US20220106333A1 - Indium precursors for vapor depositions - Google Patents
Indium precursors for vapor depositions Download PDFInfo
- Publication number
- US20220106333A1 US20220106333A1 US17/063,768 US202017063768A US2022106333A1 US 20220106333 A1 US20220106333 A1 US 20220106333A1 US 202017063768 A US202017063768 A US 202017063768A US 2022106333 A1 US2022106333 A1 US 2022106333A1
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- US
- United States
- Prior art keywords
- iii
- linear
- alkyl
- cyclic
- branched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000002243 precursor Substances 0.000 title claims abstract description 181
- 229910052738 indium Inorganic materials 0.000 title abstract description 73
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title abstract description 67
- 238000007740 vapor deposition Methods 0.000 title description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 124
- 238000000034 method Methods 0.000 claims abstract description 86
- 239000000203 mixture Substances 0.000 claims abstract description 85
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 72
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 150000002367 halogens Chemical class 0.000 claims abstract description 25
- -1 amido amino alkane Chemical class 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims description 121
- 125000004122 cyclic group Chemical group 0.000 claims description 113
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 113
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 113
- 229920002554 vinyl polymer Polymers 0.000 claims description 113
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 95
- 239000000758 substrate Substances 0.000 claims description 83
- 239000000376 reactant Substances 0.000 claims description 63
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 claims description 51
- 238000000151 deposition Methods 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 229910052794 bromium Inorganic materials 0.000 claims description 37
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 35
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 35
- 230000008021 deposition Effects 0.000 claims description 35
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 26
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 24
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 15
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 229910006400 μ-Cl Inorganic materials 0.000 claims description 13
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910003437 indium oxide Inorganic materials 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000005019 vapor deposition process Methods 0.000 claims description 6
- 150000002429 hydrazines Chemical class 0.000 claims description 5
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000846 In alloy Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- ZMFWDTJZHRDHNW-UHFFFAOYSA-N indium;trihydrate Chemical compound O.O.O.[In] ZMFWDTJZHRDHNW-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 11
- 239000011630 iodine Substances 0.000 claims 11
- 150000001805 chlorine compounds Chemical group 0.000 claims 2
- 229910000673 Indium arsenide Inorganic materials 0.000 claims 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 40
- 239000003446 ligand Substances 0.000 abstract description 30
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 8
- 238000001947 vapour-phase growth Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- QMTOADWOYGJTAJ-UHFFFAOYSA-N OC(=O)N1CCCC1=N Chemical compound OC(=O)N1CCCC1=N QMTOADWOYGJTAJ-UHFFFAOYSA-N 0.000 abstract description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 159
- 239000010408 film Substances 0.000 description 156
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 105
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 69
- 238000000231 atomic layer deposition Methods 0.000 description 56
- 239000010410 layer Substances 0.000 description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 38
- 239000002904 solvent Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000005229 chemical vapour deposition Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 26
- 229910021618 Indium dichloride Inorganic materials 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 22
- 235000012431 wafers Nutrition 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 0 C.C[5*]1[4*]2C34[6*][7*]3C21CCC=C4.C[5*]1[4*]2C34[6*][7*]3C21CCC=C4.C[5*]1[4*]2C34[6*][7*]3C21CCC=C4 Chemical compound C.C[5*]1[4*]2C34[6*][7*]3C21CCC=C4.C[5*]1[4*]2C34[6*][7*]3C21CCC=C4.C[5*]1[4*]2C34[6*][7*]3C21CCC=C4 0.000 description 18
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 18
- 238000002411 thermogravimetry Methods 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 229910052785 arsenic Inorganic materials 0.000 description 10
- 238000005137 deposition process Methods 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 238000000137 annealing Methods 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 9
- 229910052733 gallium Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CTMHWPIWNRWQEG-UHFFFAOYSA-N CC1=CCCCC1 Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 238000000859 sublimation Methods 0.000 description 7
- 230000008022 sublimation Effects 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011344 liquid material Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- UUHMWERABBLRBQ-UHFFFAOYSA-N CC1C=C=CCC1 Chemical compound CC1C=C=CCC1 UUHMWERABBLRBQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JEDUBRYCUZLFFS-UHFFFAOYSA-N CCC1C=C=CCC1 Chemical compound CCC1C=C=CCC1 JEDUBRYCUZLFFS-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229910005267 GaCl3 Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 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 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- AXTNYCDVWRSOCU-UHFFFAOYSA-N n'-tert-butyl-n-ethylmethanediimine Chemical compound CCN=C=NC(C)(C)C AXTNYCDVWRSOCU-UHFFFAOYSA-N 0.000 description 3
- 238000003947 neutron activation analysis Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical group [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 2
- PXMPVXFSOKVMLI-UHFFFAOYSA-N CC(C)N(CC1)C(C)(C)C1=N Chemical compound CC(C)N(CC1)C(C)(C)C1=N PXMPVXFSOKVMLI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910000756 V alloy Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 230000008901 benefit 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
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
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- 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
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- 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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- 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
Definitions
- the present invention relates to indium (III)-containing film forming compositions comprising In(III)-containing precursors that contain halogens, methods of synthesizing them and methods of using them to deposit the indium-containing films and/or indium-containing alloy films, in particular, to the In(III)-containing precursors containing chlorine with nitrogen based ligands suitable for vapor phase depositions (e.g., ALD, CVD) of the indium-containing films and/or indium-containing alloy films.
- In(III)-containing precursors containing chlorine with nitrogen based ligands suitable for vapor phase depositions (e.g., ALD, CVD) of the indium-containing films and/or indium-containing alloy films.
- Indium-containing alloys, thin films, and nanostructured materials are highly versatile optoelectronic materials widely applied in both research and industry, in particular the semiconductor industry, with applications in many areas including electronics and photonics.
- InGaAs is believed to be one of the stronger contenders for the future replacement of silicon in CMOS systems.
- InGaAs is also a key component of optical fiber telecommunications, serving as a high-speed, high sensitivity photodetector.
- US 20130273250 to Fujimura et al. discloses (Amide Amino Alkane) metal compounds and a method of manufacturing metal-containing thin films using said metal compounds, in which a series of novel homoleptic amide amino alkane metal complexes are used for chemical vapor deposition (CVD).
- the disclosed metal complexes include lithium, sodium, magnesium, manganese, iron, cobalt, nickel, zinc, yttrium, lanthanum, and indium complexes. Specific examples include
- Gebhard et al. discloses (“Indium-tris-guanidinates: A Promising Class of Precursors for Water Assisted Atomic Layer Deposition of Ir 2 O 3 Films,” Dalton Trans, 2014, 43, 937) syntheses of two homoleptic indium-tris-guanidinate complexes. The compounds were isolated as solids and used for indium oxide ALD processes.
- Heteroleptic indium precursors have been investigated for deposition processes.
- heteroleptic indium (III) precursors included alkyl ligands, acetate and hydroxyl ligands.
- Alkyl ligands included alkyl ligands, acetate and hydroxyl ligands.
- Kim et al. ACS Appl. Mater. Interfaces 2016, 8, 40, 26924.
- US 2016017485 to Martinson et al. discloses a method of atomic layer deposition of indium sulfide films using a synthesized indium precursor and hydrogen sulfide.
- US 20160326008 to Koh et al. discloses details heteroleptic Indium (III) precursors bis(trimethylsilyl)aminodiethylindium and dimethyl(3-dimethylaminopropyl)indium which are liquids at room temperature.
- WO 2017083483 (US 20170137360) to Curley et al. discloses details the synthesis of dicarboxylate monohydroxyl indium precursors. Several examples of this precursor being used for the solution phase synthesis of InP nanostructures are provided.
- ITO Indium tin oxide thin films prepared by dip-coating of indium diacetate monohydroxide and tin dichloride, Thin Solid Films, 2001, 388, 22-26
- ITO tin-doped In 2 O 3 films were prepared by the dip-coating method using an ethanol solution of indium diacetate monohydroxide, In(OH)(CH 3 COO) 2 , and tin dichloride, SnCl 2 .2H 2 O, with 2-aminoethanol (monoethanolamine), H 2 NC 2 H 4 OH.
- Patton et al. (Chelating Diamide Group IV Metal Olefin Polymerization. Organometallics, 2002, 21, 10, 2145) discloses dichloroindium-tert-Butyl-N,N′-diisopropylamidinate was synthesized as an intermediate en route to indium-bridged chelating diamide titanium complex used as a catalyst for olefin polymerization.
- the indium amidinate compound was isolated cleanly in 48% yield and characterized using 1 H, 13 C NMR spectroscopy and HRMS.
- WO 0146201A1 (US 20020098973A1) to Campbell et al. discloses a large range of bridged Group 4 transition metal complexes are disclosed.
- bridged group 4 transition metal complexes that contain indium, dichloroindium-tert-butyl-N,N′-diisopropylamidinate is synthesized as an intermediate.
- indium(III)-containing precursor has the formula:
- R 1 and R 2 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6 wherein R 4 , R 5 , R 6 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 3 is selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or —NR 7 R 8 where R 7 and R 8 are each independently selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the structure may exist as the dimeric structure
- R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the structure may exist as the dimeric structure [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 ))InX] 2 ( ⁇ -X) 2 ,
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 and R 5 may also be —SiR 6 R 7 R 8 where R 6 , R 7 , R 8 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Groups R 1 , R 2 , R 3 and R 5 may also be selected from fluorinated linear or aromatic groups (e.g., CF 3 , m-(CF 3 ) 2 —C 6 H 3 , etc.).
- Group R 4 may also be selected from halogens, such as F, and
- R 1 , R 2 , and R 3 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups
- R 4 is hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7 group wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the disclosed methods may include one or more of the following aspects:
- R 1 and R 2 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6 wherein R 4 , R 5 , R 6 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 3 is selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or —NR 7 R 8 where R 7 and R 8 are each independently selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups.
- the structure may exist as the dimeric structure [((R 1 ) C(R 3 ) N(R 2 ))InX] 2 ( ⁇ -X) 2 ,
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the structure may exist as the dimeric structure
- R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- n 1 or 2 to provide either a 5-membered or 6-membered metallacycle, respectively.
- the structure may exist as the dimeric structure [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 ))InX] 2 ( ⁇ -X) 2 ,
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 and R 5 may also be —SiR 6 R 7 R 8 where R 6 , R 7 , R 8 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Groups R 1 , R 2 , R 3 and R 5 may also be selected from fluorinated linear or aromatic groups (e.g., CF 3 , m-(CF 3 ) 2 —C 6 H 3 , etc.).
- Group R 4 may also be selected from halogens, such as F, and
- R 1 , R 2 , and R 3 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups
- R 4 is hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7 group wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the disclosed methods may include one or more of the following aspects:
- composition for deposition of a film comprising an indium(III)-containing precursor having the formula:
- R 1 and R 2 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6 wherein R 4 , R 5 , R 6 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 3 is selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or —NR 7 R 8 where R 7 and R 8 are each independently selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups.
- the structure may exist as the dimeric structure [((R 1 )N C(R 3 ) N(R 2 ))InX] 2 ( ⁇ -X) 2 ,
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the structure may exist as the dimeric structure
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the structure may exist as the dimeric structure [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R))InX] 2 ( ⁇ -X) 2 ,
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 and R 5 may also be —SiR 6 R 7 R 8 where R 6 , R 7 , R 8 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Groups R 1 , R 2 , R 3 and R 5 may also be selected from fluorinated linear or aromatic groups (e.g., CF 3 , m-(CF 3 ) 2 —C 6 H 3 , etc.).
- Group R 4 may also be selected from halogens, such as F, and
- R 1 , R 2 , and R 3 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups
- R 4 is hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7 group wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the disclosed methods may include one or more of the following aspects:
- room temperature in the text or in a claim means from approximately 20° C. to approximately 25° C.
- ambient temperature refers to an environment temperature approximately 20° C. to approximately 25° C.
- substrate refers to a material or materials on which a process is conducted.
- the substrate may refer to a wafer having a material or materials on which a process is conducted.
- the substrates may be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing.
- the substrate may also have one or more layers of differing materials already deposited upon it from a previous manufacturing step.
- the wafers may include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon containing layers (e.g., SiO 2 , SiN, SiON, SiCOH, etc.), metal containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.) or combinations thereof.
- the substrate may be planar or patterned.
- the substrate may be an organic patterned photoresist film.
- the substrate may include layers of oxides which are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (for example, ZrO 2 based materials, HfO 2 based materials, TiO 2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or nitride-based films (for example, TaN, TiN, NbN) that are used as electrodes.
- oxides which are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications
- ZrO 2 based materials for example, HfO 2 based materials, TiO 2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.
- nitride-based films for example, TaN, TiN, NbN
- wafer or “patterned wafer” refers to a wafer having a stack of films on a substrate and at least the top-most film having topographic features that have been created in steps prior to the deposition of the indium containing film.
- the term “aspect ratio” refers to a ratio of the height of a trench (or aperture) to the width of the trench (or the diameter of the aperture).
- film and “layer” may be used interchangeably. It is understood that a film may correspond to, or related to a layer, and that the layer may refer to the film. Furthermore, one of ordinary skill in the art will recognize that the terms “film” or “layer” used herein refer to a thickness of some material laid on or spread over a surface and that the surface may range from as large as the entire wafer to as small as a trench or a line.
- aperture may be used interchangeably to refer to an opening formed in a semiconductor structure.
- NAND refers to a “Negative AND” or “Not AND” gate
- 2D refers to 2 dimensional gate structures on a planar substrate
- 3D refers to 3 dimensional or vertical gate structures, wherein the gate structures are stacked in the vertical direction.
- a substrate temperature may correspond to, or be related to a deposition temperature, and that the deposition temperature may refer to the substrate temperature.
- precursor and “deposition compound” and “deposition gas” may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor may correspond to, or be related to a deposition compound or deposition gas, and that the deposition compound or deposition gas may refer to the precursor.
- CAS unique CAS registry numbers assigned by the Chemical Abstract Service are provided to identify the specific molecules disclosed.
- the silicon-containing films may include pure silicon (Si) layers, such as crystalline Si, polysilicon (p-Si or polycrystalline Si), or amorphous silicon; silicon nitride (Si k N l ) layers; or silicon oxide (Si n O m ) layers; or mixtures thereof, wherein k, l, m, and n, inclusively range from 0.1 to 6.
- silicon nitride is Si k N l , where k and l each range from 0.5 to 1.5. More preferably silicon nitride is Si 3 N 4 .
