CN110139945A - 锆前体、铪前体、钛前体及使用其沉积含第4族的膜 - Google Patents
锆前体、铪前体、钛前体及使用其沉积含第4族的膜 Download PDFInfo
- Publication number
- CN110139945A CN110139945A CN201780081938.2A CN201780081938A CN110139945A CN 110139945 A CN110139945 A CN 110139945A CN 201780081938 A CN201780081938 A CN 201780081938A CN 110139945 A CN110139945 A CN 110139945A
- Authority
- CN
- China
- Prior art keywords
- nme
- net
- group
- cmeet
- cme
- 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.)
- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 91
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 15
- 239000010936 titanium Substances 0.000 title description 20
- 230000008021 deposition Effects 0.000 title description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 154
- 150000003624 transition metals Chemical class 0.000 claims abstract description 153
- 239000000203 mixture Substances 0.000 claims abstract description 120
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000003446 ligand Substances 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims description 57
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract description 5
- 238000005019 vapor deposition process Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 130
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 123
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 102
- 238000000231 atomic layer deposition Methods 0.000 description 34
- 239000007789 gas Substances 0.000 description 28
- 238000000151 deposition Methods 0.000 description 24
- 239000002904 solvent Substances 0.000 description 24
- -1 Amido Titanium Chemical compound 0.000 description 23
- 238000005229 chemical vapour deposition Methods 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000004020 conductor Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 229910052718 tin Inorganic materials 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 230000008016 vaporization Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000009834 vaporization Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 238000003851 corona treatment Methods 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910003828 SiH3 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 229940031098 ethanolamine Drugs 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- SKYWAOSWRWWISV-UHFFFAOYSA-N N-propan-2-yl-N-(2-silylethyl)propan-2-amine Chemical compound C(C)(C)N(C(C)C)CC[SiH3] SKYWAOSWRWWISV-UHFFFAOYSA-N 0.000 description 2
- 229910019794 NbN Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910007245 Si2Cl6 Inorganic materials 0.000 description 2
- 229910007264 Si2H6 Inorganic materials 0.000 description 2
- 229910005096 Si3H8 Inorganic materials 0.000 description 2
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 2
- 229910003826 SiH3Cl Inorganic materials 0.000 description 2
- 229910003822 SiHCl3 Inorganic materials 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 229910052767 actinium Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004050 hot filament vapor deposition Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229960004194 lidocaine Drugs 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003235 pyrrolidines Chemical class 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- HVOAFLJLVONUSZ-UHFFFAOYSA-N 2-ethylperoxythiophene Chemical compound CCOOC1=CC=CS1 HVOAFLJLVONUSZ-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WXACXMWYHXOSIX-UHFFFAOYSA-N 5-propan-2-ylidenecyclopenta-1,3-diene Chemical compound CC(C)=C1C=CC=C1 WXACXMWYHXOSIX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910014329 N(SiH3)3 Inorganic materials 0.000 description 1
- 229910003827 NRaRb Inorganic materials 0.000 description 1
- 229910019714 Nb2O3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910004166 TaN Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- AWFPGKLDLMAPMK-UHFFFAOYSA-N dimethylaminosilicon Chemical compound CN(C)[Si] AWFPGKLDLMAPMK-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- 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
- C07F17/00—Metallocenes
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- 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
- C23C16/44—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 method of coating
- C23C16/448—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
-
- 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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
披露了形成含第4族过渡金属的膜的组合物。这些形成含第4族过渡金属的膜的组合物包含具有式L2‑M‑C5R4‑[(ER2)m‑(ER2)n‑O]‑的第4族过渡金属前体，其中M为以η5键合模式键合至环戊二烯基的Ti、Zr或Hf；每个E独立地为C、Si、B或P；m和n独立地为0、1或2；m+n>1；每个R独立地为氢或C1‑C4烃基；每个L独立地为选自由以下组成的组的‑1阴离子配体：NR′ 2、OR′、Cp、脒基、β‑二酮或酮亚胺，其中R′为H或C1‑C4烃基；并且相邻R′可接合以形成烃基环。还披露了合成和使用所披露的前体以经由气相沉积过程在基材上沉积含第4族过渡金属的膜的方法。
Description
相关申请的交叉引用
本申请要求于2016年12月30日提交的美国申请号15/396,118的权益，出于所有的目的将所述申请通过引用以其全文结合在此。
技术领域
披露了形成含第4族过渡金属的膜的组合物，其包含具有式L2-M-C5R4-[(ER2)m-(ER2)n-O]-的第4族过渡金属前体，其中M为以η5键合模式键合至环戊二烯基的Ti、Zr或Hf；每个E独立地为C、Si、B或P；m和n独立地为0、1或2；m+n>1；每个R独立地为氢或C1-C4烃基；相邻R可接合以形成烃基环；每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮或酮亚胺，其中R′为H或C1-C4烃基；并且相邻R′可接合以形成烃基环。还披露了合成和使用所披露的前体以经由气相沉积过程在一个或多个基材上沉积含第4族过渡金属的膜的方法。
背景技术
随着半导体器件按比例缩小，需要具有高介电常数的新材料。化学气相沉积(CVD)和原子层沉积(ALD)已成为此类薄膜的主要沉积技术，因为CVD和ALD可提供具有精确限定的厚度和高台阶覆盖的不同膜(金属、氧化物、氮化物等)。在CVD和ALD中，前体分子在获得具有高共形性和低杂质的高品质膜中起着关键作用。
在高-k电介质之中，基于第4族的材料如第4族氧化物TiO2、HfO2或ZrO2是非常有前景的，无论作为纯氧化物或混合氧化物还是以叠层体使用。另外，含第4族金属如TiN的膜可用于电极和/或Cu扩散阻挡应用。第4族氧化物还可由于其耐蚀刻特性用于光刻应用中，如用于硬掩模或间隔物限定的多重图案化应用。
环戊二烯基(Cp)桥联的第4族金属化合物已用作用于CVD和/或ALD含第4族金属的膜的前体。例如，Ahn等人的US 8,946,096披露了在CVD或ALD中利用的第4族金属有机化合物，其具有下式
其中M为Ti、Zr或Hf，R1为C1至C4烷基，R2和R3独立地为C1至C6烷基。
Cho等人的US 2015/0255276披露了作为沉积来源用于CVD及ALD过程中的有机金属前体，其由Xn(M)(R1)m(R2)k的化学式表示，其中M为Ti、Zr或Hf。X为M的配体并且为以下之一：6,6-二甲基富烯基、茚基、环戊二烯基及被氨基取代的环戊二烯基。R1和R2为M的配体，且各自独立地为氨基或亚乙基二氨基。n、m及k各自为正整数，且n+m+k＝3或4。
Castle等人的KR 10-2014-0078534披露了金属前体及用所述金属前体制备的含金属的薄膜，这些金属前体包括具有以下结构式的第4族络合物：
其中M选自由Zr、Hf及Ti组成的组，Xa和Xb各自独立地为NRaRb或ORc，Xc为(NRd)或O，Ra至Rd各自独立地为氢原子或C1至C5烷基，R各自独立地为氢原子或C1至C5烷基，且m为0至4的整数。
Kang等人披露了使用(CpN)Ti(NMe2)2及氧气远程等离子体形成TiO2薄膜(Kang等人,“Growth behavior and structural characteristics of TiO2 thin films using(CpN)Ti(NMe2)2and oxygen remote Plasma[使用(CpN)Ti(NMe2)2及氧气远程等离子体的TiO2薄膜的生长行为和结构特征]”,固体物理A辑(Phys.Status Solidi A),2014,212,第3期,第674-679页)。
一些Cp桥联的第4族金属化合物被合成并用于催化剂或其他目的。例如，J Okuda披露了具有经连接的胺基-环戊二烯基配体的金属有机催化剂，诸如Ti(R-Cp-SiMe2-NR-)(NR2)2(J Okuda,“Linked Amido-CycIopentadienyl Complexes of Group 3 and 4Metals:The First“Post-Metallocenes”Metalorganic Catalysts for Synthesis andPolymerization[第3和4族金属的经连接的胺基-环戊二烯基络合物：用于合成和聚合的第一“后茂金属”金属有机催化剂]”，第200-211页，1999)。Herrmann等人披露了作为潜在催化剂制备的Cp(CH2CH2-O-)Zr(NMe2)2(Herrmann等人,“Doubly Bridged vac-Metallocenesof Zirconium and Hafnium[锆和铪的双桥联vac-茂金属]”,德国应用化学英语版(Angewandte.Chem.Int.Ed.Eng),1994,33(19),第1946-1949页)。Kim等人披露了(Me4Cp-CH2-NtBu)Zr(NEt2)2和(1,3-Me2C5H2-CHPh-NtBu-κN)Zr(NMe2)2的合成(Kim等人,“sp3-C1-Bridged 1,3-Me2Cp/Amido Titanium and Zirconium Complexes and TheirReactivities towards Ethylene Polymerization[sp3-C1-桥联的1,3-Me2Cp/胺基钛和锆络合物及其针对乙烯聚合的反应性]”,欧洲无机化学(Eur.J.Inorg.Chem.)2004,第1522-1529页)。Jesus Cano和Klaus Kunz披露了一些含有P、C、Si的Cp-氨基桥联化合物的合成(Jesus Cano,Klaus Kunz,“How to synthesize a constrained geometry catalyst(CGC)–A survey[如何合成限定几何构型催化剂(CGC)-综述]”,有机金属化学杂志(Journal of Organometallic Chemistry)692,2007,第4411-4423页)。碳桥联的环戊二烯基胺基第4族金属络合物的合成于1999年报导于Piet-Jan Sinnema的PhD论文中(Piet-JanSinnema,“Carbon-Bridged Cyclopentadienyl Amido Group 4 Metal Complexes[碳桥联的环戊二烯基胺基第4族金属络合物]”,格罗宁根大学(University of Groningen),1999)。
因此，本领域技术人员继续寻求适用于在高温下以受控的厚度及组成气相薄膜沉积的高度热稳定的第4族化合物。
发明内容
披露了形成含第4族过渡金属的膜的组合物。这些形成含第4族过渡金属的膜的组合物包含具有式L2-M-C5R4-[(ER2)m-(ER2)n-O]-的第4族过渡金属前体，参考以下结构式：
其中M为以η5键合模式键合至Cp基团的Ti、Zr或Hf；每个E独立地为C、Si、B或P；m和n独立地为0、1或2；m+n>1；每个R独立地为氢或C1-C4烃基；相邻R可接合以形成烃基环；且每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基(amidinate)、β-二酮(β-diketonate)或酮亚胺(keto-iminate)，其中R′为H或C1-C4烃基且相邻R′可接合以形成烃基环。
所披露的形成含第4族过渡金属的膜的组合物可进一步包括以下方面中的一个或多个：
·M为Ti；
·M为Zr；
·M为Hf；
·每个E为C、Si、B或P；
·E为C；
·E为Si；
·E为B；
·E为P；
·m为0、1、或2；
·n为0、1、或2；
·m+n为>1；
·m为0；
·m为1；
·m为2；
·n为0；
·n为1；
·n为2；
·m为1并且n为1；
·m为2并且n为1；
·每个R独立地为H、Me、Et、nPr、iPr、nBu、sBu、iBu、或tBu；
·R为H；
·R为Me；
·R为Et；
·R为nPr；
·R为iPr；
·R为nBu；
·R为iBu；
·R为sBu；
·R为tBu；
·L为NH2；
·L为NMe2；
·L为NEt2
·L为NnPr2；
·L为NiPr2；
·L为NnBu2；
·L为NiBu2；
·L为NsBu2；
·L为NtBu2；
·L为NHMe；
·L为NHEt；
·L为NHnPr；
·L为NHiPr；
·L为NHnBu；
·L为NHiBu；
·L为NHsBu；
·L为NHtBu；
·L为NMeEt；
·L为NMenPr；
·L为NMeiPr；
·L为NMenBu；
·L为NMeiBu；
·L为NMesBu；
·L为NMetBu；
·L为NEtnPr；
·L为NEtiPr；
·L为NEtnBu；
·L为NEtiBu；
·L为NEtsBu；
·L为NEttBu；
·L为NnPriPr；
·L为NnPrnBu；
·L为NnPriBu；
·L为NnPrsBu；
·L为NnPrtBu；
·L为NiPrnBu；
·L为NiPriBu；
·L为NiPrsBu；
·L为NiPrtBu；
·L为NnBuiBu；
·L为NnBusBu；
·L为NnButBu；
·L为NiBusBu；
·L为NiButBu；
·L为NsButBu；
·L为OH；
·L为OMe；
·L为OEt；
·L为OnPr；
·L为OiPr；
·L为OnBu；
·L为OiBu；
·L为OsBu；
·L为OtBu；
·L为Cp；
·L为脒基；
·L为β-二酮；
·L为酮亚胺；
·该Cp基团具有甲基取代基；
·该Cp基团具有乙基取代基；
·该Cp基团具有异丙基取代基；
·该Cp基团具有叔丁基取代基；
·该第4族过渡金属前体为L2-Ti-C5H4-(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Ti-C5H3-1-Me-3-[(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Ti-C5H3-1-iPr-3-[(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Zr-C5H4-(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Zr-C5H3-1-Me-3-[(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Zr-C5H3-1-iPr-3-[(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Hf-C5H4-(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Hf-C5H3-1-Me-3-[(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该第4族过渡金属前体为L2-Hf-C5H3-1-iPr-3-[(CH2-CH2-O)-(其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基)；
·该形成含第4族过渡金属的膜的组合物包含在大致0.1摩尔％与大致50摩尔％之间的该第4族过渡金属前体；
·该形成含第4族过渡金属的膜的组合物具有在大致1与大致20cps之间、优选在大致1与大致5cps之间、优选约3cps的粘度；
·该形成含第4族过渡金属的膜的组合物包含在大致95％w/w至大致100％w/w之间的该第4族过渡金属前体；
·该形成含第4族过渡金属的膜的组合物包含在大致99％w/w至大致100％w/w之间的该第4族过渡金属前体；
·该形成含第4族过渡金属的膜的组合物进一步包含溶剂；
·该形成含第4族过渡金属的膜的组合物包含在大致0％w/w与5％w/w之间的烃溶剂；
·该溶剂选自由以下组成的组：C1-C16烃(不论饱和或不饱和的)、酮、醚、乙二醇二甲醚、酯、四氢呋喃(THF)、草酸二甲酯(DMO)、及其组合；
·该溶剂是C1-C16烃；
·该溶剂是四氢呋喃(THF)；
·该溶剂是DMO；
·该溶剂是醚；
·该溶剂是乙二醇二甲醚；或
·该第4族过渡金属前体的沸点与该溶剂的沸点之间的差小于100℃。
还披露了形成含第4族过渡金属的膜的组合物的递送装置，这些递送装置包括罐，该罐具有入口导管及出口导管且含有上文所披露的形成含第4族过渡金属的膜的组合物中的任一种。所披露的递送装置可包括以下方面中的一个或多个：
·该形成含第4族过渡金属的膜的组合物具有小于10ppmw的非第4族金属污染物的总浓度；
·该入口导管的一端位于该形成含第4族过渡金属的膜的组合物的表面上方且该出口导管的一端位于该形成含第4族过渡金属的膜的组合物的表面上方；
·该入口导管末端的一端位于该形成含第4族过渡金属的膜的组合物的表面上方且该出口导管的一端位于该形成含第4族过渡金属的膜的组合物的表面下方；或
·该入口导管末端的一端位于该形成含第4族过渡金属的膜的组合物的表面下方且该出口导管的一端位于该形成含第4族过渡金属的膜的组合物的表面上方。
还披露了用于在一个或多个基材上沉积含第4族过渡金属的膜的方法。将至少一种以上披露的形成含第4族过渡金属的膜的组合物引入反应器中，该反应器具有至少一个布置在其中的基材。将该第4族过渡金属前体的至少一部分沉积到该一个或多个基材上以形成含第4族过渡金属的膜。所披露的工艺可以进一步包括以下方面中的一个或多个：
·将至少一种反应物引入该反应器中；
·将该反应物进行等离子体处理；
·将该反应物进行远程等离子体处理；
·该反应物不进行等离子体处理；
·该反应物选自由以下组成的组：H2、NH3、肼(如N2H4、MeHNNH2、MeHNNHMe)、有机胺(如NMeH2、NEtH2、NMe2H、NEt2H、NMe3、NEt3、环状胺像吡咯烷或嘧啶)、二胺(如乙二胺、二甲基乙二胺、四甲基乙二胺)、氨基醇(如乙醇胺[HO-CH2-CH2-NH2]、双乙醇胺[HN(C2H5OH)2]或三乙醇胺[N(C2H5OH)3])、吡唑啉及吡啶；
·该反应物选自由以下组成的组：(SiH3)3N、氢化硅烷(如SiH4、Si2H6、Si3H8、Si4H10、Si5H10、Si6H12)、氯硅烷及氯聚硅烷(如SiHCl3、SiH2Cl2、SiH3Cl、Si2Cl6、Si2HCl5、Si3Cl8)、烷基硅烷(如Me2SiH2、Et2SiH2、MeSiH3、EtSiH3)及氨基硅烷(如三(二甲氨基硅烷)、双二乙氨基硅烷、二异丙基氨基硅烷及其他单氨基硅烷、双氨基硅烷或三氨基硅烷)；
·该反应物选自由以下组成的组：NH3、N(SiH3)3、氨基硅烷、及其混合物；
·该反应物选自三烷基铝、二烷基卤化铝、铝的烷氨基及烷氧基衍生物、及其混合物；
·该反应物为NH3；
·该反应物选自由以下组成的组：O2、O3、H2O、H2O2、NO、N2O、NO2、醇、二醇(如乙二醇)、其氧自由基、及其混合物；
·该反应物为H2O；
·该反应物为O2；
·该反应物为经等离子体处理的O2；
·该反应物为O3；
·将该形成含第4族过渡金属的膜的组合物和该反应物同时引入该反应器中；
·该反应器被配置用于化学气相沉积；
·该反应器被配置用于等离子体增强化学气相沉积；
·将该形成含第4族过渡金属的膜的组合物和该反应物顺序地引入腔室中；
·该反应器被配置用于原子层沉积；
·该反应器被配置用于等离子体增强原子层沉积；
·该反应器被配置用于空间原子层沉积；
·该含第4族过渡金属的膜为第4族过渡金属氧化物(MnOm，其中M是第4族过渡金属，并且n和m各自为从1至6范围内(包括端点)的整数)；
·该含第4族过渡金属的膜为TiO2、ZrO2或HfO2；
