 1996, 20, 2383-2384; Organometallics, 1996, 15(16), 3520-3527) possèdent des ligands silylés qui sont encombrants, rendant leur volatilité trop faible pour l'utilisation envisagée. The Ta (CH2CMe3) 2 (CHCMe3) (SiR3) type families (described by Z. Xue et al., JACS, 1994, 116 (5), 2169-70; Chem. Commun. (Cambridge), 1996, 20, 2383-2384; Organometallics, 1996, 15 (16), 3520-3527) possess silylated ligands which are bulky, making their volatility too low for the intended use.
Les familles de TaMe3(OR)2 ont une volatilité importante et sont proposées pour des dépôts d'oxyde de tantale dans US-B-5508063 Cependant, lorsqu'on réalise un dépôt de couches métalliques qui n'est pas de type oxydes, on remarque une contamination à l'oxygène dans le film réalisé, ce qui perturbe les propriétés électriques attendues de ce film. The TaMe3 (OR) 2 families have a high volatility and are proposed for tantalum oxide deposits in US-B-5508063 However, when depositing metal layers which is not of the oxide type, it is possible to notices an oxygen contamination in the film produced, which disturbs the expected electrical properties of this film.
La demande de brevet US-A-2004/0044163 décrit notamment des composés appartenant à la famille décrite par (L,)mM(L2)v_X où M est un métal de valence 2 à 6, L1 est un ligand anionique et L2 un ligand amidure silylé permettant le dépôt de silicates. En outre, seule l'utilisation de l'Hafnium (de Valence 4) est décrite, aucun élément de Valence 5 n'étant envisagé. Patent application US-A-2004/0044163 describes in particular compounds belonging to the family described by (L,) mM (L2) v_X where M is a metal of valence 2 to 6, L1 is an anionic ligand and L2 a ligand. silylated amide allowing the deposition of silicates. In addition, only the use of Hafnium (Valence 4) is described, no Valence 5 element being considered.
L'invention permet d'éviter les inconvénients cités ci-dessus. Elle concerne les molécules de précurseurs de films minces à base d'un organométallique de formule générale: M [N(SiR' R2 R3)2]2R4R5R6 avec M = Ta R', R2, R3, R4' R5' R6 = CnH2n+1 avec n=1 à 5 Par exemple, le précurseur utilisé est le Ta(CH3)3(N(TMS)2))2, ou trimethylbis[bis(trimethylsylil)amino] tantalum. Me The invention makes it possible to avoid the drawbacks mentioned above. It relates to molecules of thin film precursors based on an organometallic of general formula: M [N (SiR 'R2 R3) 2] 2R4R5R6 with M = Ta R', R2, R3, R4 'R5' R6 = CnH2n + 1 with n = 1 to 5 For example, the precursor used is Ta (CH3) 3 (N (TMS) 2)) 2, or trimethylbis [bis (trimethylsylil) amino] tantalum. Me
Me TI 'oON(SiMe3)2 I N(SiMe3)2 Me Ces précurseurs peuvent être utilisés pour la fabrication notamment de couches de carbure métalliques ou de couches métalliques nitrurocarburées ou de couches métalliques carburosiliciées ou de couches métalliques nitruro-carburo-siliciées, telles que les couches barrières de diffusion ou électrodes de grille réalisées dans la fabrication des transistors de type MOS et des circuits intégrés qui les incorporent. De préférence, on utilisera le TaMe3(N(SiMe3)2)2 qui présente les avantages d'avoir un bas point de fusion (65 C), d'être stable pendant sa fusion, de se sublimer facilement et enfin de contenir des liaisons Ta-C qui favorisent le dépôt de carbure de tantale. Me TI 'oON (SiMe3) 2 IN (SiMe3) 2 Me These precursors can be used in particular for the manufacture of metal carbide layers or nitrurocarburized metal layers or of carburosilicon metal layers or of nitride-carburosilicon metal layers, such as diffusion barrier layers or gate electrodes produced in the manufacture of MOS type transistors and integrated circuits which incorporate them. Preferably, TaMe3 (N (SiMe3) 2) 2 will be used, which has the advantages of having a low melting point (65 C), of being stable during its melting, of easily sublimating and finally of containing bonds. Ta-C which promote the deposition of tantalum carbide.
Pour déposer une couche de carbure de tantale à partir des molécules de cette famille, on pourra procéder de la façon suivante: -évaporation du mélange contenant le précurseur - mise en présence du mélange comprenant la vapeur de précurseur et d'un substrat chauffé, éventuellement en présence d'un gaz en mélange de gaz porteur (azote, argon, oxygène,...etc. ) et/ou réactifs (H2, CH4, C2H2, C2H43 C3H6)3 de façon à déposer la couche à base de tantale souhaitée. To deposit a layer of tantalum carbide from molecules of this family, one can proceed as follows: evaporation of the mixture containing the precursor - bringing together the mixture comprising the precursor vapor and a heated substrate, optionally in the presence of a gas in a mixture of carrier gas (nitrogen, argon, oxygen, etc.) and / or reactants (H2, CH4, C2H2, C2H43 C3H6) 3 so as to deposit the desired tantalum-based layer .
Le mélange contenant le précurseur peut être une solution contenant le précurseur dissous dans un solvant. Ce solvant peut être choisi, par exemple, parmi les solvants organiques tels que les alcanes linéaires (octane), ramifiés (éthylhexane), les hydrocarbures aromatiques (toluène, p-cymène, butylbenzène, sec-butylbenzène, isobutylbenzène, tertbutylbenzène), les éthers, y compris les éthers cycliques (THF), les amines et polyamines, ou un mélange des produits décrits ci-dessus. The mixture containing the precursor can be a solution containing the precursor dissolved in a solvent. This solvent can be chosen, for example, from organic solvents such as linear alkanes (octane), branched (ethylhexane), aromatic hydrocarbons (toluene, p-cymene, butylbenzene, sec-butylbenzene, isobutylbenzene, tertbutylbenzene), ethers , including cyclic ethers (THF), amines and polyamines, or a mixture of the products described above.