- SiN in the following description may be used to represent Si k N l containing layers.
- silicon oxide is Si n O m , where n ranges from 0.5 to 1.5 and m ranges from 1.5 to 3.5. More preferably, silicon oxide is SiO 2 .
- SiO in the following description may be used to represent Si n O m containing layers.
- the silicon-containing film could also be a silicon oxide based dielectric material such as organic based or silicon oxide based low-k dielectric materials such as the Black Diamond II or III material by Applied Materials, Inc. with a formula of SiOCH. Silicon-containing film may also include Si a O b N c where a, b, c range from 0.1 to 6.
- the silicon-containing films may also include dopants from group III, IV, V and VI, such as B, C, P, As and/or Ge.
- hydrocarbon refers to a saturated or unsaturated function group containing exclusively carbon and hydrogen atoms.
- alkyl group refers to saturated functional groups containing exclusively carbon and hydrogen atoms.
- An alkyl group is one type of hydrocarbon.
- alkyl group refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.
- the abbreviation “Me” refers to a methyl group
- the abbreviation “Et” refers to an ethyl group
- the abbreviation “Pr” refers to any propyl group (i.e., n-propyl or isopropyl);
- the abbreviation “iPr” refers to an isopropyl group
- the abbreviation “Bu” refers to any butyl group (n-butyl, iso-butyl, tert-butyl, sec-butyl);
- the abbreviation “tBu” refers to a tert-butyl group
- the abbreviation “sBu” refers to a sec-butyl group
- the abbreviation “iBu” refers to an iso-butyl group
- the abbreviation “Ph” refers to a phenyl group
- the abbreviation “Am” refers to any amyl group (iso
- X is chosen from chlorine, bromine and iodine, preferably chlorine
- R 1 and R 2 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6 wherein R 4 , R 5 , R 6 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl groups
- R 3 is selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or —NR 7 R 8 where R 7 and R 8 are each independently selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups.
- the structure may exist as the dimeric structure [((R 1 )N C(R 3 ) N(R 2 ))InX] 2 ( ⁇ -X) 2 .
- R 1 and R 2 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6 wherein R 4 , R 5 , R 6 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 3 is selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or —NR 7 R 8 where R 7 and R 8 are each independently selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups.
- R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 1 , R 2 , R 3 , R 4 , R 5 , R and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- the structure may exist as the dimeric structure [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 ))InX] 2 ( ⁇ -X) 2 .
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 and R 5 may also be —SiR 6 R 7 R 8 where R 6 , R 7 , R 8 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Groups R 1 , R 2 , R 3 and R 5 may also be selected from fluorinated linear or aromatic groups (e.g., CF 3 , m-(CF 3 ) 2 —C 6 H 3 , etc.).
- Group R 4 may also be selected from halogens, such as F.
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 and R 5 may also be —SiR 6 R 7 R 8 where R 6 , R 7 , R 8 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Groups R 1 , R 2 , R 3 and R 5 may also be selected from fluorinated linear or aromatic groups (e.g., CF 3 , m-(CF 3 ) 2 —C 6 H 3 , etc.).
- Group R 4 may also be selected from halogens, such as F.
- R 1 , R 2 , and R 3 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups
- R 4 is hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7 group wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- R groups independently selected relative to other R groups bearing the same or different subscripts or superscripts, but is also independently selected relative to any additional species of that same R group.
- the two or three R 1 groups may, but need not be identical to each other or to R 2 or to R 3 .
- values of R groups are independent of each other when used in different formulas.
- exemplary is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete fashion.
- the term “or” is intended to mean an inclusive “or” rather than an exclusive “or”. That is, unless specified otherwise, or clear from context, “X employs A or B” is intended to mean any of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, then “X employs A or B” is satisfied under any of the foregoing instances.
- the articles “a” and “an” as used in this application and the appended claims should generally be construed to mean “one or more” unless specified otherwise or clear from context to be directed to a singular form.
- “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” is defined herein as necessarily encompassing the more limited transitional terms “consisting essentially of” and “consisting of”; “comprising” may therefore be replaced by “consisting essentially of” or “consisting of” and remain within the expressly defined scope of “comprising”.
- Providing in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actors in the absence of express language in the claim to the contrary.
- FIG. 1 is vacuum thermogravimetric analysis (TGA) results for [(Et)N C(Me) N(tBu)]In(III)Cl 2 ;
- FIG. 2 is differential scanning calorimetry (DSC) results for [(Et)N C(Me N(tBu)]In(III)Cl 2 ;
- FIG. 3 is 1 H NMR of [(Et)N C(Me) N(tBu)]In(III)Cl 2 in C 6 D 6 ;
- FIG. 4 is TGA results of [(iPr)N CH N(iPr)]In(III)Cl 2 ;
- FIG. 5 is DSC results of [(iPr)N CH N(iPr)]In(III)Cl 2 ;
- FIG. 6 is 1 H NMR of [(iPr)N CH N(iPr)]In(III)Cl 2 in THF-d 8 ;
- FIG. 7 is TGA results of [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 ;
- FIG. 8 is DSC results of [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 ;
- FIG. 9 is 1 H NMR of [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 in C 6 D 6 ;
- FIG. 10 is TGA results of [(Et)N C(nBu) N(tBu)]In(III)Cl 2 ;
- FIG. 11 is 1 H NMR of [(Et)N C(nBu) N(tBu)]In(III)Cl 2 in C 6 D 6 ;
- FIG. 12 is TGA results of [(iPr)N C(Me) N(iPr)]In(III)Cl 2 ;
- FIG. 13 is 1 H NMR of [(iPr)N C(Me) N(iPr)]In(III)Cl 2 in C 6 D 6 .
- indium (In)-containing film and/or indium-containing alloy film forming compositions comprising In(III)-containing precursors that contain halogens, methods of synthesizing them and methods of using them to deposit the indium-containing films and/or indium-containing alloy film.
- heteroleptic compounds Although some homoleptic indium precursors exist, there is a lack of heteroleptic complexes containing halogens available for use as precursors.
- the advantage of using heteroleptic compounds is the ability to incorporate organic ligands as well as other reactivity ligands such as halogens that may be beneficial for the desired surface chemistry.
- InCl 3 has been used for deposition, however, InCl 3 has very low volatility (boiling point 800° C., I torr vapor pressure at 310° C.) making it difficult to use for most applications.
- the disclosed In(III)-containing precursors not only include at least one halogen but also include an organic ligand that greatly increases the volatility relative to InCl 3 to the point that the vapor pressure of the disclosed In(III)-containing precursors is sufficient for commercially viable vapor phase deposition (e.g.: CVD and ALD) processes.
- the disclosed In(III)-containing precursors herein are indium(III) containing precursors that will be denoted as In(III)-containing precursors throughout the entire patent application.
- the disclosed In(III)-containing precursors contain one or two halogen ligands. More preferably, the disclosed In(III)-containing precursors contain chlorine with nitrogen based ligands, which are suitable for vapor phase depositions of the indium-containing films and/or indium-containing alloy films.
- the disclosed In(III)-containing precursors include the following categories.
- the disclosed In(III)-containing precursors contains 1 or 2 amidinate ligands having the formula:
- R 1 and R 2 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6 wherein R 4 , R 5 , R 6 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups;
- R 3 is selected from H or a linear, branched or cyclic C 1 to C 8 alkyl, vinyl or aryl group or —NR 7 R 8 where R 7 and R 8 are each independently selected from H or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl, or aryl group.
- Exemplary precursors having the formula [(R 1 )N C(R 3 ) N(R 2 )]InX 2 include:
- Exemplary precursors having the formula [(R 1 )N C(R 3 ) N(R 2 )] 2 InX include:
- the structure may exists as a dimer under certain conditions with the formula [((R 1 )N C(R 3 ) N(R 2 ))InX] 2 ( ⁇ -X) 2 .
- Exemplary precursors having the formula [((R 1 )N C(R 3 ) N(R 2 ))InX] 2 ( ⁇ -X) 2 include:
- R 1 ⁇ R 2 ⁇ R 3 Me [((Me)N C(Me) N(Me))InCl] 2 ( ⁇ -Cl) 2 (N,N′-dimethyl-acetamidinato)indium(III) dichloride);
- the disclosed In(III)-containing compounds contains 1 or 2 iminopyrrolidinate ligands having the formula:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- R 1 tBu
- R 2 ⁇ R 3 Me
- R 4 ⁇ R 5 R 6 ⁇ R 7 ⁇ H
- the structure may exists as a dimer under certain conditions with the formula
- the disclosed In(III)-containing precursors contains 1 or 2 amido amino alkane ligands having the formula:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may also be —SiR 8 R 9 R 10 where R 8 , R 9 , R 10 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Exemplary precursors having the formula [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )]InX 2 include:
- Exemplary precursors having the formula [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )] 2 InX include:
- Exemplary precursors having the formula [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 ))InX] 2 ( ⁇ -X) 2 include:
- the disclosed In(III)-containing precursors contains 1 or 2 ⁇ -diketiminate ligands with the formula:
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 and R 5 may also be —SiR 6 R 7 R 8 where R 6 , R 7 , R 8 are each independently selected from a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Groups R 1 , R 2 , R 3 and R 5 may also be selected from fluorinated linear or aromatic groups (e.g., CF 3 , m-(CF 3 ) 2 —C 6 H 3 , etc.).
- Group R 4 may also be selected from halogens, such as F.
- Exemplary precursors having the formula [(R 1 )N C(R 3 ) C(R 4 ) C(R 5 ) N(R 2 )]InX 2 include:
- Exemplary precursors having the formula [(R 1 )N C(R 3 ) C(R 4 ) ⁇ C(R 5 ) N(R 2 )] 2 InX include:
- the disclosed In(III)-containing precursors contains a silyl amine ligand with the following formula:
- R 1 , R 2 , and R 3 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl groups
- R 4 is hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7 group wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen or a linear, branched or cyclic C 1 to C 9 alkyl, vinyl or aryl group.
- Exemplary precursors having the formula [N((SiR 1 R 2 R 3 )R 4 )]InX 2 include:
- the disclosed In(III)-containing precursor is [(Et)N C(Me) N(tBu)]In(III)Cl 2 having the following structure:
- the disclosed In(III)-containing precursor is [(iPr)N CH N(iPr)]In(III)Cl 2 or [((iPr)N C(H) N(iPr))InCl] 2 ( ⁇ -Cl) 2 depending on the given conditions having the following structure.
- the disclosed In(III)-containing precursor is [(Et)N C(nBu) N(tBu)]In(III)Cl 2 having the following structure.
- the disclosed In(III)-containing precursor is [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 having the following structure.
- the disclosed In(III)-containing precursor is [(iPr)N C(Me) N(iPr)]In(III)Cl 2 having the following structure.
- the vapor pressure of [(iPr)N CH N(iPr)]In(III)Cl 2 is 1 torr at 128° C.
- the vapor pressure of [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 is 1 torr at 155° C.
- the vapor pressure of [(iPr)N C(Me) N(iPr)]In(III)Cl 2 is 1 torr at 127° C. See Table 1.
- the disclosed methods for syntheses of the disclosed In(III)-containing precursors include a salt metathesis reaction as shown in examples that follow.
- the disclosed In(III)-containing precursors may be synthesized through the salt metathesis reaction by mixing either one or two equivalents of a lithiated ligand with InX 3 where X ⁇ Cl, Br, I.
- the reaction is performed by loading a reaction flask with a desired nitrogen ligand in an ethereal solvent and cooling to 0° C. or ⁇ 78° C.
- a required alkylithium reagent is added to generate the reactive lithiated species of the ligand.
- the lithiated ligand is then transferred to a suspension of the desired In(III) halide in an ethereal solvent at ⁇ 78 or 0° C.
- the reaction is allowed to stir for 12 hours.
- the solution is then filtered using Celite as a filtering agent, followed by a removal of solvent in vacuo to isolate the product.
- lithiated amidinate ligands e.g., Li[(R 1 )N C(R 3 ) N(R 2 )]
- the desired starting material is the corresponding carbodiimide [(R 1 )N ⁇ C ⁇ N(R 2 )] and the alkylithium reagent is LiR 3 .
- the disclosed methods for syntheses of the disclosed In(III)-containing precursors include a ligand exchange reaction of In(III)Cl with the generation of SiR 3 —X as shown in the example below.
- the disclosed In(III)-containing precursors may be synthesized through the ligand exchange reaction by mixing either one or two equivalents of the silylated ligand with InX 3 where X ⁇ Cl, Br, I.
- the reaction is performed by loading a reaction flask with the desired In(III) halide in an ethereal solvent at room temperature.
- the required silylated nitrogen ligand is added to the reaction at room temperature and allowed to stir for 2 to 12 hours.
- the solvent in removed in vacuo to isolate the product followed by extraction in a hydrocarbon solvent to remove any remaining Indium(III) halide.
- the disclosed In(III)-containing precursors may have the following features that make them suitable for indium and indium alloy film deposition.
- the disclosed In(III)-containing precursors have heteroleptic nature and nitrogen ligand scaffolding that render the disclosed In(III)-containing precursors much more volatile than indium trichloride (InCl 3 ) with sufficient vapor pressures at lower temperatures.
- the presence of the halogen (e.g., chloride) containing ligands in the disclosed In(III)-containing precursors allows for the use of dehalosilylation chemistries to achieve ALD at low temperatures from room temperature to 500° C., preferably 100° C.-400° C.
- the disclosed In(III)-containing precursors represent a potential new product line in semiconductor industry.
- the disclosed In(III)-containing precursors may have high thermal stability and may be used for forming high-speed, high sensitivity semiconductor layers, e.g. in CMOS systems, 3D NAND Channel or in photodetectors.
- the disclosed In(III)-containing precursors and the disclosed film forming compositions are suitable to deposit the corresponding element-containing films and its related use for deposition of the corresponding element-containing layers.
- the disclosed In(III) precursors and the disclosed film forming compositions are useful for the fabrication of indium tin oxide in displays, solar fuel, high speed electronic (InN), optoelectronic components, high-speed electronics, photovoltaics (InP), infrared detectors, diode laser (InAs), fast transistors, magnetic field, thermal image detectors (InSb), photoelectronic devices, photoelectrochemical water splitting (In 2 S 3 ), LED applications, the fabrication of copper indium gallium selenide (CIGS) in photovoltaics and optical applications, indium gallium zinc oxide (IGZO) in displays, semiconductors, Logic and memories industries, and the like.