·该含第4族过渡金属的膜为MM′iOx，其中i在从0至1的范围内；x在从1至6的范围内；并且M′选自第3族元素、不同的第4族元素(即M≠M′)、第5族元素、镧系元素、Si、Al、B、P或Ge；或
·该含第4族过渡金属的膜为MM′iNyOx，其中i在从0至1的范围内；x及y在从1至6的范围内；并且M′选自第3族元素、不同的第4族元素(即M≠M′)、第5族元素、镧系元素、Si、Al、B、P或Ge。
记法和命名法
贯穿以下说明书及权利要求书使用某些缩写、符号及术语，且其包括：
如披露的实施例中所用，不定冠词“一个/种(a或an)”意指一个/种或多个/种。
如披露的实施例中所用，“约”或“大约”或“大致”在本文或权利要求中意指所述值的±10％。
如披露的实施例中所用，术语“独立地”当在描述R基团的上下文中使用时应理解为表示主语R基团不仅相对于带有相同或不同下标或上标的其他R基团独立地选择，而且还相对于同一R基团的任何另外种类独立地选择。例如，在式MR1 x(NR2R3)(4-x)中，其中x为2或3，两个或三个R1基团可(但无需)彼此相同或与R2或R3相同。此外，应当理解，除非另外特别说明，否则当在不同式中使用时，R基团的值彼此独立。
如披露的实施例中所用，术语“烃基”是指含有碳和氢的官能团；术语“烷基”是指仅仅含有碳和氢原子的饱和官能团。烃基可以是饱和的或不饱和的。这两个术语中的任何一个是指直链的、支链的、或环状基团。直链烷基的实例包括但不限于甲基、乙基、丙基、丁基等。支链烷基的实例包括但不限于叔丁基。环烷基的实例包括但不限于环丙基、环戊基、环己基等。
如披露的实施例中所用，缩写“Me”是指甲基；缩写“Et”是指乙基；缩写“Pr”是指丙基；缩写“nPr”是指“正”或直链丙基；缩写“iPr”是指异丙基；缩写“Bu”是指丁基；缩写“nBu”是指“正”或直链丁基；缩写“tBu”是指叔丁基，也称为1,1-二甲基乙基；缩写“sBu”是指仲丁基，也称为1-甲基丙基；缩写“iBu”是指异丁基，也称为2-甲基丙基；缩写“Cp”是指环戊二烯基；并且缩写“Cp*”是指五甲基环戊二烯基。
如披露的实施例中所用，化学式L2-M-C5R4-[(ER2)m-(ER2)n-O]-是指分别具有以下结构式的化合物：
其中M为以η5键合模式键合至Cp基团的Ti、Zr或Hf；每个E独立地为C、Si、B或P；m和n独立地为0、1或2；m+n>1；每个R独立地为氢或C1-C4烃基或相邻的R对形成烃基环；且每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基或相邻的R′对形成烃基环。本文中，η5是以上前体的哈普托数，其表示该芳香族环基团的五个邻接原子与该M原子键合。例如，式(R2N)2-Ti-C5H3-1-iPr-3-(CH2-CH2-O)-表示以下结构：
披露的实施例中使用来自元素周期表中的元素的标准缩写。应当理解，可通过这些缩写提及元素(例如，Mn是指锰，Si是指硅，C是指碳等)。另外，第3族是指周期表的第3族(即Sc、Y、La、或Ac)。类似地，第4族是指周期表的第4族(即Ti、Zr、或Hf)并且第5族是指周期表的第5族(即V、Nb、或Ta)。
披露的实施例中列举的任何及所有范围包括其端点(即，x＝1至4或x在从1至4范围内包括x＝1、x＝4及x＝其间的任何数值)，不论是否使用术语“包括端点”。
请注意，所沉积的膜或层(诸如氧化硅或氮化硅)可以在整个说明书及权利要求书中在不提及其正确化学计量(即SiO2、SiO3、Si3N4)的情况下列举。这些层可以包括纯(Si)层、碳化物(SioCp)层、氮化物(SikNl)层、氧化物(SinOm)层或其混合物，其中k、l、m、n、o和p范围从1至6(包括端点)。例如，氧化硅为SinOm，其中n在从0.5至1.5的范围内并且m在从1.5至3.5的范围内。更优选地，氧化硅层为SiO2或SiO3。这些膜也可以含有氢，典型地从0at％至15at％。然而，由于没有常规测量，除非另有明确说明，否则任何给出的膜组成都忽略其H含量。
附图说明
为了进一步理解本发明的本质和目的，应结合附图来参考以下详细说明，其中：
图1为液体的形成含第4族过渡金属的膜的组合物的递送装置1的一个实施例的侧视图；
图2为该形成含第4族过渡金属的膜的组合物的递送装置1的第二实施例的侧视图；并且
图3为用于使固体的形成含第4族过渡金属的膜的组合物升华的固体前体升华器100的示例性实施例。
具体实施方式
披露了形成含第4族过渡金属的膜的组合物。这些形成含第4族过渡金属的膜的组合物进一步包含具有式L2-M-C5R4-[(ER2)m-(ER2)n-O]-的第4族过渡金属前体，参考以下结构式：
其中M为以η5键合模式键合至Cp基团的Ti、Zr或Hf；每个E独立地为C、Si、B或P；m和n独立地为0、1或2；m+n>1；每个R独立地为氢或C1-C4烃基；相邻R可形成烃基环；且每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基或相邻的R′对形成烃基环。
示例性第4族过渡金属前体(其中E为C；m+n＝2；并且每个R独立地为氢或具有最高达4个碳原子的烃基)包括但不限于(H2N)2-M-C5H4-[(CH2)2-O]-、(Me2N)2-M-C5H4-[(CH2)2-O]-、(Et2N)2-M-C5H4-[(CH2)2-O]-、(MeEtN)2-M-C5H4-[(CH2)2-O]-、(nPr2N)2-M-C5H4-[(CH2)2-O]-、(iPr2N)2-M-C5H4-[(CH2)2-O]-、(nBu2N)2-M-C5H4-[(CH2)2-O]-、(iBu2N)2-M-C5H4-[(CH2)2-O]-、(sBu2N)2-M-C5H4-[(CH2)2-O]-、(tBu2N)2-M-C5H4-[(CH2)2-O]-、(H2N)(Cp)-M-C5H4-[(CH2)2-O]-、(Me2N)(Cp)-M-C5H4-[(CH2)2-O]-、(Et2N)(Cp)-M-C5H4-[(CH2)2-O]-、(MeEtN)(Cp)-M-C5H4-[(CH2)2-O]-、(nPr2N)(Cp)-M-C5H4-[(CH2)2-O]-、(iPr2N)(Cp)-M-C5H4-[(CH2)2-O]-、(nBu2N)(Cp)-M-C5H4-[(CH2)2-O]-、(iBu2N)(Cp)-M-C5H4-[(CH2)2-O]-、(sBu2N)(Cp)-M-C5H4-[(CH2)2-O]-、(tBu2N)(Cp)-M-C5H4-[(CH2)2-O]-、(HO)-M-C5H4-[(CH2)2-O]-、(MeO)-M-C5H4-[(CH2)2-O]-、(EtO)-M-C5H4-[(CH2)2-O]-、(nPrO)-M-C5H4-[(CH2)2-O]-、(iPrO)-M-C5H4-[(CH2)2-O]-、(nBuO)-M-C5H4-[(CH2)2-O]-、(iBuO)-M-C5H4-[(CH2)2-O]-、(tBuO)-M-C5H4-[(CH2)2-O]-、(sBuO)-M-C5H4-[(CH2)2-O]-、(H2N)2-M-C5H4-[(CMe2)2-O]-、(Me2N)2-M-C5H4-[(CMe2)2-O]-、(Et2N)2-M-C5H4-[(CMe2)2-O]-、(MeEtN)2-M-C5H4-[(CMe2)2-O]-、(nPr2N)2-M-C5H4-[(CMe2)2-O]-、(iPr2N)2-M-C5H4-[(CMe2)2-O]-、(nBu2N)2-M-C5H4-[(CMe2)2-O]-、(iBu2N)2-M-C5H4-[(CMe2)2-O]-、(sBu2N)2-M-C5H4-[(CMe2)2-O]-、(tBu2N)2-M-C5H4-[(CMe2)2-O]-、(H2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(Me2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(Et2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C5H4-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C5H4-[(CMe2)2-O]-、(HO)-M-C5H4-[(CMe2)2-O]-、(MeO)-M-C5H4-[(CMe2)2-O]-、(EtO)-M-C5H4-[(CMe2)2-O]-、(nPrO)-M-C5H4-[(CMe2)2-O]-、(iPrO)-M-C5H4-[(CMe2)2-O]-、(nBuO)-M-C5H4-[(CMe2)2-O]-、(iBuO)-M-C5H4-[(CMe2)2-O]-、(tBuO)-M-C5H4-[(CMe2)2-O]-、(sBuO)-M-C5H4-[(CMe2)2-O]-、(H2N)2-M-C5H4-[(CEt2)2-O]-、(Me2N)2-M-C5H4-[(CEt2)2-O]-、(Et2N)2-M-C5H4-[(CEt2)2-O]-、(MeEtN)2-M-C5H4-[(CEt2)2-O]-、(nPr2N)2-M-C5H4-[(CEt2)2-O]-、(iPr2N)2-M-C5H4-[(CEt2)2-O]-、(nBu2N)2-M-C5H4-[(CEt2)2-O]-、(iBu2N)2-M-C5H4-[(CEt2)2-O]-、(sBu2N)2-M-C5H4-[(CEt2)2-O]-、(tBu2N)2-M-C5H4-[(CEt2)2-O]-、(H2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(Me2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(Et2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C5H4-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C5H4-[(CEt2)2-O]-、(HO)-M-C5H4-[(CEt2)2-O]-、(MeO)-M-C5H4-[(CEt2)2-O]-、(EtO)-M-C5H4-[(CEt2)2-O]-、(nPrO)-M-C5H4-[(CEt2)2-O]-、(iPrO)-M-C5H4-[(CEt2)2-O]-、(nBuO)-M-C5H4-[(CEt2)2-O]-、(iBuO)-M-C5H4-[(CEt2)2-O]-、(tBuO)-M-C5H4-[(CEt2)2-O]-、(sBuO)-M-C5H4-[(CEt2)2-O]-、(H2N)2-M-C5H4-[(CiPr2)2-O]-、(Me2N)2-M-C5H4-[(CiPr2)2-O]-、(Et2N)2-M-C5H4-[(CiPr2)2-O]-、(MeEtN)2-M-C5H4-[(CiPr2)2-O]-、(nPr2N)2-M-C5H4-[(CiPr2)2-O]-、(iPr2N)2-M-C5H4-[(CiPr2)2-O]-、(nBu2N)2-M-C5H4-[(CiPr2)2-O]-、(iBu2N)2-M-C5H4-[(CiPr2)2-O]-、(sBu2N)2-M-C5H4-[(CiPr2)2-O]-、(tBu2N)2-M-C5H4-[(CiPr2)2-O]-、(H2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C5H4-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C5H4-[(CiPr2)2-O]-、(HO)-M-C5H4-[(CiPr2)2-O]-、(MeO)-M-C5H4-[(CiPr2)2-O]-、(EtO)-M-C5H4-[(CiPr2)2-O]-、(nPrO)-M-C5H4-[(CiPr2)2-O]-、(iPrO)-M-C5H4-[(CiPr2)2-O]-、(nBuO)-M-C5H4-[(CiPr2)2-O]-、(iBuO)-M-C5H4-[(CiPr2)2-O]-、(tBuO)-M-C5H4-[(CiPr2)2-O]-、(sBuO)-M-C5H4-[(CiPr2)2-O]-、(H2N)2-M-C5H4-[(CtBu2)2-O]-、(Me2N)2-M-C5H4-[(CtBu2)2-O]-、(Et2N)2-M-C5H4-[(CtBu2)2-O]-、(MeEtN)2-M-C5H4-[(CtBu2)2-O]-、(nPr2N)2-M-C5H4-[(CtBu2)2-O]-、(iPr2N)2-M-C5H4-[(CtBu2)2-O]-、(nBu2N)2-M-C5H4-[(CtBu2)2-O]-、(iBu2N)2-M-C5H4-[(CtBu2)2-O]-、(sBu2N)2-M-C5H4-[(CtBu2)2-O]-、(tBu2N)2-M-C5H4-[(CtBu2)2-O]-、(H2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C5H4-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C5H4-[(CtBu2)2-O]-、(HO)-M-C5H4-[(CtBu2)2-O]-、(MeO)-M-C5H4-[(CtBu2)2-O]-、(EtO)-M-C5H4-[(CtBu2)2-O]-、(nPrO)-M-C5H4-[(CtBu2)2-O]-、(iPrO)-M-C5H4-[(CtBu2)2-O]-、(nBuO)-M-C5H4-[(CtBu2)2-O]-、(iBuO)-M-C5H4-[(CtBu2)2-O]-、(tBuO)-M-C5H4-[(CtBu2)2-O]-、(sBuO)-M-C5H4-[(CtBu2)2-O]-、(H2N)2-M-C5H4-[(CMeEt)2-O]-、(Me2N)2-M-C5H4-[(CMeEt)2-O]-、(Et2N)2-M-C5H4-[(CMeEt)2-O]-、(MeEtN)2-M-C5H4-[(CMeEt)2-O]-、(nPr2N)2-M-C5H4-[(CMeEt)2-O]-、(H2N)2-M-C5Me4-[(CH2)2-O]-、(Me2N)2-M-C5Me4-[(CH2)2-O]-、(Et2N)2-M-C5Me4-[(CH2)2-O]-、(MeEtN)2-M-C5Me4-[(CH2)2-O]-、(nPr2N)2-M-C5Me4-[(CH2)2-O]-、(iPr2N)2-M-C5Me4-[(CH2)2-O]-、(nBu2N)2-M-C5Me4-[(CH2)2-O]-、(iBu2N)2-M-C5Me4-[(CH2)2-O]-、(sBu2N)2-M-C5Me4-[(CH2)2-O]-、(tBu2N)2-M-C5Me4-[(CH2)2-O]-、(H2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(Me2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(Et2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(MeEtN)(Cp)-M-C5Me4-[(CH2)2-O]-、(nPr2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(iPr2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(nBu2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(iBu2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(sBu2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(tBu2N)(Cp)-M-C5Me4-[(CH2)2-O]-、(HO)-M-C5Me4-[(CH2)2-O]-、(MeO)-M-C5Me4-[(CH2)2-O]-、(EtO)-M-C5Me4-[(CH2)2-O]-、(nPrO)-M-C5Me4-[(CH2)2-O]-、(iPrO)-M-C5Me4-[(CH2)2-O]-、(nBuO)-M-C5Me4-[(CH2)2-O]-、(iBuO)-M-C5Me4-[(CH2)2-O]-、(tBuO)-M-C5Me4-[(CH2)2-O]-、(sBuO)-M-C5Me4-[(CH2)2-O]-、(H2N)2-M-C5Me4-[(CMe2)2-O]-、(Me2N)2-M-C5Me4-[(CMe2)2-O]-、(Et2N)2-M-C5Me4-[(CMe2)2-O]-、(MeEtN)2-M-C5Me4-[(CMe2)2-O]-、(nPr2N)2-M-C5Me4-[(CMe2)2-O]-、(iPr2N)2-M-C5Me4-[(CMe2)2-O]-、(nBu2N)2-M-C5Me4-[(CMe2)2-O]-、(iBu2N)2-M-C5Me4-[(CMe2)2-O]-、(sBu2N)2-M-C5Me4-[(CMe2)2-O]-、(tBu2N)2-M-C5Me4-[(CMe2)2-O]-、(H2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(Me2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(Et2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C5Me4-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C5Me4-[(CMe2)2-O]-、(HO)-M-C5Me4-[(CMe2)2-O]-、(MeO)-M-C5Me4-[(CMe2)2-O]-、(EtO)-M-C5Me4-[(CMe2)2-O]-、(nPrO)-M-C5Me4-[(CMe2)2-O]-、(iPrO)-M-C5Me4-[(CMe2)2-O]-、(nBuO)-M-C5Me4-[(CMe2)2-O]-、(iBuO)-M-C5Me4-[(CMe2)2-O]-、(tBuO)-M-C5Me4-[(CMe2)2-O]-、(sBuO)-M-C5Me4-[(CMe2)2-O]-、(H2N)2-M-C5Me4-[(CEt2)2-O]-、(Me2N)2-M-C5Me4-[(CEt2)2-O]-、(Et2N)2-M-C5Me4-[(CEt2)2-O]-、(MeEtN)2-M-C5Me4-[(CEt2)2-O]-、(nPr2N)2-M-C5Me4-[(CEt2)2-O]-、(iPr2N)2-M-C5Me4-[(CEt2)2-O]-、(nBu2N)2-M-C5Me4-[(CEt2)2-O]-、(iBu2N)2-M-C5Me4-[(CEt2)2-O]-、(sBu2N)2-M-C5Me4-[(CEt2)2-O]-、(tBu2N)2-M-C5Me4-[(CEt2)2-O]-、(H2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(Me2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(Et2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C5Me4-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C5Me4-[(CEt2)2-O]-、(HO)-M-C5Me4-[(CEt2)2-O]-、(MeO)-M-C5Me4-[(CEt2)2-O]-、(EtO)-M-C5Me4-[(CEt2)2-O]-、(nPrO)-M-C5Me4-[(CEt2)2-O]-、(iPrO)-M-C5Me4-[(CEt2)2-O]-、(nBuO)-M-C5Me4-[(CEt2)2-O]-、(iBuO)-M-C5Me4-[(CEt2)2-O]-、(tBuO)-M-C5Me4-[(CEt2)2-O]-、(sBuO)-M-C5Me4-[(CEt2)2-O]-、(H2N)2-M-C5Me4-[(CiPr2)2-O]-、(Me2N)2-M-C5Me4-[(CiPr2)2-O]-、(Et2N)2-M-C5Me4-[(CiPr2)2-O]-、(MeEtN)2-M-C5Me4-[(CiPr2)2-O]-、(nPr2N)2-M-C5Me4-[(CiPr2)2-O]-、(iPr2N)2-M-C5Me4-[(CiPr2)2-O]-、(nBu2N)2-M-C5Me4-[(CiPr2)2-O]-、(iBu2N)2-M-C5Me4-[(CiPr2)2-O]-、(sBu2N)2-M-C5Me4-[(CiPr2)2-O]-、(tBu2N)2-M-C5Me4-[(CiPr2)2-O]-、(H2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C5Me4-[(CiPr2)2-O]-、(HO)-M-C5Me4-[(CiPr2)2-O]-、(MeO)-M-C5Me4-[(CiPr2)2-O]-、(EtO)-M-C5Me4-[(CiPr2)2-O]-、(nPrO)-M-C5Me4-[(CiPr2)2-O]-、(iPrO)-M-C5Me4-[(CiPr2)2-O]-、(nBuO)-M-C5Me4-[(CiPr2)2-O]-、(iBuO)-M-C5Me4-[(CiPr2)2-O]-、(tBuO)-M-C5Me4-[(CiPr2)2-O]-、(sBuO)-M-C5Me4-[(CiPr2)2-O]-、(H2N)2-M-C5Me4-[(CtBu2)2-O]-、(Me2N)2-M-C5Me4-[(CtBu2)2-O]-、(Et2N)2-M-C5Me4-[(CtBu2)2-O]-、(MeEtN)2-M-C5Me4-[(CtBu2)2-O]-、(nPr2N)2-M-C5Me4-[(CtBu2)2-O]-、(iPr2N)2-M-C5Me4-[(CtBu2)2-O]-、(nBu2N)2-M-C5Me4-[(CtBu2)2-O]-、(iBu2N)2-M-C5Me4-[(CtBu2)2-O]-、(sBu2N)2-M-C5Me4-[(CtBu2)2-O]-、(tBu2N)2-M-C5Me4-[(CtBu2)2-O]-、(H2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C5Me4-[(CtBu2)2-O]-、(HO)-M-C5Me4-[(CtBu2)2-O]-、(MeO)-M-C5Me4-[(CtBu2)2-O]-、(EtO)-M-C5Me4-[(CtBu2)2-O]-、(nPrO)-M-C5Me4-[(CtBu2)2-O]-、(iPrO)-M-C5Me4-[(CtBu2)2-O]-、(nBuO)-M-C5Me4-[(CtBu2)2-O]-、(iBuO)-M-C5Me4-[(CtBu2)2-O]-、(tBuO)-M-C5Me4-[(CtBu2)2-O]-、(sBuO)-M-C5Me4-[(CtBu2)2-O]-、(H2N)2-M-C5Me4-[(CMeEt)2-O]-、(Me2N)2-M-C5Me4-[(CMeEt)2-O]-、(Et2N)2-M-C5Me4-[(CMeEt)2-O]-、(MeEtN)2-M-C5Me4-[(CMeEt)2-O]-、(nPr2N)2-M-C5Me4-[(CMeEt)2-O]-、(iPr2N)2-M-C5Me4-[(CMeEt)2-O]-、(nBu2N)2-M-C5Me4-[(CMeEt)2-O]-、(iBu2N)2-M-C5Me4-[(CMeEt)2-O]-、(sBu2N)2-M-C5Me4-[(CMeEt)2-O]-、(tBu2N)2-M-C5Me4-[(CMeEt)2-O]-、(H2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C5Me4-[(CMeEt)2-O]-、(HO)-M-C5Me4-[(CMeEt)2-O]-、(MeO)-M-C5Me4-[(CMeEt)2-O]-、(EtO)-M-C5Me4-[(CMeEt)2-O]-、(nPrO)-M-C5Me4-[(CMeEt)2-O]-、(iPrO)-M-C5Me4-[(CMeEt)2-O]-、(nBuO)-M-C5Me4-[(CMeEt)2-O]-、(iBuO)-M-C5Me4-[(CMeEt)2-O]-、(tBuO)-M-C5Me4-[(CMeEt)2-O]-、(sBuO)-M-C5Me4-[(CMeEt)2-O]-、(iPr2N)2-M-C5H4-[(CMeEt)2-O]-、(nBu2N)2-M-C5H4-[(CMeEt)2-O]-、(iBu2N)2-M-C5H4-[(CMeEt)2-O]-、(sBu2N)2-M-C5H4-[(CMeEt)2-O]-、(tBu2N)2-M-C5H4-[(CMeEt)2-O]-、(H2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C5H4-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C5H4-[(CMeEt)2-O]-、(HO)-M-C5H4-[(CMeEt)2-O]-、(MeO)-M-C5H4-[(CMeEt)2-O]-、(EtO)-M-C5H4-[(CMeEt)2-O]-、(nPrO)-M-C5H4-[(CMeEt)2-O]-、(iPrO)-M-C5H4-[(CMeEt)2-O]-、(nBuO)-M-C5H4-[(CMeEt)2-O]-、(iBuO)-M-C5H4-[(CMeEt)2-O]-、(tBuO)-M-C5H4-[(CMeEt)2-O]-、(sBuO)-M-C5H4-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-Me-3-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-3-[(CH2)2-O]-、(HO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(MeO