De préférence, le précurseur sera choisi avec R1=R2=R3=R4=R5=R6=Me. Preferably, the precursor will be chosen with R1 = R2 = R3 = R4 = R5 = R6 = Me.
Ce type de précurseur peut être synthétisé selon le protocole expérimental décrit par R.A. Andersen (R.A. Andersen, Inorg. Chem., 1979, 18, 12, 3622-3624) : - on met en présence dans un réacteur chimique maintenu à 0 C, les différentes molécules suivantes dans les proportions définies ci-après: - 0,0047 mol de MeLi en solution dans le diéthyléther (soit 9,5 mL) - 0,0016 mol de Ta(NSiMe3)2CI3 en solution dans le pentane (soit 40 mL) Le mélange est agité et maintenu à 0 C pendant 8h. This type of precursor can be synthesized according to the experimental protocol described by RA Andersen (RA Andersen, Inorg. Chem., 1979, 18, 12, 3622-3624): the different molecules in the proportions defined below: - 0.0047 mol of MeLi in solution in diethyl ether (i.e. 9.5 mL) - 0.0016 mol of Ta (NSiMe3) 2Cl3 in solution in pentane (i.e. 40 mL ) The mixture is stirred and maintained at 0 C for 8 h.
Après décantation du mélange, le surnageant est filtré et le filtrat évaporé à sec sous vide. After settling of the mixture, the supernatant is filtered off and the filtrate evaporated to dryness under vacuum.
Le résidu obtenu est sublimé, par exemple, entre 40 et 50 C, à une pression de l'ordre de 10-2 torr. Le produit désiré est obtenu sous forme 1 o de plaques jaune pâle, avec un rendement de 50%. Le point de fusion du produit est à 65 C. The residue obtained is sublimated, for example, between 40 and 50 ° C., at a pressure of the order of 10-2 torr. The desired product is obtained in the form of 10 pale yellow plates, with a yield of 50%. The melting point of the product is 65 C.
Le produit obtenu est donc un produit à bas point de fusion stable lors de sa fusion, et qui se sublime facilement. En outre, la présence de 3 liaisons directes Ta-C favorise l'incorporation de carbone dans le film mince métallique. The product obtained is therefore a product with a low melting point which is stable during its melting and which easily sublimes. In addition, the presence of 3 direct Ta-C bonds promotes the incorporation of carbon into the metallic thin film.
L'invention sera mieux comprise à l'aide des exemples de réalisation suivants donnés à titre non limitatif: Exemples: Dépôt de carbo-nitrure de tantale Un substrat de silicium est placé dans un réacteur de dépôt de type hot wall. On injecte 30 sccm d'azote ultra pur (qualité électronique ) sec que l'on fait buller dans un conteneur métallique contenant le précurseur (TaMe3(N(SiMe3)2)2) et chauffé de préférence à une température supérieure à 65 C. L'azote et le précurseur entraîné sont mis en contact avec 20 sccm d'H2. Le mélange gazeux est alors mis en contact avec le substrat, dans le réacteur hot wall pendant 20 min. Une couche de TaCN est obtenue d'environ 600 A.. The invention will be better understood with the aid of the following embodiments given without limitation: Examples: Deposition of tantalum carbo-nitride A silicon substrate is placed in a hot wall type deposition reactor. 30 sccm of dry ultra pure nitrogen (electronic grade) is injected which is bubbled into a metal container containing the precursor (TaMe3 (N (SiMe3) 2) 2) and preferably heated to a temperature above 65 C. The nitrogen and the entrained precursor are contacted with 20 sccm of H2. The gas mixture is then brought into contact with the substrate in the hot wall reactor for 20 min. A layer of TaCN is obtained from about 600 A ..
2890073 102890073 10
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Priority Applications (2)
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FR0552548A FR2890073A1 (en) | 2005-08-23 | 2005-08-23 | ORGANOMETAL PRECURSORS FOR THE DEPOSIT OF A TANTALUM CARBIDE OR CARBO-NITRIDE FILM AND PROCESS FOR DEPOSITING SUCH FILM |
PCT/FR2006/050809 WO2007023239A1 (en) | 2005-08-23 | 2006-08-23 | Organometallic precursors for depositing a tantalum carbonitride or carbide film and method of depositing one such film |
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FR0552548A FR2890073A1 (en) | 2005-08-23 | 2005-08-23 | ORGANOMETAL PRECURSORS FOR THE DEPOSIT OF A TANTALUM CARBIDE OR CARBO-NITRIDE FILM AND PROCESS FOR DEPOSITING SUCH FILM |
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US20040044163A1 (en) * | 2002-08-30 | 2004-03-04 | Clark Robert D. | Single source mixtures of metal siloxides |
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US20040044163A1 (en) * | 2002-08-30 | 2004-03-04 | Clark Robert D. | Single source mixtures of metal siloxides |
Non-Patent Citations (1)
Title |
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ANDERSEN RICHARD A.: "Trimethylbis[bis(trimethylsilyl)amido]tantalum(V) and [(trimethylsilyl)methyl][(trimethylsilyl)methylidene]-bis[bis(trimethylsilyl)amido]tantalum(V)", INORGANIC CHEMISTRY, vol. 18, no. 12, 1979, pages 3622 - 3623, XP002384224 * |
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