- InN high speed electronic
- optoelectronic components high-speed electronics
- Photovoltaics InP
- InAs diode laser
- InSb thermal image detectors
- LED applications the fabrication of copper indium gallium selenide (CIGS) in photovoltaics and optical applications, indium gallium zinc oxide
- the disclosure also includes processes for forming an Indium-containing film and methods for forming an oxygenated or oxygen-free indium-containing film using the disclosed In(III) precursors by vapor deposition methods, such as ALD or CVD.
- the disclosed are a deposition process where the disclosed In(III) precursors are used and introduced into a reaction chamber for deposition a film by ALD, CVD, spin-on, spray, dip coating, slit coating or any other deposition technique to form a film, in combination with or without one or more oxidants (for example O 2 and O 3 , or H 2 O and O 3 ), or with one or more reductants or nitriding agents (for example H 2 and NH 3 , N 2 and NH 3 , or NH 3 and N 2 H 4 ) introduced simultaneously and/or sequentially.
- the disclosed deposition processes using the disclosed In(III) precursors may be assisted by heating, light, direct or remote plasma, or combination thereof.
- the co-reactant may be an oxidizing gas such as one of O 2 , O 3 , H 2 O, H 2 O 2 , NO, N 2 O, NO 2 , oxygen containing radicals such as O. or OH., alcohol, silanols, aminoalcohols, carboxylic acids such as formic acid, acetic acid, propionic acid, para-formaldehyde, other oxidizing compounds and mixtures thereof.
- the oxidizing gas is selected from the group consisting of O 2 , O 3 , H 2 O 2 , and H 2 O.
- the co-reactant is plasma treated oxygen, ozone, or combinations thereof.
- the resulting In(III)-containing film will also contain oxygen.
- the co-reactant may be NH 3 , N 2 , H 2 or N 2 /H 2 , amines, diamines, cyanides, di-imines, hydrazines (for example, N 2 H 4 , MeHNNH 2 , MeHNNHMe), organic amines (for example, H 2 N(CH 3 ), H 2 N(CH 2 CH 3 ), H 2 NC(CH 3 ) 3 , N(CH 3 )H 2 , N(C 2 H 5 )H 2 , N(CH 3 ) 2 H, N(C 2 H 5 ) 2 H, N(CH 3 ) 3 , N(C 2 H 5 ) 3 , (SiMe 3 ) 2 NH), pyrazoline, pyridine, radical and plasma species, and mixtures thereof.
- amines for example, N 2 H 4 , MeHNNH 2 , MeHNNHMe
- organic amines for example, H 2 N(CH 3 ), H 2 N(CH 2 CH 3
- the co-reactant may be a primary amine, a secondary amine, a tertiary amine, trisilylamine, radicals thereof, and mixtures thereof.
- the co-reactant is NH 3 or H 2 .
- the resulting In(III)-containing film will also contain nitrogen.
- the co-reactants may include another precursor.
- the co-reactant may be treated by a plasma, in order to decompose the reactant into its radical form, at least one of H 2 , N 2 and O 2 may be utilized as a hydrogen, nitrogen or oxygen source gas, respectively, when treated with plasma.
- the plasma source may be a N 2 plasma, N 2 /He plasma, N 2 /Ar plasma, NH 3 plasma, NH 3 /He plasma, NH 2 /Ar plasma, He plasma, Ar plasma, H 2 plasma, H 2 /He plasma, H 2 /organic amine plasma, and mixtures thereof.
- the plasma may be generated with a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W.
- the plasma may be generated present within the reactor itself.
- the plasma may generally be at a location removed from the reactor, for instance, in a remotely located plasma system.
- One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
- the co-reactant may be introduced into a direct plasma reactor, which generates plasma in the reaction chamber, to produce the plasma-treated reactant in the reaction chamber.
- the co-reactant may be introduced and held in the reaction chamber prior to plasma processing.
- the plasma processing may occur simultaneously with the introduction of the reactant.
- the plasma-treated co-reactant may be produced outside of the reaction chamber, for example, a remote plasma to treat the co-reactant prior to passage into the reaction chamber.
- the disclosed film forming compositions are suitable for ALD. More particularly, the disclosed film forming compositions are capable of surface saturation, self-limited growth per cycle, and perfect step coverage on aspects ratios ranging from approximately 2:1 to approximately 200:1, and preferably from approximately 60:1 to approximately 150:1. Additionally, the disclosed film forming compositions have high decomposition temperatures, indicating good thermal stability to enable ALD. The high decomposition temperatures permit ALD at higher temperatures, resulting in films having higher purity. The disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, flat panel type devices.
- the disclosed In(III)-containing film forming compositions may be used to deposit In(III)-containing films using any deposition methods known to those of skill in the art.
- suitable deposition methods include chemical vapor deposition (CVD) or atomic layer deposition (ALD) with or without plasma enhancement.
- exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatial isolation ALD, temporal ALD, selective or not ALD, hot-wire ALD (HWALD), radicals incorporated ALD, and combinations thereof.
- the deposition method is preferably ALD, PE-ALD, or spatial ALD in order to provide suitable step coverage and film thickness control.
- Exemplary CVD methods include metal-organic CVD (MOCVD), thermal CVD, pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD) or atmospheric pressure CVD (APCVD), hot-wire CVD or hot filament CVD (also known as cat-CVD, in which a hot wire serves as an energy source for the deposition process), hot wall CVD, cold wall CVD, aerosol assisted CVD, direct liquid injection CVD, combustion CVD, hybrid physical-CVD, metalorganic CVD, rapid thermal CVD, photo-initiated CVD, laser CVD, radicals incorporated CVD, plasma enhanced CVD (PECVD) including but not limited to flowable PECVD, and combinations thereof.
- MOCVD metal-organic CVD
- PCVD pulsed CVD
- LPCVD low pressure CVD
- SACVD sub-atmospheric CVD
- APCVD atmospheric pressure CVD
- hot-wire CVD or hot filament CVD also known
- the disclosed In(III)-containing film forming composition contains less than 5% v/v, preferably less than 1% v/v, more preferably less than 0.1% v/v, and even more preferably less than 0.01% v/v of any of its analogs or other reaction products.
- This embodiment may provide better process repeatability.
- This embodiment may be produced by purification (e.g., distillation, sublimation, chromatography, etc.) of the In(III)-containing film forming composition.
- Purity of the disclosed film forming composition is greater than 93% w/w (i.e., 95.0% w/w to 100.0% w/w), preferably greater than 98% w/w (i.e., 98.0% w/w to 100.0% w/w), and more preferably greater than 99% w/w (i.e., 99.0% w/w to approximately 99.999% w/w or 99.0% w/w to 100.0% w/w).
- 93% w/w i.e., 95.0% w/w to 100.0% w/w
- 98% w/w i.e., 98.0% w/w to 100.0% w/w
- 99% w/w i.e., 99.0% w/w to approximately 99.999% w/w or 99.0% w/w to 100.0% w/w.
- the purity may be determined by NMR spectroscopy and gas or liquid chromatography with mass
- the disclosed film forming compositions may contain any of the following impurities: pyrazoles; pyridines; alkylamines; alkylimines; THF; ether, pentane; cyclohexane; heptanes; benzene; toluene; chlorinated metal compounds; lithium, sodium, potassium pyrazolyl.
- the total quantity of these impurities is preferably below 5% w/w (i.e., 0.0% w/w to 5.0% w/w), preferably below 2% w/w (i.e., 0.0% w/w to 2.0% w/w), and more preferably below 1% w/w (i.e., 0.0% w/w to 1.0% w/w).
- the disclosed film forming composition may be purified by recrystallization, sublimation, distillation, and/or passing the gas liquid through a suitable adsorbent, such as 4 ⁇ molecular sieves.
- Purification of the disclosed film forming composition may also result in metal impurities each range independently at the 0 ppbw to 1 ppmw, preferably approximately 0 to approximately 500 ppbw (part per billion weight) level, more preferably from approximately 0 ppbw to approximately 100 ppbw, and even more preferably from approximately 0 ppbw to approximately 10 ppbw.
- metal or metalloid impurities include, but are not limited to, Aluminum(Al), Arsenic(As), Barium(Ba), Beryllium(Be), Bismuth(Bi), Cadmium(Cd), Calcium(Ca), Chromium(Cr), Cobalt(Co), Copper(Cu), Gallium(Ga), Germanium (Ge), Hafnium(Hf), Zirconium(Zr), Iron(Fe), Lead(Pb), Lithium(Li), Magnesium(Mg), Manganese(Mn), Tungsten(W), Nickel(Ni), Potassium(K), Sodium(Na), Strontium(Sr), Thorium(Th), Tin(Sn), Titanium(Ti), Uranium(U), Vanadium(V) and Zinc(Zn).
- the disclosed film forming compositions may be supplied either in neat form or in a blend with a suitable solvent, such as ethyl benzene, xylene, mesitylene, decalin, decane, dodecane.
- a suitable solvent such as ethyl benzene, xylene, mesitylene, decalin, decane, dodecane.
- the disclosed precursors may be present in varying concentrations in the solvent.
- the neat blended film forming compositions are introduced into a reactor in a vapor form by conventional means, such as tubing and/or flow meters.
- the vapor form may be produced by vaporizing the neat blended composition through a conventional vaporization step such as direct vaporization, distillation, by bubbling, or by using a sublimator, such as the one disclosed in PCT Publication WO2009/087609 to Xu et al.
- the neat blended composition may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reactor.
- the neat blended composition may be vaporized by passing a carrier gas into a container containing the composition by bubbling the carrier gas into the composition.
- the carrier gas may include, but is not limited to, Ar, He, N 2 , and mixtures thereof. Bubbling with a carrier gas may also remove any dissolved oxygen present in the neat blended composition.
- the carrier gas and composition are then introduced into the reactor as a vapor,
- the container containing the disclosed film forming composition may be heated to a temperature that permits the composition to have a sufficient vapor pressure.
- the container may be maintained at temperatures in the range of, for example, approximately 0° C. to approximately 200° C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of precursor vaporized.
- the reactor may be any enclosure chamber within a device in which deposition methods take place such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, other types of deposition systems under conditions suitable to cause the compounds to react and form the layers.
- a parallel-plate type reactor such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, other types of deposition systems under conditions suitable to cause the compounds to react and form the layers.
- a parallel-plate type reactor such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, other types of deposition systems under conditions suitable to cause the compounds to react and form the layers.
- a parallel-plate type reactor such as without limitation, a cold
- the reactor contains one more substrates onto which the films will be deposited.
- a substrate is generally defined as the material on which a process is conducted.
- the substrates may be any suitable substrate used in semiconductor, photovoltaic, fiat panel, LCD-TFT device manufacturing.
- suitable substrates include wafers, such as silicon, silica, glass, GaAs wafers.
- the wafer may have one more layers of differing materials deposited on it from a previous manufacturing step.
- the wafers may include a dielectric layer.
- the wafers may include silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxy nitride layers, carbon doped silicon oxide (SiCOH) layers, metal, metal oxide metal nitride layers (Ti, Ru, Ta, etc.), and combinations thereof. Additionally, the wafers may include copper layers noble metal layers (e.g., platinum, palladium, rhodium, gold). The wafers may include barrier layers, such as manganese, manganese oxide, etc. Plastic layers, such as poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)[PEDOT:PSS] may also be used.
- the layers may be planar or patterned.
- the disclosed processes may deposit the layer directly on the wafer or directly on one or more layers on top of the wafer when patterned layers are formed on the substrate.
- the patterned layers may be alternating layers of two specific layers such as In 2 O 3 and ZrO 2 used in 3D NAND.
- film layer used herein refer to a thickness of some material laid on or spread over a surface and that the surface may be a trench a line.
- substrates for example, an indium oxide film may be deposited onto a metal oxide layer, such as a ZrO 2 layer, an HfO 2 layer, or a MoO 2 layer.
- the substrate final application is not limited to the present invention, but this technology may find particular benefits for the following types of substrates: silicon wafers, glass wafers and panels, beads, powders and nano-powders, monolithic porous media, printed circuit board, plastic sheets, etc.
- Exemplary powder substrates include a powder used in rechargeable battery technology.
- a non-limiting number of powder materials include NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.
- the temperature and the pressure within the reactor are held at conditions suitable for vapor depositions, such as ALD and CVD.
- conditions within the chamber are such that at least part of the precursor is deposited onto the substrate to form a layer.
- the pressure in the reactor or the deposition pressure may be held between about 10 ⁇ 3 torr and about 100 torr, more preferably between about 10 ⁇ 2 torr and 10 torr, as required per the deposition parameters.
- the temperature in the reactor or the deposition temperature may be held between about 100° C. and about 600° C., preferably between about 150° C. and about 500° C.
- “at least part of the precursor is deposited” means that some all of the precursor reacts with adheres to the substrate.
- the temperature to achieve optimal film growth may be controlled by either controlling the temperature of the substrate holder.
- Devices used to heat the substrate are known in the art.
- the substrate is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition.
- a non-limiting exemplary temperature range to which the substrate may be heated includes from approximately 50° C. to approximately 600° C.
- the deposition temperature is preferably less than 400° C.
- the deposition temperature may range from approximately 100° C. to approximately 600° C.
- the substrate may be heated to a sufficient temperature to obtain the desired In(III)-containing film at a sufficient growth rate and with desired physical state and composition.
- a non-limiting exemplary temperature range to which the substrate may be heated includes from room temperature to approximately 600° C.
- the temperature of the substrate remains less than or equal to 500° C.
- the ALD conditions within the chamber allow the disclosed film forming composition adsorbed or chemisorbed on the substrate surface to react and form a film on the substrate.
- plasma-treating the co-reactant may provide the co-reactant with the energy needed to react with the disclosed film forming composition.
- the exemplary ALD process becomes an exemplary PEALD process.
- the co-reactant may be treated with plasma prior subsequent to introduction into the chamber.
- the film forming composition and co-reactants may be introduced into the reactor sequentially (ALD).
- the reactor may be purged with an inert gas between the introduction of each of the film forming composition, any additional precursors, and the co-reactants.
- Another example is to introduce the co-reactant continuously and to introduce the film forming composition by pulse, while activating the co-reactant sequentially with a plasma, provided that the film forming composition and the non-activated co-reactant do not substantially react at the chamber temperature and pressure conditions (CW PEALD).
- Each pulse of the disclosed film forming composition may last for a time period ranging from about 0.001 seconds to about 120 seconds, alternatively from about 1 seconds to about 80 seconds, alternatively from about 5 seconds to about 30 seconds.