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(EtO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(nPrO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(iPrO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(nBuO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(iBuO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(tBuO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(sBuO)-M-C4H3-1-Me-3-[(CH2)2-O]-、(H2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-Me-3-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(HO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(MeO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(EtO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-Me-3-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-Me-3-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(HO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(MeO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(EtO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-Me-3-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(HO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-Me-3-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(HO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-Me-3-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(HO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(sBuO)-M-C4H3-1-Me-3-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-Et-3-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-3-[(CH2)2-O]-、(HO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(MeO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(EtO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(nPrO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(iPrO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(nBuO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(iBuO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(tBuO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(sBuO)-M-C4H3-1-Et-3-[(CH2)2-O]-、(H2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-Et-3-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(HO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(MeO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(EtO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-Et-3-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-Et-3-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(HO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(MeO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(EtO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-Et-3-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(HO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-Et-3-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(HO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-Et-3-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(HO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(sBuO)-M-C4H3-1-Et-3-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-3-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(HO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(MeO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(EtO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(nPrO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(iPrO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(nBuO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(iBuO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(tBuO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(sBuO)-M-C4H3-1-iPr-3-[(CH2)2-O]-、(H2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(HO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(MeO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(EtO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-iPr-3-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(HO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(MeO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(EtO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-iPr-3-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(HO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-iPr-3-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(HO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-iPr-3-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(HO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(sBuO)-M-C4H3-1-iPr-3-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-3-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(HO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(MeO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(EtO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(nPrO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(iPrO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(nBuO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(iBuO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(tBuO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(sBuO)-M-C4H3-1-tBu-3-[(CH2)2-O]-、(H2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(HO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(MeO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(EtO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-tBu-3-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(HO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(MeO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(EtO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-tBu-3-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(HO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-tBu-3-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(HO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-tBu-3-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(HO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(sBuO)-M-C4H3-1-tBu-3-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-Me-2-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-2-[(CH2)2-O]-、(HO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(MeO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(EtO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(nPrO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(iPrO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(nBuO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(iBuO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(tBuO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(sBuO)-M-C4H3-1-Me-2-[(CH2)2-O]-、(H2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-Me-2-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(HO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(MeO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(EtO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-Me-2-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-Me-2-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(HO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(MeO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(EtO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-Me-2-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(HO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-Me-2-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(HO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-Me-2-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(HO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(sBuO)-M-C4H3-1-Me-2-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-Et-2-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-2-[(CH2)2-O]-、(HO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(MeO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(EtO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(nPrO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(iPrO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(nBuO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(iBuO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(tBuO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(sBuO)-M-C4H3-1-Et-2-[(CH2)2-O]-、(H2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-Et-2-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(HO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(MeO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(EtO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-Et-2-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-Et-2-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(HO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(MeO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(EtO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-Et-2-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(HO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-Et-2-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(HO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-Et-2-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(HO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(sBuO)-M-C4H3-1-Et-2-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-2-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(HO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(MeO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(EtO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(nPrO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(iPrO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(nBuO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(iBuO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(tBuO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(sBuO)-M-C4H3-1-iPr-2-[(CH2)2-O]-、(H2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(HO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(MeO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(EtO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-iPr-2-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(HO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(MeO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(EtO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-iPr-2-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(HO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-iPr-2-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(HO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-iPr-2-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(HO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(sBuO)-M-C4H3-1-iPr-2-[(CMeEt)2-O]-、(H2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(Me2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(Et2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-2-[(CH2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(HO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(MeO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(EtO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(nPrO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(iPrO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(nBuO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(iBuO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(tBuO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(sBuO)-M-C4H3-1-tBu-2-[(CH2)2-O]-、(H2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(Me2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(Et2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(HO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(MeO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(EtO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(nPrO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(iPrO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(nBuO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(iBuO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(tBuO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(sBuO)-M-C4H3-1-tBu-2-[(CMe2)2-O]-、(H2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(Me2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(Et2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(HO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(MeO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(EtO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(nPrO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(iPrO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(nBuO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(iBuO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(tBuO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(sBuO)-M-C4H3-1-tBu-2-[(CEt2)2-O]-、(H2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(Me2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(Et2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(HO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(MeO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(EtO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(nPrO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(iPrO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(nBuO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(iBuO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(tBuO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(sBuO)-M-C4H3-1-tBu-2-[(CiPr2)2-O]-、(H2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(Me2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(Et2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(MeEtN)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(nPr2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(iPr2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(nBu2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(iBu2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(sBu2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(tBu2N)2-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(HO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(MeO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(EtO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(nPrO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(iPrO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(nBuO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(iBuO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(tBuO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(sBuO)-M-C4H3-1-tBu-2-[(CtBu2)2-O]-、(H2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(Me2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(Et2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(MeEtN)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(nPr2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(iPr2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(nBu2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(iBu2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(sBu2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(tBu2N)2-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(H2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(Me2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(Et2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(MeEtN)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(nPr2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(iPr2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(nBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(iBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(sBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(tBu2N)(Cp)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(HO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(MeO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(EtO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(nPrO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(iPrO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(nBuO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(iBuO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、(tBuO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-、以及(sBuO)-M-C4H3-1-tBu-2-[(CMeEt)2-O]-，其中M为以η5键合模式键合至Cp基团的Ti、Zr或Hf；除该Cp基团中那些碳之外的碳可被Si、B或P替换。
优选的Ti前体包括L2-Ti-C5H4-(CH2-CH2-O)-、L2-Ti-C5H3-1-Me-3-[(CH2-CH2-O)-、和L2-Ti-C5H3-1-iPr-3-[(CH2-CH2-O)-，分别对应于以下结构式：
其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基或相邻的R′对形成烃基环。更具体地，示例性Ti前体包括但不限于(NH2)2-Ti-C5H4-[(CH2)2-O]-、(NMe2)2-Ti-C5H4-[(CH2)2-O]-、(NEt2)2-Ti-C5H4-[(CH2)2-O]-、(NnPr2)2-Ti-C5H4-[(CH2)2-O]-、(NiPr2)2-Ti-C5H4-[(CH2)2-O]-、(NnBu2)2-Ti-C5H4-[(CH2)2-O]-、(NiBu2)2-Ti-C5H4-[(CH2)2-O]-、(NsBu2)2-Ti-C5H4-[(CH2)2-O]-、(NtBu2)2-Ti-C5H4-[(CH2)2-O]-、(NHMe)2-Ti-C5H4-[(CH2)2-O]-、(NHEt)2-Ti-C5H4-[(CH2)2-O]-、(NHnPr)2-Ti-C5H4-[(CH2)2-O]-、(NHiPr)2-Ti-C5H4-[(CH2)2-O]-、(NHnBu)2-Ti-C5H4-[(CH2)2-O]-、(NHiBu)2-Ti-C5H4-[(CH2)2-O]-、(NHsBu)2-Ti-C5H4-[(CH2)2-O]-、(NHtBu)2-Ti-C5H4-[(CH2)2-O]-、(NMeEt)2-Ti-C5H4-[(CH2)2-O]-、(NMenPr)2-Ti-C5H4-[(CH2)2-O]-、(NMeiPr)2-Ti-C5H4-[(CH2)2-O]-、(NMenBu)2-Ti-C5H4-[(CH2)2-O]-、(NMeiBu)2-Ti-C5H4-[(CH2)2-O]-、(NMesBu)2-Ti-C5H4-[(CH2)2-O]-、(NMetBu)2-Ti-C5H4-[(CH2)2-O]-、(NEtnPr)2-Ti-C5H4-[(CH2)2-O]-、(NEtiPr)2-Ti-C5H4-[(CH2)2-O]-、(NEtnBu)2-Ti-C5H4-[(CH2)2-O]-、(NEtiBu)2-Ti-C5H4-[(CH2)2-O]-、(NEtsBu)2-Ti-C5H4-[(CH2)2-O]-、(NEttBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPriPr)2-Ti-C5H4-[(CH2)2-O]-、(NnPrnBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPriBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPrsBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPrtBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPrnBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPriBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPrsBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPrtBu)2-Ti-C5H4-[(CH2)2-O]-、(NnBuiBu)2-Ti-C5H4-[(CH2)2-O]-、(NnBusBu)2-Ti-C5H4-[(CH2)2-O]-、(NnButBu)2-Ti-C5H4-[(CH2)2-O]-、(NiBusBu)2-Ti-C5H4-[(CH2)2-O]-、(NiButBu)2-Ti-C5H4-[(CH2)2-O]-、(NsButBu)2-Ti-C5H4-[(CH2)2-O]-、(NH2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMe2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEt2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPr2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPr2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NsBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NtBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHMe)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHEt)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHnPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHiPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHtBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMeEt)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMenPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMeiPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMenBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMeiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMesBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMetBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtnPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtiPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEttBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPriPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPrnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPriBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPrsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPrtBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPrnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPriBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPrsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPrtBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnBuiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnBusBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnButBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiBusBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiButBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NsButBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(OH)-Ti-C5H4-[(CH2)2-O]-、(OMe)-Ti-C5H4-[(CH2)2-O]-、(OEt)-Ti-C5H4-[(CH2)2-O]-、(OnPr)-Ti-C5H4-[(CH2)2-O]-、(OiPr)-Ti-C5H4-[(CH2)2-O]-、(OnBu)-Ti-C5H4-[(CH2)2-O]-、(OiBu)-Ti-C5H4-[(CH2)2-O]-、(OsBu)-Ti-C5H4-[(CH2)2-O]-、(OtBu)-Ti-C5H4-[(CH2)2-O]-、(NH2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OH)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OMe)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OEt)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OnPr)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OiPr)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OnBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OiBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OsBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OtBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NH2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OH)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OMe)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OEt)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OnPr)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OiPr)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OnBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OiBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OsBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、以及(OtBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-。
优选的Zr前体包括L2-Zr-C5H4-(CH2-CH2-O)-、L2-Zr-C5H3-1-Me-3-[(CH2-CH2-O)-、和L2-Zr-C5H3-1-iPr-3-[(CH2-CH2-O)-，分别对应于以下结构式：