- the co-reactant may also be pulsed into the reactor, In such embodiments, the pulse of each may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 30 seconds, alternatively from about 2 seconds to about 20 seconds.
- the vaporized film forming compositions and co-reactants may be simultaneously sprayed from different sectors of a shower head (without mixing of the composition and the reactant) under which a susceptor holding several wafers is spun (spatial ALD).
- deposition may take place for a varying length of time. Generally, deposition may be allowed to continue as long as desired necessary to produce a film with the necessary properties. Typical film thicknesses may vary from several angstroms to several hundreds of microns, and typically from 1 to 100 nm, depending on the specific deposition process. The deposition process may also be performed as many times as necessary to obtain the desired film.
- the disclosed methods for forming an In(III)-containing layer on a substrate include: placing a substrate in a reactor, delivering into the reactor a vapor of the disclosed In(III)-containing film forming composition, and contacting/adsorbing the vapor with the substrate (and typically directing the vapor to the substrate) to form an In(III)-containing layer on the surface of the substrate.
- the disclosed methods for forming an In(III)-containing layer on a substrate include: exposing the substrate to the vapor of the disclosed In(III)-containing film forming composition, and depositing an In(III)-containing layer on the surface of the substrate.
- the vapor of the In(III)-containing film forming composition is generated and then introduced into a reaction chamber containing a substrate.
- the temperature and the pressure in the reaction chamber and the temperature of the substrate are held at conditions suitable for vapor deposition of at least part of the disclosed In(III)-containing precursor onto the substrate.
- conditions within the reaction chamber are adjusted such that at least part of the precursor is deposited onto the substrate to form the In(III)-containing layer.
- at least part of the precursor is deposited means that some or all of the precursor reacts with or adheres to the substrate.
- a co-reactant may also be used to help in formation of the In(III)-containing layer.
- the disclosed film forming compositions and co-reactants may be introduced into the reactor either simultaneously (CVD), sequentially (ALD) or different combinations thereof.
- the reactor may be purged with an inert gas (e.g., N 2 or Ar) between the introduction of the film forming composition and the introduction of the co-reactant.
- an inert gas e.g., N 2 or Ar
- the co-reactant and the film forming composition may be mixed together to form a co-reactant/compound mixture, and then introduced to the reactor in a mixture form.
- Another example is to introduce the co-reactant continuously and to introduce the disclosed film forming composition by pulse (pulsed CVD).
- the vapor phase of the disclosed film forming composition such as, [(Et)N C(Me) N(tBu)]In(III)Cl 2 , is introduced into the reactor, where it is contacted with a suitable substrate, either chemisorbed or physisorbed thereon.
- Excess composition may then be removed from the reactor by purging and/or evacuating the reactor, that is, either by purging a reactor with an inert gas (e.g., N 2 , Ar, Kr or Xe), or passing the substrate in a sector under high vacuum and/or a carrier gas curtain.
- a co-reactant e.g., O 3 or NH 3
- Any excess co-reactant is removed from the reactor by purging and/or evacuating the reactor.
- the desired film is an oxide, such as In 2 O 3
- this two-step process may provide the desired film thickness by repeating until a film having the desired thickness has been obtained. By alternating the provision of the indium film forming composition and co-reactant, a film of desired composition and thickness can be deposited.
- the two-step process above may be inserted by introduction of the vapor of an additional precursor compound into the reactor (three-step process).
- the additional precursor compound will be selected based on the nature of the film being deposited.
- the additional elements may include gallium (Ga), nitrogen (N), sulfur (S), phosphorous (P), Tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof.
- the resultant film deposited on the substrate contains indium and co-reactant in combination with the additional element.
- a nanolaminate film is obtained.
- the additional precursor compound is contacted or adsorbed with the substrate.
- any excess precursor compound is removed from the reactor by purging and/or evacuating the reactor.
- a co-reactant such as NH 3
- an additional precursor may be introduced into the reactor to react with the indium precursor compound. Excess co-reactant or precursor is removed from the reactor by purging and/or evacuating the reactor.
- the remaining co-reactant or precursor may be introduced into the reactor and removal of excess is removed by purging and/or evacuation of the reactor.
- the entire three-step process may be repeated until a desired film thickness has been achieved.
- the three-step process above may be inserted by introduction of the vapor of another additional precursor compound into the reactor (four-step process).
- the other additional precursor compound will be selected based on the nature of the film being deposited.
- the additional elements may include gallium (Ga), nitrogen (N), sulfur (S), phosphorous (P), tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof.
- the resultant film deposited on the substrate contains indium in combination with the additional three elements.
- the precursors may include an indium precursor such as [(iPr)N CH N(iPr)]In(III)Cl 2 , a Ga precursor such as GaCl 3 or Ga(NO 3 ) 3 , a Zn precursor such as Zn(NO 3 ) 2 in combination with a co-reactant O 3 .
- an indium precursor such as [(iPr)N CH N(iPr)]In(III)Cl 2
- Ga precursor such as GaCl 3 or Ga(NO 3 ) 3
- a Zn precursor such as Zn(NO 3 ) 2 in combination with a co-reactant O 3 .
- the Indium-containing films may contain a second element selected from P, N, S, Ga, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, Zn, one or more lanthanides, or combinations thereof.
- indium oxide can serve as a semiconductor material, forming heterojunctions with p-InP, n-GaAs, n-Si, and other materials.
- Thin films of indium oxide can be used as diffusion barriers (“barrier metals”) in semiconductors (e.g., to inhibit diffusion between aluminum and silicon).
- the film may be subject to further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV e-beam curing, and/or plasma gas exposure.
- further processing such as thermal annealing, furnace-annealing, rapid thermal annealing, UV e-beam curing, and/or plasma gas exposure.
- the In 2 O 3 film may be exposed to a temperature ranging from approximately 200° C. and approximately 100° C. for a time ranging from approximately 0.1 second to approximately 7200 seconds under an inert atmosphere, an 0-containing atmosphere, and combinations thereof. Most preferably, the temperature range is 350° C. to 450° C. for 3600-7200 seconds under an inert atmosphere or an 0-containing atmosphere.
- the resulting film may contain fewer impurities and therefore may have an improved density resulting in improved leakage current.
- the annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber, with the annealing/flash annealing process being performed in a separate apparatus. Any of the above post-treatment methods, but especially thermal annealing, has been found effective to reduce carbon and nitrogen contamination of the In 2 O 3 film. This in turn tends to improve the resistivity of the film.
- the films deposited by any of the disclosed processes may have a bulk resistivity at room temperature of approximately 50 ⁇ ohm ⁇ cm to approximately 1,000 ⁇ ohm ⁇ cm. Room temperature is approximately 20° C. to approximately 25° C. depending on the season. Bulk resistivity is also known as volume resistivity.
- the bulk resistivity is measured at room temperature on the films that are typically approximately 50 nm thick. The bulk resistivity typically increases for thinner films due to changes in the electron transport mechanism. The bulk resistivity also increases at higher temperatures.
- FIG. 2 is 1 H NMR of [(Et)N C(Me) N(tBu)]In(III)Cl 2 in C 6 D 6 .
- Example 2 The same procedure was followed for Example 1. Reagents used were N,N′-bis(1-methylethyl)methanimidamide (0.95 equiv, 0.039 mol, 5.00 g) methyllithium (0.97 equiv, 0.040 mol, 24.9 ml) and indium (III) chloride (1.0 equiv. 0.041 mol, 9.09 g). The product was isolated (6.10 g, 50% yield) as a white solid which melted at 91° C. 1 H-NMR (THF-d 8 , ⁇ (ppm)): 1.16 (12H, d, 6.5 Hz), 3.57 (2H, spt, 6.5 Hz), 7.69 (1H, s).
- FIG. 4 shows single step evaporation with ⁇ 5% residue remaining at 210° C. for [(iPr)N CH N(iPr)]In(III)Cl 2 .
- the vacuum TGA result for InCl 3 is also added.
- volatility of [(iPr)N CH N(iPr)]In(III)Cl 2 precursor increases relative to that of InCl 3 .
- FIG. 5 The DSC results for [(iPr)N CH N(iPr)]In(III)Cl 2 is shown in FIG. 5 .
- [(iPr)N CH N(iPr)]In(III)Cl 2 has a vapor pressure of 1 torr at 128° C.
- FIG. 6 is 1 H NMR of [(iPr)N CH N(iPr)]In(III)Cl 2 in THF-d 8 .
- Example 2 The same procedure was followed for Example 1. Reagents used were N,N′-diisopropylcarbodiimide (0.95 equiv, 0.046 mol, 5.75 g), n-butyllithium (0.97 equiv, 0.047 mol, 29.1 ml) and indium (III) chloride (1.0 equiv. 0.048 mol, 10.64 g). The precursor [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 was isolated as a viscous liquid (12.91 g, 73% yield).
- Example 2 The same procedure was followed for Example 1. Reagents used were 1-tert-butyl-3-ethylcarbodiimide (0.95 equiv, 0.048 mol, 5.99 g), n-butyllithium (0.97 equiv, 0.049 mol, 30.3 ml) and indium (III) chloride (1.0 equiv. 0.05 mol, 11.09 g). The precursor [(Et)N C(nBu) N(tBu)]In(III)Cl 2 was isolated as a viscous liquid (12.18 g, 66% yield).
- FIG. 11 is 1 H NMR of [(Et)N C(nBu) N(tBu)]In(III)Cl 2 in C 6 D 6 .
- Example 2 The same procedure was followed for Example 1. Reagents used were diisopropylcarbodiimide (0.95 equiv, 0.14 mol, 22.7 mL) methyllithium (0.97 equiv, 0.15 mol, 90.9 ml) and indium (III) chloride (1.0 equiv. 0.15 mol, 33.3 g). The product was isolated (25.1 g, 51% yield) as a white solid which melted at 110° C. 1 H-NMR (benzene-d 6 , ⁇ (ppm): 1.20 (13H, d, 6.5 Hz), 1.41 (3H, s), 3.46 (2H, spt, 6.5 Hz).
- the TGA results for [(iPr)N C(Me) N(iPr)]In(III)Cl 2 is shown in FIG. 12 , which shows single step evaporation with ⁇ 5% residue remaining at 200° C. for [(iPr)N C(Me) N(iPr)]In(III)Cl 2 .
- the vacuum TGA result for InCl 3 is also added. As shown, volatility of [(iPr)N C(Me) N(iPr)]In(III)Cl 2 precursor increases relative to that of InCl 3 .
- FIG. 13 is 1 H NMR of [(iPr)N C(Me) N(iPr)]In(III)Cl 2 in CD 6 .
- 1-tert-butyl-3-ethylcarbodiimide (2.0 equiv, 0.08 mol, 10.10 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to ⁇ 78° C.
- Methyllithium (2.0 equiv, 0.08 mol, 50 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring.
- isopropyl-imino-2,2-dimethylpyrrolidine (1.0 equiv, 0.040 mol, 6.17 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to ⁇ 78° C.
- Methyllithium (1.0 equiv, 0.040 mol, 25 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring.
- isopropyl-imino-2,2-dimethylpyrrolidine (2.0 equiv, 0.080 mol, 12.34 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to ⁇ 78° C.
- Methyllithium (2.0 equiv, 0.080 mol, 50 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring.
- N,N,N′-triethylethylenediamine (1.0 equiv, 0.040 mol, 5.77 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to ⁇ 78° C.
- Methyllithium (1.0 equiv, 0.040 mol, 25 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring.
- N,N,N′-triethylethylenediamine (1.0 equiv, 0.080 mol, 11.54 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to ⁇ 78° C.
- Methyllithium (1.0 equiv, 0.080 mol, 50 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring.
- ALD was performed using alternating exposures of [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 and O 3 in an ALD reactor.
- N 2 carrier gas is used to transport the vapor of [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 into the ALD reactor.
- the ALD sequences are expressed the exposure for the precursor [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 , the purge following the precursor exposure, afterward, the exposure of the co-reactant O 3 , and then the purge following the exposure to 0.
- In 2 O 3 ALD films may be deposited on 2 cm by 2 cm Si(100) and glass substrates.
- the deposition temperature may be 250° C. in 1 torr.
- SEM images are acquired of the resulting In 2 O 3 film.
- An energy dispersive analysis of X-rays (EDAX) detector is used to acquire elemental analysis.
- AFM, XRD and ellipsometric measurements of the resulting In 2 O 3 films deposited on Si(100) surfaces are performed.
- AA atomic absorption
- MS-GC nuclear magnetic resonance
- NMR nuclear magnetic resonance
- FT-IR neutron activation analysis
- EDAX energy dispersive analysis by X-rays
- RBS Rutherford back-scattering analysis
- X-ray analyses are used to help understand the fundamental mechanism of the resulting In 2 O 3 film.
- [(iPr)N C(Me) N(iPr)]In(III)Cl 2 and P(SiMe 3 ) 3 are used as the In and P sources, respectively.
- the film deposition occurs using N 2 as the carrier gas for precursor delivery.
- a purge step of sufficient duration occurs after each precursor is dosed into the thermal ALD reactor.
- the cycle is initiated by dosing the [(iPr)N C(Me) N(iPr)]In(III)Cl 2 precursor into the reactor.
- P(SiMe 3 ) 3 is then introduced into the reactor to close the cycle. By transporting the precursors to the substrate, the precursors are adsorbed on the substrate surface.
- the reactive species thus diffuse at the surface to preferential sites and react in a heterogeneous phase to give rise to the formation of the InP film.
- the deposition may require no catalyst and may be carried out on a variety of substrates, such as thin Si or oxide substrates.
- the substrate temperature is maintained at approximately 150° C.
- the resulting InP films can then undergo further processing, such as a thermal annealing step.
- the InP films are characterized by various techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy dispersive analysis by X-rays (EDAX), Rutherford back-scattering analysis (RBS), and X-ray analyses, etc., which are used to help understand the fundamental mechanism of the ALD growth.
- [(iPr)N C(Me) N(iPr)]In(III)Cl 2 , GaCl 3 and As(SiMe 3 ) 3 are used as the In, Ga and As sources, respectively.
- the film deposition occurs using an ACBC-type supercycle in which N 2 is used as the carrier gas for precursor delivery.
- a purge step of sufficient duration occurs after each precursor is dosed into the thermal ALD reactor.
- the cycle is initiated by dosing the [(iPr)N C(Me) N(iPr)]In(III)Cl 2 precursor into the reactor.
- As(SiMe 3 ) 3 is introduced into the reactor.
- GaCl 3 is then dosed into the chamber.