其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基或相邻的R′对形成烃基环。更具体地，示例性含Zr前体包括但不限于(NH2)2-Zr-C5H4-[(CH2)2-O]-、(NMe2)2-Zr-C5H4-[(CH2)2-O]-、(NEt2)2-Zr-C5H4-[(CH2)2-O]-、(NnPr2)2-Zr-C5H4-[(CH2)2-O]-、(NiPr2)2-Zr-C5H4-[(CH2)2-O]-、(NnBu2)2-Zr-C5H4-[(CH2)2-O]-、(NiBu2)2-Zr-C5H4-[(CH2)2-O]-、(NsBu2)2-Zr-C5H4-[(CH2)2-O]-、(NtBu2)2-Zr-C5H4-[(CH2)2-O]-、(NHMe)2-Zr-C5H4-[(CH2)2-O]-、(NHEt)2-Zr-C5H4-[(CH2)2-O]-、(NHnPr)2-Zr-C5H4-[(CH2)2-O]-、(NHiPr)2-Zr-C5H4-[(CH2)2-O]-、(NHnBu)2-Zr-C5H4-[(CH2)2-O]-、(NHiBu)2-Zr-C5H4-[(CH2)2-O]-、(NHsBu)2-Zr-C5H4-[(CH2)2-O]-、(NHtBu)2-Zr-C5H4-[(CH2)2-O]-、(NMeEt)2-Zr-C5H4-[(CH2)2-O]-、(NMenPr)2-Zr-C5H4-[(CH2)2-O]-、(NMeiPr)2-Zr-C5H4-[(CH2)2-O]-、(NMenBu)2-Zr-C5H4-[(CH2)2-O]-、(NMeiBu)2-Zr-C5H4-[(CH2)2-O]-、(NMesBu)2-Zr-C5H4-[(CH2)2-O]-、(NMetBu)2-Zr-C5H4-[(CH2)2-O]-、(NEtnPr)2-Zr-C5H4-[(CH2)2-O]-、(NEtiPr)2-Zr-C5H4-[(CH2)2-O]-、(NEtnBu)2-Zr-C5H4-[(CH2)2-O]-、(NEtiBu)2-Zr-C5H4-[(CH2)2-O]-、(NEtsBu)2-Zr-C5H4-[(CH2)2-O]-、(NEttBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPriPr)2-Zr-C5H4-[(CH2)2-O]-、(NnPrnBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPriBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPrsBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPrtBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPrnBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPriBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPrsBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPrtBu)2-Zr-C5H4-[(CH2)2-O]-、(NnBuiBu)2-Zr-C5H4-[(CH2)2-O]-、(NnBusBu)2-Zr-C5H4-[(CH2)2-O]-、(NnButBu)2-Zr-C5H4-[(CH2)2-O]-、(NiBusBu)2-Zr-C5H4-[(CH2)2-O]-、(NiButBu)2-Zr-C5H4-[(CH2)2-O]-、(NsButBu)2-Zr-C5H4-[(CH2)2-O]-、(NH2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMe2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEt2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPr2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPr2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NsBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NtBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHMe)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHEt)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHnPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHiPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHtBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMeEt)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMenPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMeiPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMenBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMeiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMesBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMetBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtnPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtiPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEttBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPriPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPrnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPriBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPrsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPrtBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPrnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPriBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPrsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPrtBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnBuiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnBusBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnButBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiBusBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiButBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NsButBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(OH)-Zr-C5H4-[(CH2)2-O]-、(OMe)-Zr-C5H4-[(CH2)2-O]-、(OEt)-Zr-C5H4-[(CH2)2-O]-、(OnPr)-Zr-C5H4-[(CH2)2-O]-、(OiPr)-Zr-C5H4-[(CH2)2-O]-、(OnBu)-Zr-C5H4-[(CH2)2-O]-、(OiBu)-Zr-C5H4-[(CH2)2-O]-、(OsBu)-Zr-C5H4-[(CH2)2-O]-、(OtBu)-Zr-C5H4-[(CH2)2-O]-、(NH2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OH)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OMe)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OEt)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OnPr)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OiPr)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OnBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OiBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OsBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OtBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NH2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OH)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OMe)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OEt)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OnPr)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OiPr)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OnBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OiBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OsBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、以及(OtBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-。
优选的Hf前体包括L2-Hf-C5H4-(CH2-CH2-O)-、L2-Hf-C5H3-1-Me-3-[(CH2-CH2-O)-、和L2-Hf-C5H3-1-iPr-3-[(CH2-CH2-O)-，分别对应于以下结构式：
其中每个L独立地为选自由以下组成的组的-1阴离子配体：NR′2、OR′、Cp、脒基、β-二酮、或酮亚胺，其中R′为H或C1-C4烃基或相邻的R′对形成烃基环。更具体地，示例性含Hf前体包括但不限于(NH2)2-Hf-C5H4-[(CH2)2-O]-、(NMe2)2-Hf-C5H4-[(CH2)2-O]-、(NEt2)2-Hf-C5H4-[(CH2)2-O]-、(NnPr2)2-Hf-C5H4-[(CH2)2-O]-、(NiPr2)2-Hf-C5H4-[(CH2)2-O]-、(NnBu2)2-Hf-C5H4-[(CH2)2-O]-、(NiBu2)2-Hf-C5H4-[(CH2)2-O]-、(NsBu2)2-Hf-C5H4-[(CH2)2-O]-、(NtBu2)2-Hf-C5H4-[(CH2)2-O]-、(NHMe)2-Hf-C5H4-[(CH2)2-O]-、(NHEt)2-Hf-C5H4-[(CH2)2-O]-、(NHnPr)2-Hf-C5H4-[(CH2)2-O]-、(NHiPr)2-Hf-C5H4-[(CH2)2-O]-、(NHnBu)2-Hf-C5H4-[(CH2)2-O]-、(NHiBu)2-Hf-C5H4-[(CH2)2-O]-、(NHsBu)2-Hf-C5H4-[(CH2)2-O]-、(NHtBu)2-Hf-C5H4-[(CH2)2-O]-、(NMeEt)2-Hf-C5H4-[(CH2)2-O]-、(NMenPr)2-Hf-C5H4-[(CH2)2-O]-、(NMeiPr)2-Hf-C5H4-[(CH2)2-O]-、(NMenBu)2-Hf-C5H4-[(CH2)2-O]-、(NMeiBu)2-Hf-C5H4-[(CH2)2-O]-、(NMesBu)2-Hf-C5H4-[(CH2)2-O]-、(NMetBu)2-Hf-C5H4-[(CH2)2-O]-、(NEtnPr)2-Hf-C5H4-[(CH2)2-O]-、(NEtiPr)2-Hf-C5H4-[(CH2)2-O]-、(NEtnBu)2-Hf-C5H4-[(CH2)2-O]-、(NEtiBu)2-Hf-C5H4-[(CH2)2-O]-、(NEtsBu)2-Hf-C5H4-[(CH2)2-O]-、(NEttBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPriPr)2-Hf-C5H4-[(CH2)2-O]-、(NnPrnBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPriBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPrsBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPrtBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPrnBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPriBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPrsBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPrtBu)2-Hf-C5H4-[(CH2)2-O]-、(NnBuiBu)2-Hf-C5H4-[(CH2)2-O]-、(NnBusBu)2-Hf-C5H4-[(CH2)2-O]-、(NnButBu)2-Hf-C5H4-[(CH2)2-O]-、(NiBusBu)2-Hf-C5H4-[(CH2)2-O]-、(NiButBu)2-Hf-C5H4-[(CH2)2-O]-、(NsButBu)2-Hf-C5H4-[(CH2)2-O]-、(NH2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMe2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEt2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPr2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPr2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NsBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NtBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHMe)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHEt)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHnPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHiPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHtBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMeEt)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMenPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMeiPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMenBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMeiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMesBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMetBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtnPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtiPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEttBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPriPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPrnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPriBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPrsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPrtBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPrnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPriBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPrsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPrtBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnBuiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnBusBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnButBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiBusBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiButBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NsButBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(OH)-Hf-C5H4-[(CH2)2-O]-、(OMe)-Hf-C5H4-[(CH2)2-O]-、(OEt)-Hf-C5H4-[(CH2)2-O]-、(OnPr)-Hf-C5H4-[(CH2)2-O]-、(OiPr)-Hf-C5H4-[(CH2)2-O]-、(OnBu)-Hf-C5H4-[(CH2)2-O]-、(OiBu)-Hf-C5H4-[(CH2)2-O]-、(OsBu)-Hf-C5H4-[(CH2)2-O]-、(OtBu)-Hf-C5H4-[(CH2)2-O]-、(NH2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OH)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OMe)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OEt)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OnPr)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OiPr)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OnBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OiBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OsBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OtBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NH2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OH)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OMe)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OEt)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OnPr)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OiPr)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OnBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OiBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OsBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、以及(OtBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-。
本发明人认识到，与US 8,946,096的例如具有稳定的热稳定性及高蒸气压的Cp-氨基桥连前体相比，所披露的具有以上结构(即，在Cp基团与第4族过渡金属之间具有桥、一种氧配体在该桥中)的第4族过渡金属前体可提供类似或更好的热稳定性。另外，所披露的第4族过渡金属前体的液态可用于直接液体注入(DLI)，其中前体以液态进料，且然后在将其引入反应器中之前汽化。
这些第4族过渡金属前体可以展现(i)足够的挥发性以提供从储存它们的容器快速和可再现的递送到反应腔室中，(ii)高热稳定性以避免在罐中存储期间分解并且使得能够在高温(典型地>275℃)下以ALD模式自限制生长，(iii)对基材末端官能团和与反应气体的适当反应性以易于转化成所希望的膜，和(iv)高纯度以获得具有低杂质的膜。
虽然前体理想地为液体且在鼓泡器或直接液体注入系统中汽化，但使用升华器，诸如Xu等人的PCT公开WO2009/087609中所披露的升华器，将固体前体用于ALD及CVD前体汽化也为有可能的。可替代地，固体前体可混合或溶解于溶剂中以达到直接液体注入系统所使用的可用熔点及粘度。
优选地，含第4族过渡金属的前体中的R在Cp基团上为H或Me或iPr，因为其在大气压热重分析中的极佳汽化结果，留下少量最终剩余物。
所披露的含第4族过渡金属的前体可通过以下方式合成：在低温下，使对应的卤化的含第4族过渡金属的R基团化合物(即，RMX3，其中R及M是上文所定义的且X为Cl、Br或I)与对应的烷醇胺及烷基胺在适合的溶剂诸如二氯甲烷、THF或醚中进行反应。RMX3、烷醇胺及烷基胺是可商购的。完成加成后，在搅拌下混合物升温至室温。在真空下移除溶剂。将剩余物溶解于溶剂诸如甲苯中。过滤所得混合物。溶剂的移除产生粗的含第4族过渡金属的前体。
可替代地，所披露的含第4族过渡金属的前体可通过以下方式合成：在低温下，使对应的含第4族过渡金属的烷氧基及R基团化合物(即，RM(OR″)3)，其中R及M是上文所定义的且R″是C1-C6烷基)与对应的烷醇胺在适合的溶剂诸如庚烷、二氯甲烷、THF或醚中进行反应。RM(OR″)3及烷醇胺是可商购的。完成加成后，在搅拌下混合物升温至室温。在真空下移除溶剂以产生粗的含第4族过渡金属的前体。
在另一替代方案中，所披露的含第4族过渡金属的前体可通过以下方式合成：在低温下，使对应的含第4族过渡金属的胺基及R基团化合物(即，RM(NR″′2)3，其中R及M是上文所定义的且R″′是C1-C6烷基)与对应的烷醇胺在适合的溶剂诸如庚烷、二氯甲烷、THF或醚中进行反应。RM(NR″′2)3及烷醇胺是可商购的。完成加成后，在搅拌下混合物升温至室温。在真空下移除溶剂以产生粗的含第4族过渡金属的前体。
在另一替代方案中，所披露的含第4族过渡金属的前体可通过以下方式合成：在低温下，使对应的含第4族过渡金属的胺化物(即，M(NR″′2)4)，其中M是上文所定义的且R″′为C1-C6烷基)与对应的含Cp的胺或含Cp*的胺在适合的溶剂诸如甲苯、庚烷、二氯甲烷、THF或醚中进行反应。M(NR″′2)4及含Cp的胺或含Cp*的胺是可商购的。完成加成后，在搅拌下混合物升温至室温。在真空下移除溶剂以产生粗的含第4族过渡金属的前体。
为了确保过程可靠性，在使用之前，形成含第4族过渡金属的膜的组合物可通过连续或部分分批蒸馏或升华纯化至在从大致93％w/w至大致100％w/w范围内、优选在从大致99％w/w至大致100％w/w范围内的纯度。形成含第4族过渡金属的膜的组合物可含有以下杂质中的任一种：不希望的同属物种；溶剂；氯化的金属化合物；或其他反应产物。在一个替代方案中，这些杂质的总量低于0.1％w/w。
经纯化的形成含第4族过渡金属的膜的组合物中，己烷、戊烷、二甲醚或苯甲醚中的每一者的浓度可在从大致0％w/w至大致5％w/w、优选从大致0％w/w至大致0.1％w/w范围内。在组合物的合成中可以使用溶剂。如果两者具有相似的沸点，则可能难以从前体分离溶剂。冷却混合物可在液体溶剂中产生固体前体，可通过过滤将其分离。也可以使用真空蒸馏，前提是前体产物不加热至高于大致其分解点。
在一个替代方案中，所披露的形成含第4族过渡金属的膜的组合物含有小于5％v/v、优选小于1％v/v、更优选小于0.1％v/v且甚至更优选小于0.01％v/v的其不希望的同属物种、反应物或其他反应产物中的任一者。此替代方案可提供更好的过程可重复性。此替代方案可通过蒸馏含第4族过渡金属的前体来产生。
在另一替代方案中，特定地当混合物提供改良的过程参数或对目标化合物的分离太困难或昂贵时，所披露的形成含第4族过渡金属的膜的组合物可含有在5％v/v与50％v/v之间的同属含第4族过渡金属的前体、反应物或其他反应产物中的一者或多者。例如，两种第4族过渡金属前体的混合物可产生适用于气相沉积的稳定的液体混合物。
经纯化的形成含第4族过渡金属的膜的组合物中痕量金属及类金属的浓度可各自在从大致0ppb至大致100ppb且更优选从大致0ppb至大致10ppb范围内。这些金属杂质包括但不限于铝(Al)、砷(As)、钡(Ba)、铍(Be)、铋(Bi)、镉(Cd)、钙(Ca)、铬(Cr)、钴(Co)、铜(Cu)、镓(Ga)、锗(Ge)、铪(Hf)、锆(Zr)、铟(In)、铁(Fe)、铅(Pb)、锂(Li)、镁(Mg)、锰(Mn)、钨(W)、镍(Ni)、钾(K)、钠(Na)、锶(Sr)、钍(Th)、锡(Sn)、钛(Ti)、铀(U)、钒(V)及锌(Zn)。