- a final dose of As(SiMe 3 ) 3 closes the cycle.
- the precursors By transporting the precursors to the substrate, the precursors are adsorbed on the substrate surface.
- the reactive species thus diffuse at the surface to preferential sites and react in a heterogeneous phase to give rise to the formation of the InGaAs film.
- Such a cycle can be used to provide films with compositions of In 0.5 Ga 0.5 As 1 .
- the steps of thermal ALD of InGaAs can also be adjusted to provide films of varying compositions.
- the deposition may require no catalyst and may be carried out on a variety of substrates, such as thin Si or oxide substrates.
- the substrate temperature is maintained at approximately 150° C.
- the resulting InGaAs films can then undergo further processing, such as a thermal annealing step.
- the InGaAs films are characterized by various techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy dispersive analysis by X-rays (EDAX), Rutherford back-scattering analysis (RBS), and X-ray analyses, etc., which are used to help understand the fundamental mechanism of the ALD growth.
- AA atomic absorption
- MS-GC MS-GC
- NMR nuclear magnetic resonance
- FT-IR nuclear magnetic resonance
- NAA neutron activation analysis
- EDAX energy dispersive analysis by X-rays
- RBS Rutherford back-scattering analysis
- X-ray analyses etc.
Abstract
Description
- The present invention relates to indium (III)-containing film forming compositions comprising In(III)-containing precursors that contain halogens, methods of synthesizing them and methods of using them to deposit the indium-containing films and/or indium-containing alloy films, in particular, to the In(III)-containing precursors containing chlorine with nitrogen based ligands suitable for vapor phase depositions (e.g., ALD, CVD) of the indium-containing films and/or indium-containing alloy films.
- Indium-containing alloys, thin films, and nanostructured materials are highly versatile optoelectronic materials widely applied in both research and industry, in particular the semiconductor industry, with applications in many areas including electronics and photonics. For example, InGaAs is believed to be one of the stronger contenders for the future replacement of silicon in CMOS systems. InGaAs is also a key component of optical fiber telecommunications, serving as a high-speed, high sensitivity photodetector. Despite the impressive physical properties of indium alloys and, indeed, all group III-V alloys, these materials are hamstrung by two key challenges. The synthesis of these materials is either limited to slow growth processes, such as molecular beam epitaxy, or by metalorganic chemical vapor deposition, which requires enormous amounts of material and challenging engineering to achieve throughput, uniformity, and reproducibility. The next challenge relates specifically to the semiconductor industry. Combining group III-V semiconductors with silicon is extremely challenging and has prevented the rapid development of high-performance devices. The development of new precursors for group III-V alloys, including indium, which are compatible with high-throughput production and ease of device integration is highly desirable to multiple industries.
- Homoleptic indium precursors have been investigated for deposition processes. For example, Kim et al. (“Obtaining a Low and Wide Atomic Layer Deposition Window (150-275° C.) for In2O3 Films Using an InIII Amidinate and H2O”, Chem. Eur. J. 2018, 24, 9525) disclose two new In complexes for ALD of In2O3 including tris(N,N′-diisopropylformamidinato)indium(III). Results are compared to homoleptic alkyl and aryl indium complexes, (CH3CH2)3In, (CH3)3In, and CpIn (Cp=cyclopentadienyl).
- US 20130273250 to Fujimura et al. discloses (Amide Amino Alkane) metal compounds and a method of manufacturing metal-containing thin films using said metal compounds, in which a series of novel homoleptic amide amino alkane metal complexes are used for chemical vapor deposition (CVD). The disclosed metal complexes include lithium, sodium, magnesium, manganese, iron, cobalt, nickel, zinc, yttrium, lanthanum, and indium complexes. Specific examples include
- which was isolated as a semi-solid wax that distilled under reduced pressure (130° C. 13.3 Pa).
- Gebhard et al. discloses (“Indium-tris-guanidinates: A Promising Class of Precursors for Water Assisted Atomic Layer Deposition of Ir2O3Films,” Dalton Trans, 2014, 43, 937) syntheses of two homoleptic indium-tris-guanidinate complexes. The compounds were isolated as solids and used for indium oxide ALD processes.
- McCarthy et al. (“Oxygen-Free Atomic Layer Deposition of Indium Sulfide”, ACS Appl. Mater.
Interfaces 2014, 6, 12137) discloses indium (III) amidinate complexes used for ALD of indium sulfide using hydrogen sulfide. - Heteroleptic indium precursors have been investigated for deposition processes. Examples of heteroleptic indium (III) precursors included alkyl ligands, acetate and hydroxyl ligands. For example, Low-temperature growth of indium oxide thin film by plasma-enhance ALD using liquid dimethyl(N-ethoxy-2,2-dimethylpropanamido)indium for high-mobility thin film transistor application. Kim et al., ACS Appl. Mater.
Interfaces 2016, 8, 40, 26924. - US 2016017485 to Martinson et al. discloses a method of atomic layer deposition of indium sulfide films using a synthesized indium precursor and hydrogen sulfide. US 20160326008 to Koh et al. discloses details heteroleptic Indium (III) precursors bis(trimethylsilyl)aminodiethylindium and dimethyl(3-dimethylaminopropyl)indium which are liquids at room temperature.
- Gebhard et al. (New amidinate complexes of indium(III): Promising CVD precursors for transparent and conductive In2O3 thin films, Dalton Trans., 2013, 00, 1-3) disclose details the synthesis of two new heteroleptic indium precursors: [InCl(amd)2] and [InMe(amd)2], However the chlorine-containing precursor was only synthesized and not used for deposition or investigated for its thermal properties.
- WO 2017083483 (US 20170137360) to Curley et al. discloses details the synthesis of dicarboxylate monohydroxyl indium precursors. Several examples of this precursor being used for the solution phase synthesis of InP nanostructures are provided.
- Seki et al. (Indium tin oxide thin films prepared by dip-coating of indium diacetate monohydroxide and tin dichloride, Thin Solid Films, 2001, 388, 22-26) discloses tin-doped In2O3 (ITO) films were prepared by the dip-coating method using an ethanol solution of indium diacetate monohydroxide, In(OH)(CH3COO)2, and tin dichloride, SnCl2.2H2O, with 2-aminoethanol (monoethanolamine), H2NC2H4OH.
- Patton et al. (Chelating Diamide Group IV Metal Olefin Polymerization. Organometallics, 2002, 21, 10, 2145) discloses dichloroindium-tert-Butyl-N,N′-diisopropylamidinate was synthesized as an intermediate en route to indium-bridged chelating diamide titanium complex used as a catalyst for olefin polymerization. The indium amidinate compound was isolated cleanly in 48% yield and characterized using 1H, 13C NMR spectroscopy and HRMS.
- WO 0146201A1 (US 20020098973A1) to Campbell et al. discloses a large range of bridged
Group 4 transition metal complexes are disclosed. For those bridgedgroup 4 transition metal complexes that contain indium, dichloroindium-tert-butyl-N,N′-diisopropylamidinate is synthesized as an intermediate. - Debnicke et al. (N, N, N′-tris(trimethylsilyl) as reagents in complex chemistry, J. Organomet. Chem, 1988, 352, (1-2), C1) disclose dichloroindium-phenyl-N,N′-Bis(trimethylsilyl)amidinate was synthesized as during a screen of the reaction of N, N, N′-tris(trimethylsilyl) organoamidines with main group and transition metal halides. Isolation or characterization of the indium complex was not reported.
- Kottmair-Maieron et al. (Monomeric dialkyl metal complexes of R2M(NR′)2XR type with M=aluminum, gallium, indium, thallium; x=sulfur, carbon and R, R′=alkyl and silyl, Z. Anorg. Allg. Chem, 1991, 593, 111) disclose a series of group III compounds using the amidinate scaffold were reported. The synthesis of dichloroindium-methyl-N,N′-diisopropylamidinate was reported as a low melting solid and characterized by NMR and IR spectroscopy; no further applications of molecules were reported.
- Hwang et al. (J. Cryst. Growth, 1981, vol. 55, Iss. 1, 116-124) disclose that indium trichloride acetonitrile adduct, InCl3(NCCH3), combined with CuCl(NCCH3)n as the copper source (both dissolved in acetonitrile solvent, NCCH3), and hydrogen sulfide H2S, as the sulfur source, was applied as precursor for the growth of CuInS2 layers on GaP substrates by MOCVD. The precursor vapor generated by bubbling N2 through the sources dissolved in acetonitrile.
- Disclosed is a method for forming an indium(III)-containing film on a substrate, the method comprising the steps of:
- exposing the substrate to a vapor of a film forming composition that contains an indium(III)-containing precursor; and
- depositing at least part of the indium(III)-containing precursor onto the substrate to form the indium(III)-containing film on the substrate through a vapor deposition process,
- wherein the indium(III)-containing precursor has the formula:
- wherein X is chosen from chlorine, bromine and iodine, preferably chlorine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R8 where R7 and R8 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3, the structure may exist as the dimeric structure [((R1)N=C(R3)N(R2))InX]2(μ-X)2,
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3 the structure may exist as the dimeric structure
-
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or -
[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c) - where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5. R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. For these In(III) containing precursors, n=1 or 2 will provide either a 5-membered or 6-membered metallacycle, respectively. Groups R6 and R7 on each C are not required to be identical for structures where n=2. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3 and n=1, the structure may exist as the dimeric structure [((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2,
- where X is a halogen, preferably chlorine. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups (e.g., CF3, m-(CF3)2—C6H3, etc.). Group R4 may also be selected from halogens, such as F, and
-
[N((SiR1R2R3)R4)]InX2 (e) - where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
- The disclosed methods may include one or more of the following aspects:
-
- X being chloride;
- the indium(III)-containing precursor being [(Et)NC(Me)N(tBu)]In(III)Cl2;
- the indium(III)-containing precursor being [(iPr)NCHN(iPr)]In(III)Cl2 or [((iPr)NC(H)N(iPr))InCl]2(μ-Cl)2;
- the indium(III)-containing precursor being [(Et)NC(nBu)N(tBu)]In(III)Cl2;
- the indium(III)-containing precursor being [(iPr)NC(nBu)N(iPr)]In(III)Cl2;
- the indium(III)-containing film being an indium oxide film, or a binary, ternary and quaternary indium alloy film;
- the indium(III)-containing film being a layer of, but not limited to, InGaAs, InxOy (x=0.5 to 1.5, y=0.5 to 1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, or In(OH)3;
- the indium(III)-containing film being a pure indium (In(0)) layer;
- the Indium-containing film containing a second element selected from P, N, S, Ga, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, Zn, one or more lanthanides, or combinations thereof;
- the vapor deposition process being a ALD process, a CVD process or a combination thereof;
- the vapor deposition process being a PEALD process or a spatial ALD process;
- further comprising the step of exposing the substrate to a co-reactant;
- the co-reactant being selected from O3, O2, H2O, NO, N2O, NO2, H2O2, O radicals and combinations thereof;
- the co-reactant being O3 or O2;
- the co-reactant being selected from NH3, NO, N2O, hydrazines, N2 plasma, N2/H2 plasma, NH3 plasma, amines and combinations thereof;
- the co-reactant being NH3;
- the co-reactant being N2 plasma;
- the co-reactant being treated by a plasma;
- the substrate being a powder;
- the powder comprising one or more of NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials;
- the deposition pressure being held between about 10−3 Torr and about 100 Torr;
- the deposition pressure being held between about 10−2 Torr and 100 Torr;
- the deposition temperature being held between about 100° C. and about 600° C.:
- the deposition temperature being held between about 150° C. and about 500°; and
- the deposition reactor wall being heated from approximately 50° C. to approximately 600° C.
- Also disclosed is a method for forming an indium(III)-containing film on a substrate, the method comprising the steps of:
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- forming a chemisorbed and/or physisorbed film, on the surface of the substrate, of an indium(III)-containing precursor having the formula:
- wherein X is chosen from chlorine, bromine and iodine, preferably chlorine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R8 where R7 and R8 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3, the structure may exist as the dimeric structure [((R1)C(R3)N(R2))InX]2(μ-X)2,
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3, the structure may exist as the dimeric structure
-
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or -
[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c) - where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5. R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. For In(III) containing precursors, n=1 or 2 to provide either a 5-membered or 6-membered metallacycle, respectively. Groups R6 and R7 are not required to be identical for structures where n=2. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3 and n=1, the structure may exist as the dimeric structure [((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2,
- where X is a halogen, preferably chlorine. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups (e.g., CF3, m-(CF3)2—C6H3, etc.). Group R4 may also be selected from halogens, such as F, and
-
[N((SiR1R2R3)R4)]InX2 (e) - where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
- The disclosed methods may include one or more of the following aspects:
-
- further comprising the step of chemically reacting the chemisorbed and/or physisorbed film comprising the indium(III)-containing precursor with a co-reactant;
- the co-reactant reacting with the indium(III)-containing precursor in the chemisorbed and/or physisorbed film producing a reaction product that forms the indium(III)-containing film on the surface of the substrate;
- the co-reactant being selected from O3, O2, H2O, NO, N2O, NO2, H2O2, O radicals and combinations thereof; and
- the co-reactant being selected from NH3, NO, N2O, hydrazines, N2 plasma, N2/H2 plasma, NH3 plasma, amines and combinations thereof.
- Also disclosed is a composition for deposition of a film comprising an indium(III)-containing precursor having the formula:
- wherein X is chosen from chlorine, bromine and iodine, preferably chlorine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R8 where R7 and R8 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3, the structure may exist as the dimeric structure [((R1)NC(R3)N(R2))InX]2(μ-X)2,
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3, the structure may exist as the dimeric structure
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[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or -
[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c) - where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. For these In(III) containing precursors, n=1 or 2 will provide either a 5-membered or 6-membered metallacycle, respectively. Groups R6 and R7 are not required to be identical for structures where n=2. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3 and n=1, the structure may exist as the dimeric structure [((R2R3)N—(CR6R7)n—C(R4R5)—N(R))InX]2(μ-X)2,
- where X is a halogen, preferably chlorine. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups (e.g., CF3, m-(CF3)2—C6H3, etc.). Group R4 may also be selected from halogens, such as F, and
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[N((SiR1R2R3)R4)]InX2 (e) - where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
- The disclosed methods may include one or more of the following aspects:
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- X being chloride;
- the indium(III)-containing precursor being selected from [(Et)NC(Me)N(tBu)]In(III)Cl2, [(iPr)NCHN(iPr)]In(III)Cl2, [(Et)NC(Me)N(tBu)]In(III)Cl2 or [(iPr)NC(nBu)N(iPr)]In(III)Cl2;
- the indium(III)-containing precursor being [(Et)NC(Me)N(tBu)]In(III)Cl2;
- the indium(III)-containing precursor being [(iPr)NCHN(iPr)]In(III)Cl2;
- the indium(III)-containing precursor being [(Et)NC(Me)N(tBu)]In(III)Cl2;
- the indium(III)-containing precursor being [(iPr)NC(nBu)N(iPr)]In(III)Cl2;
- the indium(III)-containing precursor having a purity ranging from approximately 93% w/w to approximately 100% w/w; and
- the indium(III)-containing precursor having a purity ranging from approximately 99% w/w to approximately 99.999% w/w.
- The following detailed description and claims utilize a number of abbreviations, symbols, and terms, which are generally well known in the art. Certain abbreviations, symbols, and terms are used throughout the following description and claims, and include:
- As used herein, the indefinite article “a” or “an” means one or more.
- As used herein, “about” or “around” or “approximately” in the text or in a claim means ±10% of the value stated.
- As used herein, “room temperature” in the text or in a claim means from approximately 20° C. to approximately 25° C.
- The term “ambient temperature” refers to an environment temperature approximately 20° C. to approximately 25° C.
- The term “substrate” refers to a material or materials on which a process is conducted. The substrate may refer to a wafer having a material or materials on which a process is conducted. The substrates may be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. The substrate may also have one or more layers of differing materials already deposited upon it from a previous manufacturing step. For example, the wafers may include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon containing layers (e.g., SiO2, SiN, SiON, SiCOH, etc.), metal containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.) or combinations thereof. Furthermore, the substrate may be planar or patterned. The substrate may be an organic patterned photoresist film. The substrate may include layers of oxides which are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (for example, ZrO2 based materials, HfO2 based materials, TiO2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or nitride-based films (for example, TaN, TiN, NbN) that are used as electrodes. One of ordinary skill in the art will recognize that the terms “film” or “layer” used herein refer to a thickness of some material laid on or spread over a surface and that the surface may be a trench or a line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as substrates.
- The term “wafer” or “patterned wafer” refers to a wafer having a stack of films on a substrate and at least the top-most film having topographic features that have been created in steps prior to the deposition of the indium containing film.
- The term “aspect ratio” refers to a ratio of the height of a trench (or aperture) to the width of the trench (or the diameter of the aperture).
- Note that herein, the terms “film” and “layer” may be used interchangeably. It is understood that a film may correspond to, or related to a layer, and that the layer may refer to the film. Furthermore, one of ordinary skill in the art will recognize that the terms “film” or “layer” used herein refer to a thickness of some material laid on or spread over a surface and that the surface may range from as large as the entire wafer to as small as a trench or a line.
- Note that herein, the terms “aperture”, “via”, “hole” and “trench” may be used interchangeably to refer to an opening formed in a semiconductor structure.
- As used herein, the abbreviation “NAND” refers to a “Negative AND” or “Not AND” gate; the abbreviation “2D” refers to 2 dimensional gate structures on a planar substrate; the abbreviation “3D” refers to 3 dimensional or vertical gate structures, wherein the gate structures are stacked in the vertical direction.
- Note that herein, the terms “deposition temperature” and “substrate temperature” may be used interchangeably. It is understood that a substrate temperature may correspond to, or be related to a deposition temperature, and that the deposition temperature may refer to the substrate temperature.
- Note that herein, the terms “precursor” and “deposition compound” and “deposition gas” may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor may correspond to, or be related to a deposition compound or deposition gas, and that the deposition compound or deposition gas may refer to the precursor.
- The standard abbreviations of the elements from the periodic table of elements are used herein. It should be understood that elements may be referred to by these abbreviation (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).
- The unique CAS registry numbers (i.e., “CAS”) assigned by the Chemical Abstract Service are provided to identify the specific molecules disclosed.
- Please note that the silicon-containing films, such as SiN and SiO, are listed throughout the specification and claims without reference to their proper stoichoimetry. The silicon-containing films may include pure silicon (Si) layers, such as crystalline Si, polysilicon (p-Si or polycrystalline Si), or amorphous silicon; silicon nitride (SikNl) layers; or silicon oxide (SinOm) layers; or mixtures thereof, wherein k, l, m, and n, inclusively range from 0.1 to 6. Preferably, silicon nitride is SikNl, where k and l each range from 0.5 to 1.5. More preferably silicon nitride is Si3N4. Herein, SiN in the following description may be used to represent SikNl containing layers. Preferably silicon oxide is SinOm, where n ranges from 0.5 to 1.5 and m ranges from 1.5 to 3.5. More preferably, silicon oxide is SiO2. Herein, SiO in the following description may be used to represent SinOm containing layers. The silicon-containing film could also be a silicon oxide based dielectric material such as organic based or silicon oxide based low-k dielectric materials such as the Black Diamond II or III material by Applied Materials, Inc. with a formula of SiOCH. Silicon-containing film may also include SiaObNc where a, b, c range from 0.1 to 6. The silicon-containing films may also include dopants from group III, IV, V and VI, such as B, C, P, As and/or Ge.
- As used herein, the term “hydrocarbon” refers to a saturated or unsaturated function group containing exclusively carbon and hydrogen atoms. As used herein, the term “alkyl group” refers to saturated functional groups containing exclusively carbon and hydrogen atoms. An alkyl group is one type of hydrocarbon. Further, the term “alkyl group” refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.
- As used herein, the abbreviation “Me” refers to a methyl group; the abbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refers to any propyl group (i.e., n-propyl or isopropyl); the abbreviation “iPr” refers to an isopropyl group; the abbreviation “Bu” refers to any butyl group (n-butyl, iso-butyl, tert-butyl, sec-butyl); the abbreviation “tBu” refers to a tert-butyl group; the abbreviation “sBu” refers to a sec-butyl group; the abbreviation “iBu” refers to an iso-butyl group; the abbreviation “Ph” refers to a phenyl group; the abbreviation “Am” refers to any amyl group (iso-amyl, sec-amyl, tert-amyl); the abbreviation “Cy” refers to a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); the abbreviation “Ar” refers to an aromatic hydrocarbon, group (phenyl, xylyl, mesityl, etc.).
-
- wherein X is chosen from chlorine, bromine and iodine, preferably chlorine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R8 where R7 and R8 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3, the structure may exist as the dimeric structure [((R1)NC(R3)N(R2))InX]2(μ-X)2.
-
- wherein X is chosen from chlorine, bromine and iodine, preferably chlorine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R8 where R7 and R8 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups.
- As used herein, the formulas,
- are represented by the following structures:
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5. R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3, the structure may exist as the dimeric structure
- As used herein, the formula
- is represented by the following structure:
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
- As used herein, the formulas, [(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2 or [((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, are represented by the following structures:
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5. R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. For these In(III) containing precursors, n=1 or 2 will provide either a 5-membered or 6-membered metallacycle, respectively. Groups R6 and R7 are not required to be identical for structures where n=2. Under certain conditions when the disclosed In(III)-containing precursors have sufficiently small R1, R2 and R3 and n=1, the structure may exist as the dimeric structure [((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2.
- As used herein, the formula, [(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, is represented by the following structure:
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
-
- where X is a halogen, preferably chlorine. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups (e.g., CF3, m-(CF3)2—C6H3, etc.). Group R4 may also be selected from halogens, such as F.
-
- where X is a halogen, preferably chlorine. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups (e.g., CF3, m-(CF3)2—C6H3, etc.). Group R4 may also be selected from halogens, such as F.
- As used herein, the formula, [N((SiR1R2R3)R4)]InX2, is represented by the following structure:
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
- Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range. Any and all ranges recited herein are inclusive of their endpoints (i.e., x=1 to 4 or x ranges from 1 to 4 includes x=1, x=4, and x=any number in between), irrespective of whether the term “inclusively” is used.
- Reference herein to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the invention. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term “implementation.”
- As used herein, the term “independently” when used in the context of describing R groups should be understood to denote that the subject R group is not only independently selected relative to other R groups bearing the same or different subscripts or superscripts, but is also independently selected relative to any additional species of that same R group. For example in the formula MR1 x (NR2R3)(4-x), where x is 2 or 3, the two or three R1 groups may, but need not be identical to each other or to R2 or to R3. Further, it should be understood that unless specifically stated otherwise, values of R groups are independent of each other when used in different formulas.
- As used in this application, the word “exemplary” is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete fashion.
- Additionally, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or”. That is, unless specified otherwise, or clear from context, “X employs A or B” is intended to mean any of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, then “X employs A or B” is satisfied under any of the foregoing instances. In addition, the articles “a” and “an” as used in this application and the appended claims should generally be construed to mean “one or more” unless specified otherwise or clear from context to be directed to a singular form.
- “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” is defined herein as necessarily encompassing the more limited transitional terms “consisting essentially of” and “consisting of”; “comprising” may therefore be replaced by “consisting essentially of” or “consisting of” and remain within the expressly defined scope of “comprising”.
- “Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actors in the absence of express language in the claim to the contrary.
- For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements are given the same or analogous reference numbers and wherein:
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- Disclosed are indium (In)-containing film and/or indium-containing alloy film forming compositions comprising In(III)-containing precursors that contain halogens, methods of synthesizing them and methods of using them to deposit the indium-containing films and/or indium-containing alloy film.
- Although some homoleptic indium precursors exist, there is a lack of heteroleptic complexes containing halogens available for use as precursors. The advantage of using heteroleptic compounds is the ability to incorporate organic ligands as well as other reactivity ligands such as halogens that may be beneficial for the desired surface chemistry. InCl3 has been used for deposition, however, InCl3 has very low volatility (boiling point 800° C., I torr vapor pressure at 310° C.) making it difficult to use for most applications. The disclosed In(III)-containing precursors not only include at least one halogen but also include an organic ligand that greatly increases the volatility relative to InCl3 to the point that the vapor pressure of the disclosed In(III)-containing precursors is sufficient for commercially viable vapor phase deposition (e.g.: CVD and ALD) processes. The disclosed In(III)-containing precursors herein are indium(III) containing precursors that will be denoted as In(III)-containing precursors throughout the entire patent application.
- The disclosed In(III)-containing precursors contain one or two halogen ligands. More preferably, the disclosed In(III)-containing precursors contain chlorine with nitrogen based ligands, which are suitable for vapor phase depositions of the indium-containing films and/or indium-containing alloy films.
- The disclosed In(III)-containing precursors include the following categories.
- In the first embodiment, the disclosed In(III)-containing precursors contains 1 or 2 amidinate ligands having the formula:
- or
- wherein X is chosen from chlorine, bromine and iodine, preferably chlorine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C8 alkyl, vinyl or aryl group or —NR7R8 where R7 and R8 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl, or aryl group.
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- In the second embodiment, the disclosed In(III)-containing compounds contains 1 or 2 iminopyrrolidinate ligands having the formula:
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
- Exemplary precursors having the formula
- include:
- R1=tBu, R2═R3=Me, R4═R5=R6═R7═H,
- (tert-butyl-imino-2,2-dimethylpyrrolidinate-N,N′)indium(III) dichloride;
- X═Cl, R1=tBu, R2═R3=Et, R4═R5=R6═R7═H,
- (tert-butyl-imino-2,2-diethylpyrrolidinate-N,N′)indium(III) dichloride; and
- X═Cl, R1=tBu, R2=Et, R3=Me, R4═R5=R5═R7═H,
- (tert-butyl-imino-2-ethyl-2-methylpyrrolidinate-N,N′)indium(III) dichloride.
- Exemplary precursors having the formula
- include:
- X═Cl, R1=iPr, R2═R3=Me, R4═R5=R6═R7═H,
- (bis-(isopropyl-imino-2,2-dimethylpyrrolidinate-N,N′)indium(III)chloride;
- X═Cl, R1=tBu, R2═R3=Me, R4═R5=R6═R7═H,
- bis-(tert-butyl-imino-2,2-dimethylpyrrolidinate-N,N′)indium(III)chloride;
- X═Cl, R1=tBu, R2═R3=Et, R4═R5=R8═R7═H,
- (bis-(tert-butyl-imino-2,2-diethylpyrrolidinate-N,N′)indium(III)chloride; and
- X═Cl, R1=tBu, R2=Et, R3=Me, R4═R5=R8═RT═H,
- (bis-(tert-butyl-imino-2-ethyl-2-methylpyrrolidinate-N,N′)indium(III) chloride.
- When the disclosed Indium (III) precursors have sufficiently small R1, R2 and R3, the structure may exists as a dimer under certain conditions with the formula
- Exemplary precursors having the formula
- include:
- X═Cl, R1═R2═R3=R4═R5=R6═R7═H,
- X═Cl, R1═R2═R3=Me, R4═R5=R6═R7═H,
- X═Cl, R1=Me, R2═R3=R4═R5=R6═R7═H,
- X═Cl, R1=iPr, R2═R3=R4═R5=R6═R7═H,
- In the third embodiment, the disclosed In(III)-containing precursors contains 1 or 2 amido amino alkane ligands having the formula:
-
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2, -
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, -
[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, - or
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. For these In(III) containing precursors, n=1 or 2 will provide either a 5-membered or 6-membered metallacycle, respectively. Groups R6 and R7 are not required to be identical for structures wherein n=2.
- Exemplary precursors having the formula [(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2 include:
- X═Cl, R1═R2═R3 iPr, R4═R5=R6═R7═H, n=1, [(iP2)N—CH2—CH2—N(iPr)]InCl2 (1-isopropylamide-2-diisopropyllaminoethane-N,N′)Indium(III) dichloride);
- X═Cl, R1=tBu, R2═R3=Me, R4═R5=R6═R7═H, n=1, [(Me2)N—CH2—CH2—N(tBu)]InCl2 (1-tert-butylamide-2-dimethylaminoethane-N,N′)Indium(III) dichloride);
- X═Cl, R1=tBu, R2═R3=Me, R4═R5=R6═R7═H, n=2, [(Me2)N—CH2—CH2—CH2—N(tBu)]InCl2 (1-tert-butylamide-3-dimethylaminopropane-N,N′)Indium(III) dichloride); and
- X═Cl, R1=tBu, R2═R3═R4=Me, R5═R6=R7═H, n=1, [(Me2)N—CH2—CH2—CH2—N(tBu)]InCl2 (1-tert-butylamide-2-dimethylaminopropane-N,N′)Indium(III) dichloride).