还披露了用于使用气相沉积工艺在基材上形成含第4族过渡金属的层的方法。该方法可以在制造半导体、光伏、LCD-TFT、或平板型装置中是有用的。所披露的形成含第4族过渡金属的膜的组合物可用于使用本领域技术人员已知的任何沉积方法沉积含第4族过渡金属的薄膜。合适的气相沉积方法的实例包括化学气相沉积(CVD)或原子层沉积(ALD)。示例性CVD方法包括热CVD、等离子体增强的CVD(PECVD)、脉冲CVD(PCVD)、低压CVD(LPCVD)、低于大气压的CVD(SACVD)或大气压CVD(APCVD)、热丝CVD(HWCVD，还被称为cat-CVD，其中热丝充当用于沉积工艺的能量来源)、自由基结合的CVD、以及其组合。示例性ALD方法包括热ALD、等离子体增强的ALD(PEALD)、空间隔离ALD、热丝ALD(HWALD)、自由基结合的ALD、以及其组合。也可以使用超临界流体沉积。沉积方法优选为ALD、空间ALD或PE-ALD，以提供合适的台阶覆盖和膜厚度控制。另外，所披露的形成含第4族过渡金属的膜的组合物特别适用于ALD过程，因为其热稳定性使得能够实现完美的自限制生长。
申请人相信，所披露的含第4族过渡金属的前体的N-M键可稳定前体，使其热稳健，这可在共形ALD沉积期间在高纵横比结构方面有帮助。O-M键可提供与基材表面上的任何羟基的良好的反应性，允许ALD沉积中所希望的所需的物理或化学吸附。最后，当R为Cp(经取代或未经取代)时，申请人相信Cp可如同伞一般保持在表面上的M原子上方且确保完美的自我ALD生长。
所披露的形成含第4族过渡金属的膜的组合物可以以纯形式供应或可进一步包含适合的溶剂，诸如乙苯、二甲苯、均三甲苯、癸烷和/或十二烷。所披露的第4族过渡金属前体可以以不同浓度存在于溶剂中。
通过常规器件如管道系统和/或流量计将纯的或共混的形成含第4族过渡金属的膜的组合物以蒸气形式引入反应器内。该蒸气形式可以通过以下方式产生：通过常规汽化步骤(如直接汽化、蒸馏)汽化该纯的或共混的组合物、或通过鼓泡、或通过使用升华器(如Xu等人的PCT公开WO2009/087609中披露的那种)。在将该组合物引入反应器中之前，可将其以液态进料到汽化器(直接液体注入或“DLI”)，在该汽化器中使其汽化。可替代地，可通过将载气传送至含有该化合物的容器中或通过将载气鼓泡进该化合物中使该组合物汽化。载气可包括但不限于Ar、He、N2及其混合物。用载气鼓泡还可移除纯的或共混的化合物溶液中存在的任何溶解氧。载气和组合物的蒸气形式然后作为蒸气被引入反应器中。
如果必要，容器可以被加热到允许组合物处于其液相并具有足够的蒸气压的温度。可以将容器维持在例如大致50℃至大致180℃的范围内的温度下。本领域技术人员认识到可以按已知方式调整容器的温度以控制汽化的组合物的量。
形成含第4族过渡金属的膜的组合物可通过所披露的形成含第4族过渡金属的膜的组合物递送装置递送至半导体加工工具中。图1及图2示出所披露的递送装置1的两个实施例。
图1是形成含第4族过渡金属的膜的组合物的递送装置1的一个实施例的侧视图。在图1中，所披露的形成含第4族过渡金属的膜的组合物11包含在具有至少两个导管(入口导管3和出口导管4)的容器2内。前体领域的普通技术人员将认识到，容器2、入口导管3和出口导管4被制造成即使在升高的温度和压力下，也能防止气态形式的形成含第4族过渡金属的膜的组合物11逸出。
合适的阀包括弹簧加载阀或束缚隔膜阀。阀可进一步包含限流孔(RFO)。递送装置1应连接至气体歧管并且在外壳中。气体歧管应允许当替换递送装置1时可能暴露于空气的管道被安全排空并且吹扫，使得任何残留量的材料不发生反应。
递送装置1必须是不漏的且配备有关闭时不允许即使微小量的材料逸出的阀。递送装置1经由阀6和7流体地连接到半导体加工工具的其他部件，例如以上披露的气柜。优选地，容器2、入口导管3、阀6、出口导管4和阀7典型地由316L EP不锈钢制成。
在图1中，入口导管3的端8位于形成含第4族过渡金属的膜的组合物11的表面上方，而出口导管4的端9位于形成含第4族过渡金属的膜的组合物11的表面下方。在该实施例中，形成含第4族过渡金属的膜的组合物11优选呈液体形式。包括但不限于氮气、氩气、氦气及其混合物的惰性气体可被引入到入口导管3中。惰性气体对容器2加压，使得迫使液体的形成含第4族过渡金属的膜的组合物11通过出口导管4且进入半导体加工工具中的部件(未示出)中。半导体加工工具可包括汽化器，其使用或不使用载气(诸如氦气、氩气、氮气或其混合物)将液体的形成含第4族过渡金属的膜的组合物11转变成蒸气，以便将该蒸气递送至其中定位有待修复晶片且处理以蒸气相发生的腔室中。可替代地，液体的形成含第4族过渡金属的膜的组合物11可以作为射流或气溶胶直接递送到晶片表面上。
图2为该形成含第4族过渡金属的膜的组合物的递送装置1的第二实施例的侧视图。在图2中，入口导管3的端8位于形成含第4族过渡金属的膜的组合物11的表面下方，而出口导管4的端9位于形成含第4族过渡金属的膜的组合物11的表面上方。图2还包括任选的加热元件14，其可以升高形成含第4族过渡金属的膜的组合物11的温度。形成含第4族过渡金属的膜的组合物11可以呈固体或液体形式。包括但不限于氮气、氩气、氦气及其混合物的惰性气体被引入到入口导管3中。惰性气体流经形成含第4族过渡金属的膜的组合物11并将惰性气体和汽化的形成含第4族过渡金属的膜的组合物11的混合物携载至出口导管4和半导体加工工具中的部件。
图1和图2二者都包括阀6和7。本领域普通技术人员将认识到，阀6和7可以被置于打开或关闭位置，以分别允许流过导管3和4。如果形成含第4族过渡金属的膜的组合物11呈蒸气形式或如果在固/液相上方存在足够的蒸气压，则可以使用图1或图2中的递送装置1，或具有终止于存在的任何固体或液体表面上方的单个导管的更简单的递送装置。在这种情况下，仅通过分别打开图1中的阀6或图2中的阀7，将形成含第4族过渡金属的膜的组合物11以蒸气形式通过导管3或4递送。递送装置1可以例如通过使用任选的加热元件14维持在合适的温度，以便为待以蒸气形式递送的形成含第4族过渡金属的膜的组合物11提供足够的蒸气压。
虽然图1和图2披露了形成含第4族过渡金属的膜的组合物的递送装置1的两个实施例，但是本领域普通技术人员将认识到，入口导管3和出口导管4二者都可以位于形成含第4族过渡金属的膜的组合物11的表面上方而不背离本文中的披露内容。此外，入口导管3可为填充端口。
当形成含第4族过渡金属的膜的组合物是固体时，可以使用升华器将它们的蒸气递送到反应器中。图3示出了合适的升华器100的一个实施例。升华器100包括容器33。容器33可以是圆柱形容器，或可替代地，可以是但不限于任何形状。容器33由以下材料构造，这些材料如但不限于不锈钢、镍及其合金、石英、玻璃、以及其他化学上相容的材料。在某些情况下，容器33由另一种金属或金属合金构造(没有限制)。在某些情况下，容器33具有从约8厘米至约55厘米的内径，并且可替代地，从约8厘米至约30厘米的内径。如由本领域技术人员理解的，替代配置可以具有不同的尺寸。
容器33包括可密封的顶部15、密封件18、以及垫片20。可密封的顶部15被配置成密封容器33与外部环境隔开。可密封的顶部15被配置成允许进入容器33。另外，可密封的顶部15被配置成用于使导管通入容器33中。可替代地，可密封的顶部15被配置成允许流体流入容器33中。可密封的顶部15被配置成接收并且穿过包括浸入管92的导管以保持与容器33处于流体接触。具有控制阀90和配件95的浸入管92被配置成用于使载气流动到容器33中。在某些情况下，浸入管92沿着容器33的中心轴向下延伸。进一步地，可密封的顶部15被配置成接收并且穿过包括出口管12的导管。将载气以及形成含第4族过渡金属的膜的组合物的蒸气通过出口管12从容器33中移除。出口管12包括控制阀10和配件5。在某些情况下，将出口管12流体联接至气体递送歧管，用于将载气从升华器100引导至膜沉积腔室。
容器33和可密封的顶部15被至少两个密封件18，可替代地，被至少约四个密封件密封。在某些情况下，可密封的顶部15被至少约八个密封件18密封到容器33上。如由本领域技术人员理解的，密封件18可释放地将可密封的顶部15联接到容器33上，并且与垫片20形成耐受气体的密封。密封件18可以包括对于本领域技术人员已知的用于密封容器33的任何合适的器件。在某些情况下，密封件18包括翼形螺钉。
如图3中所示，容器33进一步包括至少一个布置在其中的盘。盘包括用于固体材料的搁架或水平支承件。在某些实施例中，内部盘30被环状地布置在容器33内，使得盘30包括小于容器33的内径或周长的外径或周长，形成开口31。外部盘86被周向地布置在容器33内，使得盘86包括与容器33的内径相同、大约相同、或总体上一致的外径或周长。外部盘86形成布置在该盘的中心处的开口87。多个盘被布置在容器33内。这些盘以交替方式堆叠，其中内部盘30、34、36、44与交替的外部盘62、78、82、86在该容器内竖直地堆叠。在实施例中，内部盘30、34、36、44环状地向外延伸，并且外部盘62、78、82、86环状地朝向容器33的中心延伸。如图3的实施例中所示，内部盘30、34、36、44不与外部盘62、78、82、86处于物理接触。
组装的升华器100包括内部盘30、34、36、44，这些内部盘包括对齐且联接的支承脚50，内部通道51，同心壁40、41、42，以及同心槽缝47、48、49。内部盘30、34、36、44竖直地堆叠，并且围绕浸入管92环状地定向。另外，升华器包括外部盘62、78、82、86。如图3中所示，外部盘62、78、82、86应该紧密地配合到容器33中用于良好接触以将热量从容器33传导至盘62、78、82、86。优选地，外部盘62、78、82、86被联接至容器33的内壁，或者处于与该内壁物理接触。
如所示，外部盘62、78、82、86和内部盘30、34、36、44堆叠在容器33内部。当在容器33中组装以形成升华器100时，内部盘30、34、36、44在组装的外部盘62、78、82、86之间形成外部气体通道31、35、37、45。进一步地，外部盘62、78、82、86与内部盘30、34、36、44的支承脚形成内部气体通道56、79、83、87。内部盘30、34、36、44的壁40、41、42形成用于保持固体前体的带凹槽的槽缝。外部盘62、78、82、86包括用于保持固体前体的壁68、69、70。在组装期间，将固体前体装载到内部盘30、34、36、44的环形槽缝47、48、49以及外部盘62、78、82、86的环形槽缝64、65、66中。
虽然图3披露了能够将任何固体的形成含第4族过渡金属的膜的组合物的蒸气递送至反应器的升华器的一个实施例，但本领域普通技术人员将认识到，其他升华器设计也可以是合适的，而不脱离本文的传授内容。最后，本领域技术人员将认识到，可使用其他递送装置(诸如Jurcik等人的WO 2006/059187中所披露的安瓿)将所披露的形成含第4族过渡金属的膜的组合物11递送至半导体加工工具中，而不脱离本文的传授内容。
反应腔室可为在其中进行沉积法的装置的任何密闭室或腔室，诸如但不限于平行板型反应器、冷壁型反应器、热壁型反应器、单晶片反应器、多晶片反应器、或其他此类类型的沉积系统。所有这些示例性反应腔室都能够充当ALD反应腔室。反应腔室可维持在从约0.5毫托至约20托范围内、优选在约0.1托与约5托之间的压力下。另外，该反应腔室内的温度可以在从约50℃至约600℃的范围内。本领域普通技术人员将认识到，可以实验方式确定每种含第4族过渡金属的前体的理想沉积温度范围，以实现所期望的结果。
反应器含有一个或多个其上将沉积薄膜的基材。基材一般定义为在其上进行工艺的材料。基材可以是用于半导体、光伏、平板或LCD-TFT装置制造中的任何合适的基材。适合基材的实例包括晶片，诸如硅、SiGe、二氧化硅、玻璃或Ge。也可使用塑料基材诸如聚(3,4-亚乙基二氧噻吩)聚(苯乙烯磺酸酯)[PEDOT:PSS]。基材还可具有一个或多个已从先前制造步骤沉积于其上的不同材料层。例如，晶片可包括硅层(结晶、无定形、多孔等)、氧化硅层、氮化硅层、氮氧化硅层、碳掺杂的氧化硅(SiCOH)层或其组合。另外，晶片可包括铜、钴、钌、钨和/或其他金属层(例如，铂、钯、镍、钌或金)。晶片可包括阻挡层或电极，诸如钽、氮化钽等。也可使用塑料层诸如聚(3,4-亚乙基二氧噻吩)聚(苯乙烯磺酸酯)[PEDOT:PSS]。层可以是平坦的或图案化的。基材可为有机图案化光阻膜。基材可包括在MIM、DRAM或FeRam技术中用作介电材料(例如，基于ZrO2的材料、基于HfO2的材料、基于TiO2的材料、基于稀土氧化物的材料、基于三元氧化物的材料等)或来自用作电极的基于氮化物的膜(例如，TaN、TiN、NbN)的氧化物层。所披露的工艺可直接在晶片上或直接在晶片顶部的一个或多于一个(当图案化层形成该基材时)层上沉积该含第4族的层。此外，本领域普通技术人员将认识到，本文所用的术语“膜”或“层”是指铺设或铺展在表面上的一些材料的厚度并且该表面可为沟槽或线。贯穿本说明书和权利要求书，晶片及其上的任何相关层被称为基材。所用的实际基材也可取决于所用的具体前体实施例。然而，在许多情况下，所用的优选基材将选自TiN、NbN、Ru、Si及SiGe型基材，诸如多晶硅或结晶硅基材。例如，第4族金属氧化物膜可沉积到TiN基材上。在后续加工中，TiN层可沉积于第4族金属氧化物层上，形成用作DRAM电容器的TiN/第4族金属氧化物/TiN堆叠体。金属氧化物层本身可由各种金属氧化物的若干层的堆叠体制成，这些金属氧化物通常选自第4族金属氧化物、第5组金属氧化物、Al2O3、SiO2、和MoO2。
反应器内的温度和压力保持在适用于气相沉积的条件下。换言之，在将汽化的组合物引入腔室中之后，腔室内的条件是使得该汽化的含第4族过渡金属的前体的至少一部分沉积到基材上以形成含第4族过渡金属的膜。例如，根据每个沉积参数所要求的，反应器中的压力可以保持在约1Pa与约105Pa之间，更优选在约25Pa与约103Pa之间。同样，反应器中的温度可以保持在约100℃与约500℃之间，优选在约200℃与约450℃之间。本领域普通技术人员将认识到，“该汽化的含第4族过渡金属的前体的至少一部分沉积”意指一些或全部前体与基材反应或粘附至基材。
可以通过控制基材固持器的温度或控制反应器壁的温度来控制反应器的温度。用于加热基材的装置在本领域中是已知的。反应器壁被加热至足够温度以便以足够生长速率并且以所希望的物理状态和组成获得所希望的膜。非限制性示例性温度范围(可以将反应器壁加热到该温度范围)包括从大致100℃至大致500℃。当利用等离子体沉积工艺时，沉积温度可在从大致50℃至大致400℃的范围内。可替代地，当进行热工艺时，沉积温度可在从大致200℃至大致450℃的范围内。
除所披露的形成含第4族过渡金属的膜的组合物以外，还可将反应物引入反应器中。反应物可以是氧化气体，诸如以下项之一：O2、O3、H2O、H2O2、NO、N2O、NO2、二醇(诸如乙二醇或水合六氟丙酮)、含氧自由基诸如O·或OH·、NO、NO2、羧酸、甲酸、乙酸、丙酸、及其混合物。优选地，氧化气体选自下组，该组由以下各项组成：O2、O3、H2O、H2O2、其含氧自由基如O·或OH·、及其混合物。
可替代地，反应物可为H2、NH3、肼(诸如N2H4、MeHNNH2、Me2NNH2、MeHNNHMe、苯肼)、有机胺(诸如NMeH2、NEtH2、NMe2H、NEt2H、NMe3、NEt3、(SiMe3)2NH、环状胺像吡咯烷或嘧啶)、二胺(诸如乙二胺、二甲基乙二胺、四甲基乙二胺)、氨基醇(诸如乙醇胺[HO-CH2-CH2-NH2]、双乙醇胺[HN(C2H5OH)2]或三乙醇胺[N(C2H5OH)3])、吡唑啉、吡啶、其自由基、或其混合物。优选地，反应物为H2、NH3、其自由基、或其混合物。
在另一替代方案中，反应物可为(SiH3)3N、氢化硅烷(如SiH4、Si2H6、Si3H8、Si4H10、Si5H10、或Si6H12)、氯硅烷及氯聚硅烷(如SiHCl3、SiH2Cl2、SiH3Cl、Si2Cl6、Si2HCl5、或Si3Cl8)、烷基硅烷(如Me2SiH2、Et2SiH2、MeSiH3、EtSiH3、或苯基硅烷)及氨基硅烷(如三(二甲氨基硅烷)、双二乙氨基硅烷、二异丙基氨基硅烷或其他单氨基硅烷、双氨基硅烷或三氨基硅烷)、其自由基、或其混合物。优选地，反应物为(SiH3)3N或氨基硅烷。
反应物可通过等离子体处理，以便使反应物分解成其自由基形式。当用等离子体处理时，N2还可以被用作还原气体。例如，可以用从约50W至约2500W、优选地从约100W至约400W范围内的功率产生等离子体。等离子体可产生或存在于反应器本身内。可替代地，等离子体通常可以处于远离反应器的位置处，例如在远程定位的等离子体系统中。本领域技术人员将认识到适合于此种等离子体处理的方法和设备。
例如，反应物可以被引入直接等离子体反应器(其在反应腔室中产生等离子体)中，以在该反应腔室中产生等离子体处理过的反应物。示例性的直接等离子体反应器包括由垂恩技术公司(Trion Technologies)生产的TitanTM PECVD系统。反应物可以在等离子体加工之前被引入并保持在反应腔室中。可替代地，等离子体加工可以与引入反应物同时发生。原位等离子体典型地是在喷淋头与基材固持器之间产生的13.56MHz RF电感耦合等离子体。根据是否发生正离子碰撞，基材或喷淋头可以是被供电电极。原位等离子体产生器中的典型施加功率为从大致30W至大致1000W。优选地，在所披露的方法中使用从大致30W至大致600W的功率。更优选地，功率的范围从大致100W至大致500W。使用原位等离子体的反应物的解离典型地小于对于相同功率输入使用远程等离子体源实现的，并且因此在反应物解离中不如远程等离子体系统有效，这可能有利于将含第4族过渡金属的膜沉积在容易被等离子体损坏的基材上。
可替代地，等离子体处理过的反应物可以在反应腔室外产生。MKS仪器公司的反应性气体产生器可以用于在通入反应腔室之前处理反应物。在2.45GHz、7kW等离子体功率和从大致0.5托至大致10托范围内的压力下操作，反应物O2可分解成两个O·自由基。优选地，可以用范围从约1kW至约10kW、更优选地从约2.5kW至约7.5kW的功率产生远程等离子体。
腔室内的气相沉积条件允许所披露的形成含第4族过渡金属的膜的组合物及反应物反应，并在基材上形成含第4族过渡金属的膜。在一些实施例中，申请人相信等离子体处理反应物可以向反应物提供与所披露的组合物反应所需的能量。
根据希望沉积哪种类型的膜，可以将另外的前体化合物引入反应器中。前体可用于向含第4族过渡金属的膜提供另外的元素。另外的元素可包括镧系元素(例如，镱、铒、镝、钆、镨、铈、镧、钇)、锗、硅、铝、硼、磷、第3族元素(即Sc、Y、La或Ac)、不同的第4族元素或第5族元素(即V、Nb或Ta)、或这些的混合物。当利用另外的前体化合物时，所得的沉积在基材上的膜含有与至少一种另外的元素组合的第4族过渡金属。
可以将形成含第4族过渡金属的膜的组合物和反应物同时(化学气相沉积)、顺序地(原子层沉积)或其不同组合引入到反应器中。可以在引入组合物与引入反应物之间用惰性气体吹扫反应器。可替代地，反应物和组合物可以混合在一起以形成反应物/化合物混合物，并且然后以混合物形式引入反应器中。另一个实例是连续引入反应物并通过脉冲(脉冲化学气相沉积)引入形成含第4族过渡金属的膜的组合物。
汽化的组合物和反应物可以顺序地或同时(例如脉冲CVD)脉冲进入反应器。组合物的每次脉冲可持续范围从约0.01秒至约100秒、可替代地从约0.3秒至约30秒、可替代地从约0.5秒至约10秒的一段时间。反应物也可以脉冲进入反应器。在此类实施例中，每种气体的脉冲可持续从约0.01秒至约100秒、可替代地从约0.3秒至约30秒、可替代地从约0.5秒至约10秒。在另一个替代方案中，可以同时地从喷淋头喷射该汽化的组合物和一种或多种反应物，保持若干晶片的基座在该喷淋头下旋转(空间ALD)。
根据具体的工艺参数，沉积可能进行不同的时间长度。通常，可使沉积继续所希望或所必需长度的时间以产生具有必需特性的膜。根据具体的沉积工艺，典型的膜厚度可以从几埃到几百微米变化。沉积工艺也可以进行获得所希望的膜所必需的很多次。
在一个非限制性的示例性CVD型过程中，将所披露的形成含第4族过渡金属的膜的组合物的蒸气相和反应物同时引入到反应器中。两者反应以形成所得的含第4族过渡金属的薄膜。当在此示例性CVD工艺中的反应物用等离子体处理时，示例性CVD工艺变成示例性的PECVD工艺。反应物可以在引入到腔室中之前或之后用等离子体处理。
在一种非限制性示例性ALD型过程中，将所披露的形成含第4族过渡金属的膜的组合物的蒸气相引入反应器中，其中含第4族过渡金属的前体以物理或化学方式吸附于基材上。然后可通过吹扫和/或排空反应器从该反应器中去除过量的组合物。将所希望的气体(例如，O3)引入反应器中，在该反应器中使其以自限制的方式与物理吸附或化学吸附的前体反应。通过吹扫和/或排空反应器从该反应器中去除任何过量的还原气体。如果所希望的膜是第4族过渡金属膜，此两步工艺可以提供所希望的膜厚度，或者可以重复直到获得具有必需厚度的膜。
可替代地，如果所希望的膜含有第4族过渡金属和第二种元素，则可以在以上两步工艺之后将另外的前体化合物的蒸气引入反应器中。另外的前体化合物将基于所沉积的第4族过渡金属膜的性质来选择。在引入反应器中之后，使该另外的前体化合物与基材接触。通过吹扫和/或排空该反应器从该反应器中去除任何过量的前体化合物。再次，可以将所希望的气体引入反应器中以与前体化合物反应。通过吹扫和/或排空反应器从该反应器中去除过量气体。如果已经实现了所希望的膜厚度，则可终止工艺。然而，如果较厚的膜是所希望的，则可重复整个四步骤工艺。通过交替提供含第4族过渡金属的化合物、另外的前体化合物和反应物，可以沉积具有所希望的组成和厚度的膜。
当在此示例性ALD工艺中的反应物用等离子体处理时，示例性ALD工艺变成示例性的PEALD工艺。反应物可以在引入到腔室中之前或之后用等离子体处理。
在第二非限制性示例性ALD型过程中，将所披露的含Zr前体之一(例如Me5CpZr((-O-CH2-CH2-)3N))的蒸气相引入反应器中，在该反应器中其与TiN基材接触。然后可通过吹扫和/或排空该反应器从该反应器中去除过量的含Zr前体。将所希望的气体(例如，O3)引入反应器中，在该反应器中使其以自限制的方式与吸收的含Zr前体反应以形成ZrO2膜。通过吹扫和/或排空反应器从该反应器中去除任何过量的氧化气体。可以重复这两个步骤，直到ZrO2膜获得所希望的厚度。所得TiN/ZrO2/TiN堆叠体可用于DRAM电容器中。ZrO2金属氧化物膜可包括在含有各种金属氧化物的叠层体的更复杂的堆叠体内。典型地，使用ZrO2/Al2O3/ZrO2堆叠体，但也使用TiO2/ZrO2/Al2O3/ZrO2、ZrO2/Nb2O3/ZrO2、ZrO2/HfO2/TiO2/ZrO2等。
由上文所论述的过程产生的含第4族过渡金属的膜可包括第4族过渡金属氧化物(MM′iOx，其中i在从0至1的范围内；x在从1至6的范围内；且M′选自第3族元素、不同的第4族元素(即M≠M′)、第5族元素、镧系元素、Si、Al、B、P或Ge)或第4族过渡金属氮氧化物(MM′iNyOx，其中i在从0至1的范围内；x及y在从1至6的范围内；并且M′选自第3族元素、不同的第4族元素(即M≠M′)、第5族元素、镧系元素、Si、Al、B、P或Ge)。本领域普通技术人员将认识到，通过适当的所披露化合物、任选的前体化合物以及反应物物种的明断选择，可以获得所希望的膜组成。
一经获得所希望的膜厚度，可以使膜经受另外的加工，如热退火、炉退火、快速热退火、UV或电子束固化、和/或等离子体气体暴露。本领域技术人员认识到用于进行这些另外的加工步骤的系统和方法。例如，含第4族过渡金属的膜可在惰性气氛、含H气氛、含N气氛、含O气氛或其组合下，在从大致200℃与大致1000℃范围内的温度下暴露从大致0.1秒至大致7200秒范围内的时间。最优选地，在含H气氛或含O气氛下，温度为400℃持续3600秒。所得膜可含有较少的杂质，并且因此可具有改善的密度，导致改善的泄漏电流。退火步骤可以在进行沉积工艺的同一反应腔室中进行。可替代地，可以从反应腔室中移除基材，其中在单独的设备中进行退火/快速退火工艺。已经发现任何以上后处理方法、但尤其是热退火有效地减少含第4族过渡金属的膜的碳和氮污染。这进而倾向于改善膜的电阻率。
应当理解，由本领域技术人员可在如所附权利要求中所表述的本发明的原则和范围内做出在此已经描述且阐明以解释本发明的本质的细节、材料、步骤和零件安排上的许多附加的改变。因此，本发明不旨在限于以上给出的实例和/或附图中的具体实施例。
Claims (14)
1.一种形成含第4族过渡金属的膜的组合物，该组合物包含具有式L2-M-C5R4-[(ER2)m-(ER2)n-O]-的第4族过渡金属前体，参考以下结构式：
其中M为以η5键合模式键合至Cp基团的Ti、Zr或Hf；每个E独立地为C、Si、B或P；m和n独立地为0、1或2；m+n>1；每个R独立地为氢或C1-C4烃基；且每个L独立地为-1阴离子配体。
2.如权利要求1所述的形成含第4族过渡金属的膜的组合物，其中，该-1阴离子配体选自由以下组成的组：NR′2、OR′、Cp、脒基、β-二酮及酮亚胺，其中R′为H或C1-C4烃基。
3.如权利要求2所述的形成含第4族过渡金属的膜的组合物，其中，E为C。
4.如权利要求3所述的形成含第4族过渡金属的膜的组合物，其中，M为Ti。
5.如权利要求4所述的形成含第4族过渡金属的膜的组合物，其中，该第4族过渡金属前体选自由以下组成的组：(NH2)2-Ti-C5H4-[(CH2)2-O]-、(NMe2)2-Ti-C5H4-[(CH2)2-O]-、(NEt2)2-Ti-C5H4-[(CH2)2-O]-、(NnPr2)2-Ti-C5H4-[(CH2)2-O]-、(NiPr2)2-Ti-C5H4-[(CH2)2-O]-、(NnBu2)2-Ti-C5H4-[(CH2)2-O]-、(NiBu2)2-Ti-C5H4-[(CH2)2-O]-、(NsBu2)2-Ti-C5H4-[(CH2)2-O]-、(NtBu2)2-Ti-C5H4-[(CH2)2-O]-、(NHMe)2-Ti-C5H4-[(CH2)2-O]-、(NHEt)2-Ti-C5H4-[(CH2)2-O]-、(NHnPr)2-Ti-C5H4-[(CH2)2-O]-、(NHiPr)2-Ti-C5H4-[(CH2)2-O]-、(NHnBu)2-Ti-C5H4-[(CH2)2-O]-、(NHiBu)2-Ti-C5H4-[(CH2)2-O]-、(NHsBu)2-Ti-C5H4-[(CH2)2-O]-、(NHtBu)2-Ti-C5H4-[(CH2)2-O]-、(NMeEt)2-Ti-C5H4-[(CH2)2-O]-、(NMenPr)2-Ti-C5H4-[(CH2)2-O]-、(NMeiPr)2-Ti-C5H4-[(CH2)2-O]-、(NMenBu)2-Ti-C5H4-[(CH2)2-O]-、(NMeiBu)2-Ti-C5H4-[(CH2)2-O]-、(NMesBu)2-Ti-C5H4-[(CH2)2-O]-、(NMetBu)2-Ti-C5H4-[(CH2)2-O]-、(NEtnPr)2-Ti-C5H4-[(CH2)2-O]-、(NEtiPr)2-Ti-C5H4-[(CH2)2-O]-、(NEtnBu)2-Ti-C5H4-[(CH2)2-O]-、(NEtiBu)2-Ti-C5H4-[(CH2)2-O]-、(NEtsBu)2-Ti-C5H4-[(CH2)2-O]-、(NEttBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPriPr)2-Ti-C5H4-[(CH2)2-O]-、(NnPrnBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPriBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPrsBu)2-Ti-C5H4-[(CH2)2-O]-、(NnPrtBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPrnBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPriBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPrsBu)2-Ti-C5H4-[(CH2)2-O]-、(NiPrtBu)2-Ti-C5H4-[(CH2)2-O]-、(NnBuiBu)2-Ti-C5H4-[(CH2)2-O]-、(NnBusBu)2-Ti-C5H4-[(CH2)2-O]-、(NnButBu)2-Ti-C5H4-[(CH2)2-O]-、(NiBusBu)2-Ti-C5H4-[(CH2)2-O]-、(NiButBu)2-Ti-C5H4-[(CH2)2-O]-、(NsButBu)2-Ti-C5H4-[(CH2)2-O]-、(NH2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMe2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEt2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPr2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPr2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NsBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NtBu2)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHMe)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHEt)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHnPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHiPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NHtBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMeEt)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMenPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMeiPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMenBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMeiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMesBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NMetBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtnPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtiPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEtsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NEttBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPriPr)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPrnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPriBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPrsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnPrtBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPrnBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPriBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPrsBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiPrtBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnBuiBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnBusBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NnButBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiBusBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NiButBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(NsButBu)(Cp)-Ti-C5H4-[(CH2)2-O]-、(OH)-Ti-C5H4-[(CH2)2-O]-、(OMe)-Ti-C5H4-[(CH2)2-O]-、(OEt)-Ti-C5H4-[(CH2)2-O]-、(OnPr)-Ti-C5H4-[(CH2)2-O]-、(OiPr)-Ti-C5H4-[(CH2)2-O]-、(OnBu)-Ti-C5H4-[(CH2)2-O]-、(OiBu)-Ti-C5H4-[(CH2)2-O]-、(OsBu)-Ti-C5H4-[(CH2)2-O]-、(OtBu)-Ti-C5H4-[(CH2)2-O]-、(NH2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)2-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)(Cp)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OH)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OMe)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OEt)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OnPr)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OiPr)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OnBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OiBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OsBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(OtBu)-Ti-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)2-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NH2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)(Cp)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OH)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OMe)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OEt)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OnPr)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OiPr)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OnBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OiBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、(OsBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-、以及(OtBu)-Ti-C5H3-1-iPr-3-[(CH2)2-O]-。
6.如权利要求3所述的形成含第4族过渡金属的膜的组合物，其中，M为Zr。
7.如权利要求6所述的形成含第4族过渡金属的膜的组合物，其中，该第4族过渡金属前体选自由以下组成的组：(NH2)2-Zr-C5H4-[(CH2)2-O]-、(NMe2)2-Zr-C5H4-[(CH2)2-O]-、(NEt2)2-Zr-C5H4-[(CH2)2-O]-、(NnPr2)2-Zr-C5H4-[(CH2)2-O]-、(NiPr2)2-Zr-C5H4-[(CH2)2-O]-、(NnBu2)2-Zr-C5H4-[(CH2)2-O]-、(NiBu2)2-Zr-C5H4-[(CH2)2-O]-、(NsBu2)2-Zr-C5H4-[(CH2)2-O]-、(NtBu2)2-Zr-C5H4-[(CH2)2-O]-、(NHMe)2-Zr-C5H4-[(CH2)2-O]-、(NHEt)2-Zr-C5H4-[(CH2)2-O]-、(NHnPr)2-Zr-C5H4-[(CH2)2-O]-、(NHiPr)2-Zr-C5H4-[(CH2)2-O]-、(NHnBu)2-Zr-C5H4-[(CH2)2-O]-、(NHiBu)2-Zr-C5H4-[(CH2)2-O]-、(NHsBu)2-Zr-C5H4-[(CH2)2-O]-、(NHtBu)2-Zr-C5H4-[(CH2)2-O]-、(NMeEt)2-Zr-C5H4-[(CH2)2-O]-、(NMenPr)2-Zr-C5H4-[(CH2)2-O]-、(NMeiPr)2-Zr-C5H4-[(CH2)2-O]-、(NMenBu)2-Zr-C5H4-[(CH2)2-O]-、(NMeiBu)2-Zr-C5H4-[(CH2)2-O]-、(NMesBu)2-Zr-C5H4-[(CH2)2-O]-、(NMetBu)2-Zr-C5H4-[(CH2)2-O]-、(NEtnPr)2-Zr-C5H4-[(CH2)2-O]-、(NEtiPr)2-Zr-C5H4-[(CH2)2-O]-、(NEtnBu)2-Zr-C5H4-[(CH2)2-O]-、(NEtiBu)2-Zr-C5H4-[(CH2)2-O]-、(NEtsBu)2-Zr-C5H4-[(CH2)2-O]-、(NEttBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPriPr)2-Zr-C5H4-[(CH2)2-O]-、(NnPrnBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPriBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPrsBu)2-Zr-C5H4-[(CH2)2-O]-、(NnPrtBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPrnBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPriBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPrsBu)2-Zr-C5H4-[(CH2)2-O]-、(NiPrtBu)2-Zr-C5H4-[(CH2)2-O]-、(NnBuiBu)2-Zr-C5H4-[(CH2)2-O]-、(NnBusBu)2-Zr-C5H4-[(CH2)2-O]-、(NnButBu)2-Zr-C5H4-[(CH2)2-O]-、(NiBusBu)2-Zr-C5H4-[(CH2)2-O]-、(NiButBu)2-Zr-C5H4-[(CH2)2-O]-、(NsButBu)2-Zr-C5H4-[(CH2)2-O]-、(NH2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMe2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEt2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPr2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPr2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NsBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NtBu2)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHMe)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHEt)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHnPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHiPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NHtBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMeEt)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMenPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMeiPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMenBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMeiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMesBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NMetBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtnPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtiPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEtsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NEttBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPriPr)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPrnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPriBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPrsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnPrtBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPrnBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPriBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPrsBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiPrtBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnBuiBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnBusBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NnButBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiBusBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NiButBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(NsButBu)(Cp)-Zr-C5H4-[(CH2)2-O]-、(OH)-Zr-C5H4-[(CH2)2-O]-、(OMe)-Zr-C5H4-[(CH2)2-O]-、(OEt)-Zr-C5H4-[(CH2)2-O]-、(OnPr)-Zr-C5H4-[(CH2)2-O]-、(OiPr)-Zr-C5H4-[(CH2)2-O]-、(OnBu)-Zr-C5H4-[(CH2)2-O]-、(OiBu)-Zr-C5H4-[(CH2)2-O]-、(OsBu)-Zr-C5H4-[(CH2)2-O]-、(OtBu)-Zr-C5H4-[(CH2)2-O]-、(NH2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)2-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)(Cp)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OH)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OMe)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OEt)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OnPr)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OiPr)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OnBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OiBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OsBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(OtBu)-Zr-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)2-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NH2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)(Cp)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OH)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OMe)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OEt)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OnPr)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OiPr)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OnBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OiBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、(OsBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-、以及(OtBu)-Zr-C5H3-1-iPr-3-[(CH2)2-O]-。
8.如权利要求3所述的形成含第4族过渡金属的膜的组合物，其中，M为Hf。