- Exemplary precursors having the formula [(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX include:
- X═Cl, R1=iPr, R2═R3=Me, R4═R5=R6═R7═H, n=1, [(Me2)N—CH2—CH2—N(iPr)]2InCl (bis-(1-isopropylamide-2-dimethylaminoethane-N,N′)Indium(III) chloride));
- X═Cl, R1═R2═R3=Et, R4═R5=R6═R7═H, n=1, [(Et2)N—CH2—CH2—N(Et)]2InCl (bis-(1-ethylamide-2-diethylaminoethane-N,N′)Indium(III) chloride)):
- X═Cl, R1═R2═R3=Me, R4═R5=R6═R7═H, n=2, [(Me2)N—CH2—CH2—CH2—N(Me)]2InCl (bis-(1-methylamide-2-dimethylaminopropane-N,N′)Indium(III) chloride));
- X═Cl, R1=tBu, R2═R3=Me, R4═R5=R6═R7═H, n=2, [(Me2)N—CH2—CH2—CH2—N(tBu)]2InCl (bis-(1-tert-butylamide-2-dimethylaminopropane-N,N′)Indium(III) chloride)).
- Exemplary precursors having the formula [((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2 include:
- X═Cl, R1=Me, R2═R3═H, R4═R5=R6═R7═H, n=1, [((H2)N—CH2—CH2—N(Me))InCl]2(μ-Cl)2;
- X═Cl, R1═R2═R3=Me, R4═R5=R6═R7═H, n=1, [((Me2)N—CH2—CH2—N(Me))InCl]2(μ-Cl)2; and
- X═Cl, R1═R2═R3=Et, R4═R5=R6═R7═H, n=1, [((Et2)N—CH2—CH2—N(Et))InCl]2(μ-Cl)2.
- In the fourth embodiment, the disclosed In(III)-containing precursors contains 1 or 2 μ-diketiminate ligands with the formula:
- where X is a halogen, preferably chlorine. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups (e.g., CF3, m-(CF3)2—C6H3, etc.). Group R4 may also be selected from halogens, such as F.
-
-
-
-
-
-
-
-
-
-
-
- In the fifth embodiment, the disclosed In(III)-containing precursors contains a silyl amine ligand with the following formula:
-
[N((SiR1R2R3)R4)]InX2 - or
- where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group.
- Exemplary precursors having the formula [N((SiR1R2R3)R4)]InX2 include:
- X═Cl, R1═R2═R3=Me, R4═H, [N((SiMe3)H)]InCl2 (trimethylsilyl)amino)indium(III) dichloride;
- X═Cl, R1═R2═R3=Et, R4═H, [N((SiEt3)H)]InCl2 (triethylsilyl)amino)indium(III) dichloride; and
- X═Cl, R1═R2=Me, R3═H, R4═SiHMe2, [N(SiMe2H)2]InCl2 (bis(dimethylsilyl)amino)indium(III) chloride.
-
-
-
-
-
- The vapor pressure of [(Et)NC(Me)=N(tBu)]In(III)Cl2 is 1 torr at 145° C. The vapor pressure of [(iPr)NCHN(iPr)]In(III)Cl2 is 1 torr at 128° C. The vapor pressure of [(iPr)NC(nBu)N(iPr)]In(III)Cl2 is 1 torr at 155° C. The vapor pressure of [(iPr)NC(Me)N(iPr)]In(III)Cl2 is 1 torr at 127° C. See Table 1.
-
TABLE 1 In(III)-containing precursors DSC Vacuum Temperature In(III) precursor Structure (Endotherms) TGA (1 torr VP) [(Et)N C(Me) N(tBu)]In(III)Cl2 89° C. and 303° C. < 3% residue at 220° C. 145° C. [(iPr)N CH N(iPr)]In(III)Cl2 or [((iPr)N C(H) N(iPr))InCl]2(μ—Cl2) 91° C. and 284° C. < 5% residue at 210° C. 128° C. [(iPr)N C(nBu) N(iPr)]In(III)Cl2 296° C. < 3% residue at 250° C. 155° C. [(iPr)N C(Me) N(iPr)]In(III)Cl2 101° C. and 303° C. < 5% residue at 200° C. 127° C. InCl3 456° C. < 3% residue at 400° C. (310° C.) - The disclosed methods for syntheses of the disclosed In(III)-containing precursors include a salt metathesis reaction as shown in examples that follow. The disclosed In(III)-containing precursors may be synthesized through the salt metathesis reaction by mixing either one or two equivalents of a lithiated ligand with InX3 where X═Cl, Br, I. The reaction is performed by loading a reaction flask with a desired nitrogen ligand in an ethereal solvent and cooling to 0° C. or −78° C. A required alkylithium reagent is added to generate the reactive lithiated species of the ligand. The lithiated ligand is then transferred to a suspension of the desired In(III) halide in an ethereal solvent at −78 or 0° C. The reaction is allowed to stir for 12 hours. The solution is then filtered using Celite as a filtering agent, followed by a removal of solvent in vacuo to isolate the product. In the case of lithiated amidinate ligands (e.g., Li[(R1)NC(R3)N(R2)] the desired starting material is the corresponding carbodiimide [(R1)N═C═N(R2)] and the alkylithium reagent is LiR3.
- The disclosed methods for syntheses of the disclosed In(III)-containing precursors include a ligand exchange reaction of In(III)Cl with the generation of SiR3—X as shown in the example below.
- The disclosed In(III)-containing precursors may be synthesized through the ligand exchange reaction by mixing either one or two equivalents of the silylated ligand with InX3 where X═Cl, Br, I. The reaction is performed by loading a reaction flask with the desired In(III) halide in an ethereal solvent at room temperature. The required silylated nitrogen ligand is added to the reaction at room temperature and allowed to stir for 2 to 12 hours. The solvent in removed in vacuo to isolate the product followed by extraction in a hydrocarbon solvent to remove any remaining Indium(III) halide.
- The disclosed In(III)-containing precursors may have the following features that make them suitable for indium and indium alloy film deposition. In one aspect, the disclosed In(III)-containing precursors have heteroleptic nature and nitrogen ligand scaffolding that render the disclosed In(III)-containing precursors much more volatile than indium trichloride (InCl3) with sufficient vapor pressures at lower temperatures. In another aspect, the presence of the halogen (e.g., chloride) containing ligands in the disclosed In(III)-containing precursors allows for the use of dehalosilylation chemistries to achieve ALD at low temperatures from room temperature to 500° C., preferably 100° C.-400° C. The disclosed In(III)-containing precursors represent a potential new product line in semiconductor industry.
- The disclosed In(III)-containing precursors may have high thermal stability and may be used for forming high-speed, high sensitivity semiconductor layers, e.g. in CMOS systems, 3D NAND Channel or in photodetectors. The disclosed In(III)-containing precursors and the disclosed film forming compositions are suitable to deposit the corresponding element-containing films and its related use for deposition of the corresponding element-containing layers.
- The disclosed In(III) precursors and the disclosed film forming compositions are suitable for forming indium-containing thin films, such as InGaAs, InxOy (x=0.5-1.5, y=0.5-1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, etc. used in electronic fields. The disclosed In(III) precursors and the disclosed film forming compositions are useful for the fabrication of indium tin oxide in displays, solar fuel, high speed electronic (InN), optoelectronic components, high-speed electronics, photovoltaics (InP), infrared detectors, diode laser (InAs), fast transistors, magnetic field, thermal image detectors (InSb), photoelectronic devices, photoelectrochemical water splitting (In2S3), LED applications, the fabrication of copper indium gallium selenide (CIGS) in photovoltaics and optical applications, indium gallium zinc oxide (IGZO) in displays, semiconductors, Logic and memories industries, and the like.
- The disclosure also includes processes for forming an Indium-containing film and methods for forming an oxygenated or oxygen-free indium-containing film using the disclosed In(III) precursors by vapor deposition methods, such as ALD or CVD. The disclosed are a deposition process where the disclosed In(III) precursors are used and introduced into a reaction chamber for deposition a film by ALD, CVD, spin-on, spray, dip coating, slit coating or any other deposition technique to form a film, in combination with or without one or more oxidants (for example O2 and O3, or H2O and O3), or with one or more reductants or nitriding agents (for example H2 and NH3, N2 and NH3, or NH3 and N2H4) introduced simultaneously and/or sequentially. The disclosed deposition processes using the disclosed In(III) precursors may be assisted by heating, light, direct or remote plasma, or combination thereof.
- When the target is a dielectric film, the co-reactant may be an oxidizing gas such as one of O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen containing radicals such as O. or OH., alcohol, silanols, aminoalcohols, carboxylic acids such as formic acid, acetic acid, propionic acid, para-formaldehyde, other oxidizing compounds and mixtures thereof. Preferably, the oxidizing gas is selected from the group consisting of O2, O3, H2O2, and H2O. Preferably, when an ALD process is performed, the co-reactant is plasma treated oxygen, ozone, or combinations thereof. When an oxidizing agent is used as the co-reactant, the resulting In(III)-containing film will also contain oxygen.
- When the target is a conductive film, the co-reactant may be NH3, N2, H2 or N2/H2, amines, diamines, cyanides, di-imines, hydrazines (for example, N2H4, MeHNNH2, MeHNNHMe), organic amines (for example, H2N(CH3), H2N(CH2CH3), H2NC(CH3)3, N(CH3)H2, N(C2H5)H2, N(CH3)2H, N(C2H5)2H, N(CH3)3, N(C2H5)3, (SiMe3)2NH), pyrazoline, pyridine, radical and plasma species, and mixtures thereof. The co-reactant may be a primary amine, a secondary amine, a tertiary amine, trisilylamine, radicals thereof, and mixtures thereof. Preferably, the co-reactant is NH3 or H2. When a N-containing reducing agent is used, the resulting In(III)-containing film will also contain nitrogen.
- When the desired In(III)-containing film also contains another element, for example and without limitation, P, Ga, As, B, Ge, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, Sb, Bi, Sn, Pb, Co, lanthanides (such as Er), or combinations thereof, the co-reactants may include another precursor.
- Furthermore, the co-reactant may be treated by a plasma, in order to decompose the reactant into its radical form, at least one of H2, N2 and O2 may be utilized as a hydrogen, nitrogen or oxygen source gas, respectively, when treated with plasma. The plasma source may be a N2 plasma, N2/He plasma, N2/Ar plasma, NH3 plasma, NH3/He plasma, NH2/Ar plasma, He plasma, Ar plasma, H2 plasma, H2/He plasma, H2/organic amine plasma, and mixtures thereof. For instance, the plasma may be generated with a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W. The plasma may be generated present within the reactor itself. Alternatively, the plasma may generally be at a location removed from the reactor, for instance, in a remotely located plasma system. One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
- For example, the co-reactant may be introduced into a direct plasma reactor, which generates plasma in the reaction chamber, to produce the plasma-treated reactant in the reaction chamber. The co-reactant may be introduced and held in the reaction chamber prior to plasma processing. Alternatively, the plasma processing may occur simultaneously with the introduction of the reactant.
- Alternatively, the plasma-treated co-reactant may be produced outside of the reaction chamber, for example, a remote plasma to treat the co-reactant prior to passage into the reaction chamber.
- Also disclosed are methods for forming indium (III)-containing layers on a substrate using a vapor deposition process. Applicants believe that the disclosed film forming compositions are suitable for ALD. More particularly, the disclosed film forming compositions are capable of surface saturation, self-limited growth per cycle, and perfect step coverage on aspects ratios ranging from approximately 2:1 to approximately 200:1, and preferably from approximately 60:1 to approximately 150:1. Additionally, the disclosed film forming compositions have high decomposition temperatures, indicating good thermal stability to enable ALD. The high decomposition temperatures permit ALD at higher temperatures, resulting in films having higher purity. The disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, flat panel type devices.
- The disclosed In(III)-containing film forming compositions may be used to deposit In(III)-containing films using any deposition methods known to those of skill in the art. Examples of suitable deposition methods include chemical vapor deposition (CVD) or atomic layer deposition (ALD) with or without plasma enhancement. Exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatial isolation ALD, temporal ALD, selective or not ALD, hot-wire ALD (HWALD), radicals incorporated ALD, and combinations thereof. The deposition method is preferably ALD, PE-ALD, or spatial ALD in order to provide suitable step coverage and film thickness control. Exemplary CVD methods include metal-organic CVD (MOCVD), thermal CVD, pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD) or atmospheric pressure CVD (APCVD), hot-wire CVD or hot filament CVD (also known as cat-CVD, in which a hot wire serves as an energy source for the deposition process), hot wall CVD, cold wall CVD, aerosol assisted CVD, direct liquid injection CVD, combustion CVD, hybrid physical-CVD, metalorganic CVD, rapid thermal CVD, photo-initiated CVD, laser CVD, radicals incorporated CVD, plasma enhanced CVD (PECVD) including but not limited to flowable PECVD, and combinations thereof.
- The disclosed In(III)-containing film forming composition contains less than 5% v/v, preferably less than 1% v/v, more preferably less than 0.1% v/v, and even more preferably less than 0.01% v/v of any of its analogs or other reaction products. This embodiment may provide better process repeatability. This embodiment may be produced by purification (e.g., distillation, sublimation, chromatography, etc.) of the In(III)-containing film forming composition.
- Purity of the disclosed film forming composition is greater than 93% w/w (i.e., 95.0% w/w to 100.0% w/w), preferably greater than 98% w/w (i.e., 98.0% w/w to 100.0% w/w), and more preferably greater than 99% w/w (i.e., 99.0% w/w to approximately 99.999% w/w or 99.0% w/w to 100.0% w/w). One of ordinary skill in the art will recognize that the purity may be determined by NMR spectroscopy and gas or liquid chromatography with mass spectrometry. The disclosed film forming compositions may contain any of the following impurities: pyrazoles; pyridines; alkylamines; alkylimines; THF; ether, pentane; cyclohexane; heptanes; benzene; toluene; chlorinated metal compounds; lithium, sodium, potassium pyrazolyl. The total quantity of these impurities is preferably below 5% w/w (i.e., 0.0% w/w to 5.0% w/w), preferably below 2% w/w (i.e., 0.0% w/w to 2.0% w/w), and more preferably below 1% w/w (i.e., 0.0% w/w to 1.0% w/w). The disclosed film forming composition may be purified by recrystallization, sublimation, distillation, and/or passing the gas liquid through a suitable adsorbent, such as 4 Å molecular sieves.