9.如权利要求8所述的形成含第4族过渡金属的膜的组合物，其中，该第4族过渡金属前体选自由以下组成的组：(NH2)2-Hf-C5H4-[(CH2)2-O]-、(NMe2)2-Hf-C5H4-[(CH2)2-O]-、(NEt2)2-Hf-C5H4-[(CH2)2-O]-、(NnPr2)2-Hf-C5H4-[(CH2)2-O]-、(NiPr2)2-Hf-C5H4-[(CH2)2-O]-、(NnBu2)2-Hf-C5H4-[(CH2)2-O]-、(NiBu2)2-Hf-C5H4-[(CH2)2-O]-、(NsBu2)2-Hf-C5H4-[(CH2)2-O]-、(NtBu2)2-Hf-C5H4-[(CH2)2-O]-、(NHMe)2-Hf-C5H4-[(CH2)2-O]-、(NHEt)2-Hf-C5H4-[(CH2)2-O]-、(NHnPr)2-Hf-C5H4-[(CH2)2-O]-、(NHiPr)2-Hf-C5H4-[(CH2)2-O]-、(NHnBu)2-Hf-C5H4-[(CH2)2-O]-、(NHiBu)2-Hf-C5H4-[(CH2)2-O]-、(NHsBu)2-Hf-C5H4-[(CH2)2-O]-、(NHtBu)2-Hf-C5H4-[(CH2)2-O]-、(NMeEt)2-Hf-C5H4-[(CH2)2-O]-、(NMenPr)2-Hf-C5H4-[(CH2)2-O]-、(NMeiPr)2-Hf-C5H4-[(CH2)2-O]-、(NMenBu)2-Hf-C5H4-[(CH2)2-O]-、(NMeiBu)2-Hf-C5H4-[(CH2)2-O]-、(NMesBu)2-Hf-C5H4-[(CH2)2-O]-、(NMetBu)2-Hf-C5H4-[(CH2)2-O]-、(NEtnPr)2-Hf-C5H4-[(CH2)2-O]-、(NEtiPr)2-Hf-C5H4-[(CH2)2-O]-、(NEtnBu)2-Hf-C5H4-[(CH2)2-O]-、(NEtiBu)2-Hf-C5H4-[(CH2)2-O]-、(NEtsBu)2-Hf-C5H4-[(CH2)2-O]-、(NEttBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPriPr)2-Hf-C5H4-[(CH2)2-O]-、(NnPrnBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPriBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPrsBu)2-Hf-C5H4-[(CH2)2-O]-、(NnPrtBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPrnBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPriBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPrsBu)2-Hf-C5H4-[(CH2)2-O]-、(NiPrtBu)2-Hf-C5H4-[(CH2)2-O]-、(NnBuiBu)2-Hf-C5H4-[(CH2)2-O]-、(NnBusBu)2-Hf-C5H4-[(CH2)2-O]-、(NnButBu)2-Hf-C5H4-[(CH2)2-O]-、(NiBusBu)2-Hf-C5H4-[(CH2)2-O]-、(NiButBu)2-Hf-C5H4-[(CH2)2-O]-、(NsButBu)2-Hf-C5H4-[(CH2)2-O]-、(NH2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMe2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEt2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPr2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPr2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NsBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NtBu2)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHMe)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHEt)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHnPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHiPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NHtBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMeEt)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMenPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMeiPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMenBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMeiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMesBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NMetBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtnPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtiPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEtsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NEttBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPriPr)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPrnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPriBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPrsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnPrtBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPrnBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPriBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPrsBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiPrtBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnBuiBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnBusBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NnButBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiBusBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NiButBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(NsButBu)(Cp)-Hf-C5H4-[(CH2)2-O]-、(OH)-Hf-C5H4-[(CH2)2-O]-、(OMe)-Hf-C5H4-[(CH2)2-O]-、(OEt)-Hf-C5H4-[(CH2)2-O]-、(OnPr)-Hf-C5H4-[(CH2)2-O]-、(OiPr)-Hf-C5H4-[(CH2)2-O]-、(OnBu)-Hf-C5H4-[(CH2)2-O]-、(OiBu)-Hf-C5H4-[(CH2)2-O]-、(OsBu)-Hf-C5H4-[(CH2)2-O]-、(OtBu)-Hf-C5H4-[(CH2)2-O]-、(NH2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)2-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMe2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEt2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPr2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPr2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NtBu2)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHMe)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHEt)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NHtBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeEt)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMenBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMesBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NMetBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NEttBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NnButBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NiButBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NsButBu)(Cp)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OH)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OMe)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OEt)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OnPr)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OiPr)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OnBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OiBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OsBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(OtBu)-Hf-C5H3-1-Me-3-[(CH2)2-O]-、(NH2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)2-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NH2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMe2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEt2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPr2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPr2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NtBu2)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHMe)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHEt)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NHtBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeEt)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMenBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMeiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMesBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NMetBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEtsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NEttBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriPr)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPriBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnPrtBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrnBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPriBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrsBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiPrtBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBuiBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnBusBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NnButBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiBusBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NiButBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(NsButBu)(Cp)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OH)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OMe)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OEt)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OnPr)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OiPr)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OnBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OiBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、(OsBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-、以及(OtBu)-Hf-C5H3-1-iPr-3-[(CH2)2-O]-。
10.一种用于将含第4族过渡金属的膜沉积在基材上的方法，该方法包括以下步骤：
将如权利要求1至9中任一项所述的形成含第4族过渡金属的膜的组合物的蒸气引入具有布置在其中的基材的反应器内；以及
将该含第4族过渡金属的前体的至少一部分沉积到该基材上。
11.如权利要求10所述的方法，进一步包括将至少一种反应物引入该反应器中。
12.如权利要求11所述的方法，其中，该反应物选自由以下组成的组：O2、O3、H2O、H2O2、NO、N2O、NO2、其氧自由基、以及其混合物。
13.如权利要求11所述的方法，其中，该反应物是含M′的前体，并且该含第4族过渡金属的膜为MM′iOx，其中i在从0至1的范围内；x在从1至6的范围内；并且M′选自第3族元素、不同的第4族元素、第5族元素、镧系元素、Si、Al、B、P或Ge。
14.如权利要求11所述的方法，其中，该形成含第4族过渡金属的膜的组合物用于形成DRAM电容器。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/396,118 | 2016-12-30 | ||
| US15/396,118 US20170107612A1 (en) | 2016-12-30 | 2016-12-30 | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same |
| PCT/IB2017/001654 WO2018122601A1 (en) | 2016-12-30 | 2017-12-14 | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110139945A true CN110139945A (zh) | 2019-08-16 |
Family
ID=58522879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780081938.2A Pending CN110139945A (zh) | 2016-12-30 | 2017-12-14 | 锆前体、铪前体、钛前体及使用其沉积含第4族的膜 |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20170107612A1 (zh) |
| JP (1) | JP2020504785A (zh) |
| KR (1) | KR20190094436A (zh) |
| CN (1) | CN110139945A (zh) |
| WO (1) | WO2018122601A1 (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10465289B2 (en) | 2016-12-30 | 2019-11-05 | L'Air Liquide, Société Anonyme pour l'Etude at l'Exploitation des Procédés Georges Claude | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same |
| US10364259B2 (en) | 2016-12-30 | 2019-07-30 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same |
| US10337104B2 (en) | 2016-12-30 | 2019-07-02 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same |
| KR20240073582A (ko) | 2022-11-18 | 2024-05-27 | 에스케이트리켐 주식회사 | 아미디네이트 리간드를 포함하는 4족 전이금속 함유 박막 형성용 전구체, 이를 이용한 4족 전이금속 함유 박막 형성 방법 및 상기 4족 전이금속 함유 박막을 포함하는 반도체 소자. |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100804413B1 (ko) * | 2006-06-21 | 2008-02-20 | (주)디엔에프 | 지르코늄 산화물 박막 증착용 유기금속 선구물질 및 이의제조 방법 |
| CN101528759A (zh) * | 2006-10-26 | 2009-09-09 | 乔治洛德方法研究和开发液化空气有限公司 | 新型含有v族金属的前体及其对含有金属的膜的沉积的应用 |
| CN102040620A (zh) * | 2009-10-23 | 2011-05-04 | 气体产品与化学公司 | 用于含金属膜的第4族金属前体 |
| KR20140078534A (ko) * | 2012-12-17 | 2014-06-25 | 솔브레인씨그마알드리치 유한회사 | 금속 전구체 및 이를 이용하여 제조된 금속 함유 박막 |
| CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
| KR101684660B1 (ko) * | 2016-07-08 | 2016-12-09 | (주)이지켐 | 지르코늄 박막 형성용 전구체 조성물 및 이를 이용한 지르코늄 박막의 형성 방법 |
-
2016
- 2016-12-30 US US15/396,118 patent/US20170107612A1/en not_active Abandoned
-
2017
- 2017-12-14 JP JP2019536031A patent/JP2020504785A/ja active Pending
- 2017-12-14 KR KR1020197020773A patent/KR20190094436A/ko unknown
- 2017-12-14 CN CN201780081938.2A patent/CN110139945A/zh active Pending
- 2017-12-14 WO PCT/IB2017/001654 patent/WO2018122601A1/en active Application Filing
-
2020
- 2020-01-17 US US16/745,631 patent/US20200149165A1/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100804413B1 (ko) * | 2006-06-21 | 2008-02-20 | (주)디엔에프 | 지르코늄 산화물 박막 증착용 유기금속 선구물질 및 이의제조 방법 |
| CN101528759A (zh) * | 2006-10-26 | 2009-09-09 | 乔治洛德方法研究和开发液化空气有限公司 | 新型含有v族金属的前体及其对含有金属的膜的沉积的应用 |
| CN102040620A (zh) * | 2009-10-23 | 2011-05-04 | 气体产品与化学公司 | 用于含金属膜的第4族金属前体 |
| CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
| KR20140078534A (ko) * | 2012-12-17 | 2014-06-25 | 솔브레인씨그마알드리치 유한회사 | 금속 전구체 및 이를 이용하여 제조된 금속 함유 박막 |
| KR101684660B1 (ko) * | 2016-07-08 | 2016-12-09 | (주)이지켐 | 지르코늄 박막 형성용 전구체 조성물 및 이를 이용한 지르코늄 박막의 형성 방법 |
Non-Patent Citations (1)
| Title |
|---|
| WOLFGANG A. HERRMANN ET.AL.: "Doubly Bridged vac-Metallocenes", 《ANGEW.CHEM.INT.ED.ENGL.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018122601A1 (en) | 2018-07-05 |
| JP2020504785A (ja) | 2020-02-13 |
| US20200149165A1 (en) | 2020-05-14 |
| KR20190094436A (ko) | 2019-08-13 |
| US20170107612A1 (en) | 2017-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10364259B2 (en) | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same | |
| CN110088357A (zh) | 锆前体、铪前体、钛前体及使用其沉积含第4族的膜 | |
| US20200149165A1 (en) | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same | |
| JP2020524905A (ja) | ニオブ含有膜形成用組成物及びニオブ含有膜の蒸着 | |
| US10584039B2 (en) | Titanium-containing film forming compositions for vapor deposition of titanium-containing films | |
| US11168099B2 (en) | Titanium-containing film forming compositions for vapor deposition of titanium-containing films | |
| US20200032397A1 (en) | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same | |
| US20220205099A1 (en) | Group iv element containing precursors and deposition of group iv element containing films | |
| US20210221830A1 (en) | Methods for vapor deposition of group 4 transition metal-containing films using group 4 transition metal-containing films forming compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190816 |
|
| WD01 | Invention patent application deemed withdrawn after publication |