- Purification of the disclosed film forming composition may also result in metal impurities each range independently at the 0 ppbw to 1 ppmw, preferably approximately 0 to approximately 500 ppbw (part per billion weight) level, more preferably from approximately 0 ppbw to approximately 100 ppbw, and even more preferably from approximately 0 ppbw to approximately 10 ppbw. These metal or metalloid impurities include, but are not limited to, Aluminum(Al), Arsenic(As), Barium(Ba), Beryllium(Be), Bismuth(Bi), Cadmium(Cd), Calcium(Ca), Chromium(Cr), Cobalt(Co), Copper(Cu), Gallium(Ga), Germanium (Ge), Hafnium(Hf), Zirconium(Zr), Iron(Fe), Lead(Pb), Lithium(Li), Magnesium(Mg), Manganese(Mn), Tungsten(W), Nickel(Ni), Potassium(K), Sodium(Na), Strontium(Sr), Thorium(Th), Tin(Sn), Titanium(Ti), Uranium(U), Vanadium(V) and Zinc(Zn).
- Care should be taken to prevent exposure of the disclosed In(III)-containing film forming compositions to water as this may result in decomposition of the In(III)-containing precursors to an indium oxide (e.g., In2O3).
- The disclosed film forming compositions may be supplied either in neat form or in a blend with a suitable solvent, such as ethyl benzene, xylene, mesitylene, decalin, decane, dodecane. The disclosed precursors may be present in varying concentrations in the solvent.
- The neat blended film forming compositions are introduced into a reactor in a vapor form by conventional means, such as tubing and/or flow meters. The vapor form may be produced by vaporizing the neat blended composition through a conventional vaporization step such as direct vaporization, distillation, by bubbling, or by using a sublimator, such as the one disclosed in PCT Publication WO2009/087609 to Xu et al. The neat blended composition may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reactor. Alternatively, the neat blended composition may be vaporized by passing a carrier gas into a container containing the composition by bubbling the carrier gas into the composition. The carrier gas may include, but is not limited to, Ar, He, N2, and mixtures thereof. Bubbling with a carrier gas may also remove any dissolved oxygen present in the neat blended composition. The carrier gas and composition are then introduced into the reactor as a vapor,
- If necessary, the container containing the disclosed film forming composition may be heated to a temperature that permits the composition to have a sufficient vapor pressure. The container may be maintained at temperatures in the range of, for example, approximately 0° C. to approximately 200° C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of precursor vaporized.
- The reactor may be any enclosure chamber within a device in which deposition methods take place such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, other types of deposition systems under conditions suitable to cause the compounds to react and form the layers. One of ordinary skill in the art will recognize that any of these reactors may be used for either ALD or CVD deposition processes.
- The reactor contains one more substrates onto which the films will be deposited. A substrate is generally defined as the material on which a process is conducted. The substrates may be any suitable substrate used in semiconductor, photovoltaic, fiat panel, LCD-TFT device manufacturing. Examples of suitable substrates include wafers, such as silicon, silica, glass, GaAs wafers. The wafer may have one more layers of differing materials deposited on it from a previous manufacturing step. For example, the wafers may include a dielectric layer. Furthermore, the wafers may include silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxy nitride layers, carbon doped silicon oxide (SiCOH) layers, metal, metal oxide metal nitride layers (Ti, Ru, Ta, etc.), and combinations thereof. Additionally, the wafers may include copper layers noble metal layers (e.g., platinum, palladium, rhodium, gold). The wafers may include barrier layers, such as manganese, manganese oxide, etc. Plastic layers, such as poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)[PEDOT:PSS] may also be used. The layers may be planar or patterned. The disclosed processes may deposit the layer directly on the wafer or directly on one or more layers on top of the wafer when patterned layers are formed on the substrate. The patterned layers may be alternating layers of two specific layers such as In2O3 and ZrO2 used in 3D NAND. Furthermore, one of ordinary skill in the art will recognize that the terms “film” “layer” used herein refer to a thickness of some material laid on or spread over a surface and that the surface may be a trench a line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as substrates. For example, an indium oxide film may be deposited onto a metal oxide layer, such as a ZrO2 layer, an HfO2 layer, or a MoO2 layer.
- The substrate final application is not limited to the present invention, but this technology may find particular benefits for the following types of substrates: silicon wafers, glass wafers and panels, beads, powders and nano-powders, monolithic porous media, printed circuit board, plastic sheets, etc. Exemplary powder substrates include a powder used in rechargeable battery technology. A non-limiting number of powder materials include NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.
- The temperature and the pressure within the reactor are held at conditions suitable for vapor depositions, such as ALD and CVD. In other words, after introduction of the vaporized disclosed film forming composition into the chamber, conditions within the chamber are such that at least part of the precursor is deposited onto the substrate to form a layer. For instance, the pressure in the reactor or the deposition pressure may be held between about 10−3 torr and about 100 torr, more preferably between about 10−2 torr and 10 torr, as required per the deposition parameters. Likewise, the temperature in the reactor or the deposition temperature may be held between about 100° C. and about 600° C., preferably between about 150° C. and about 500° C. One of ordinary skill in the art will recognize that “at least part of the precursor is deposited” means that some all of the precursor reacts with adheres to the substrate.
- The temperature to achieve optimal film growth may be controlled by either controlling the temperature of the substrate holder. Devices used to heat the substrate are known in the art. The substrate is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition. A non-limiting exemplary temperature range to which the substrate may be heated includes from approximately 50° C. to approximately 600° C. When a plasma deposition process is utilized, the deposition temperature is preferably less than 400° C. Alternatively, when a thermal process is performed, the deposition temperature may range from approximately 100° C. to approximately 600° C.
- Alternatively, the substrate may be heated to a sufficient temperature to obtain the desired In(III)-containing film at a sufficient growth rate and with desired physical state and composition. A non-limiting exemplary temperature range to which the substrate may be heated includes from room temperature to approximately 600° C. Preferably, the temperature of the substrate remains less than or equal to 500° C.
- The ALD conditions within the chamber allow the disclosed film forming composition adsorbed or chemisorbed on the substrate surface to react and form a film on the substrate. In some embodiments, Applicants believe that plasma-treating the co-reactant may provide the co-reactant with the energy needed to react with the disclosed film forming composition. When the co-reactant in this exemplary ALD process is treated with a plasma, the exemplary ALD process becomes an exemplary PEALD process. The co-reactant may be treated with plasma prior subsequent to introduction into the chamber.
- The film forming composition and co-reactants may be introduced into the reactor sequentially (ALD). The reactor may be purged with an inert gas between the introduction of each of the film forming composition, any additional precursors, and the co-reactants. Another example is to introduce the co-reactant continuously and to introduce the film forming composition by pulse, while activating the co-reactant sequentially with a plasma, provided that the film forming composition and the non-activated co-reactant do not substantially react at the chamber temperature and pressure conditions (CW PEALD).
- Each pulse of the disclosed film forming composition may last for a time period ranging from about 0.001 seconds to about 120 seconds, alternatively from about 1 seconds to about 80 seconds, alternatively from about 5 seconds to about 30 seconds. The co-reactant may also be pulsed into the reactor, In such embodiments, the pulse of each may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 30 seconds, alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized film forming compositions and co-reactants may be simultaneously sprayed from different sectors of a shower head (without mixing of the composition and the reactant) under which a susceptor holding several wafers is spun (spatial ALD).
- Depending on the particular process parameters, deposition may take place for a varying length of time. Generally, deposition may be allowed to continue as long as desired necessary to produce a film with the necessary properties. Typical film thicknesses may vary from several angstroms to several hundreds of microns, and typically from 1 to 100 nm, depending on the specific deposition process. The deposition process may also be performed as many times as necessary to obtain the desired film.
- The disclosed methods for forming an In(III)-containing layer on a substrate include: placing a substrate in a reactor, delivering into the reactor a vapor of the disclosed In(III)-containing film forming composition, and contacting/adsorbing the vapor with the substrate (and typically directing the vapor to the substrate) to form an In(III)-containing layer on the surface of the substrate. Alternatively, the disclosed methods for forming an In(III)-containing layer on a substrate include: exposing the substrate to the vapor of the disclosed In(III)-containing film forming composition, and depositing an In(III)-containing layer on the surface of the substrate.
- The vapor of the In(III)-containing film forming composition is generated and then introduced into a reaction chamber containing a substrate. The temperature and the pressure in the reaction chamber and the temperature of the substrate are held at conditions suitable for vapor deposition of at least part of the disclosed In(III)-containing precursor onto the substrate. In other words, after introduction of the vaporized composition into the reaction chamber, conditions within the reaction chamber are adjusted such that at least part of the precursor is deposited onto the substrate to form the In(III)-containing layer. One of ordinary skill in the art will recognize that “at least part of the precursor is deposited” means that some or all of the precursor reacts with or adheres to the substrate. Herein, a co-reactant may also be used to help in formation of the In(III)-containing layer.
- The disclosed film forming compositions and co-reactants may be introduced into the reactor either simultaneously (CVD), sequentially (ALD) or different combinations thereof. The reactor may be purged with an inert gas (e.g., N2 or Ar) between the introduction of the film forming composition and the introduction of the co-reactant. Alternatively, the co-reactant and the film forming composition may be mixed together to form a co-reactant/compound mixture, and then introduced to the reactor in a mixture form. Another example is to introduce the co-reactant continuously and to introduce the disclosed film forming composition by pulse (pulsed CVD).
- In a non-limiting exemplary ALD process of forming an indium-containing film containing two elements, such as In2O3, InN, InS, etc., the vapor phase of the disclosed film forming composition, such as, [(Et)NC(Me)N(tBu)]In(III)Cl2, is introduced into the reactor, where it is contacted with a suitable substrate, either chemisorbed or physisorbed thereon. Excess composition may then be removed from the reactor by purging and/or evacuating the reactor, that is, either by purging a reactor with an inert gas (e.g., N2, Ar, Kr or Xe), or passing the substrate in a sector under high vacuum and/or a carrier gas curtain. A co-reactant (e.g., O3 or NH3) is introduced into the reactor where it reacts with the adsorbed film forming composition in a self-limiting manner. Any excess co-reactant is removed from the reactor by purging and/or evacuating the reactor. If the desired film is an oxide, such as In2O3, this two-step process may provide the desired film thickness by repeating until a film having the desired thickness has been obtained. By alternating the provision of the indium film forming composition and co-reactant, a film of desired composition and thickness can be deposited.
- Alternatively, if the desired indium-containing film contains three elements, such as InGaN, the two-step process above (for example, forming InN film) may be inserted by introduction of the vapor of an additional precursor compound into the reactor (three-step process). The additional precursor compound will be selected based on the nature of the film being deposited. The additional elements may include gallium (Ga), nitrogen (N), sulfur (S), phosphorous (P), Tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof. When the additional precursor compound is utilized, the resultant film deposited on the substrate contains indium and co-reactant in combination with the additional element. When the additional precursor and the In(III) precursor are used in more than one ALD super cycle sequences, a nanolaminate film is obtained. After introduction into the reactor, the additional precursor compound is contacted or adsorbed with the substrate. Afterward, any excess precursor compound is removed from the reactor by purging and/or evacuating the reactor. Depending on process requirements, a co-reactant, such as NH3, or an additional precursor may be introduced into the reactor to react with the indium precursor compound. Excess co-reactant or precursor is removed from the reactor by purging and/or evacuating the reactor. In the final steps of the cycle, the remaining co-reactant or precursor may be introduced into the reactor and removal of excess is removed by purging and/or evacuation of the reactor. The entire three-step process may be repeated until a desired film thickness has been achieved. By alternating the provision of the indium film forming composition, additional precursor compound, and co-reactant, a film of desired composition and thickness can be deposited.
- Alternatively, if the desired indium-containing film contains four elements such as InGaZnO (IGZO), the three-step process above may be inserted by introduction of the vapor of another additional precursor compound into the reactor (four-step process). The other additional precursor compound will be selected based on the nature of the film being deposited. The additional elements may include gallium (Ga), nitrogen (N), sulfur (S), phosphorous (P), tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof. When another additional precursor compound is utilized, the resultant film deposited on the substrate contains indium in combination with the additional three elements. When the additional two precursors and the In(III) precursor are used in more than one ALD super cycle sequences, a nanolaminate film is obtained. In case of forming IGZO films the precursors may include an indium precursor such as [(iPr)NCHN(iPr)]In(III)Cl2, a Ga precursor such as GaCl3 or Ga(NO3)3, a Zn precursor such as Zn(NO3)2 in combination with a co-reactant O3. By alternating the provision of the indium film forming composition, additional precursor compound, another additional precursor and co-reactant, a film of desired composition and thickness can be deposited.
- The indium-containing films resulting from the processes discussed above may include InxOy (x=0.5 to 1.5, y=0.5 to 1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, or combination thereof or a pure indium (In(0)) layer. The Indium-containing films may contain a second element selected from P, N, S, Ga, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, Zn, one or more lanthanides, or combinations thereof. One of ordinary skill in the art will recognize that by appropriate selection of the film forming composition and co-reactants, the desired film composition may be obtained. The disclosed methods may be useful in the manufacture of a semiconductor material, for example, indium oxide can serve as a semiconductor material, forming heterojunctions with p-InP, n-GaAs, n-Si, and other materials. Thin films of indium oxide can be used as diffusion barriers (“barrier metals”) in semiconductors (e.g., to inhibit diffusion between aluminum and silicon).
- Upon obtaining a desired film thickness, the film may be subject to further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV e-beam curing, and/or plasma gas exposure. Those skilled in the art recognize the systems and methods utilized to perform these additional processing steps. For example, the In2O3 film may be exposed to a temperature ranging from approximately 200° C. and approximately 100° C. for a time ranging from approximately 0.1 second to approximately 7200 seconds under an inert atmosphere, an 0-containing atmosphere, and combinations thereof. Most preferably, the temperature range is 350° C. to 450° C. for 3600-7200 seconds under an inert atmosphere or an 0-containing atmosphere. The resulting film may contain fewer impurities and therefore may have an improved density resulting in improved leakage current. The annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber, with the annealing/flash annealing process being performed in a separate apparatus. Any of the above post-treatment methods, but especially thermal annealing, has been found effective to reduce carbon and nitrogen contamination of the In2O3 film. This in turn tends to improve the resistivity of the film.
- After annealing, the films deposited by any of the disclosed processes may have a bulk resistivity at room temperature of approximately 50 μohm·cm to approximately 1,000 μohm·cm. Room temperature is approximately 20° C. to approximately 25° C. depending on the season. Bulk resistivity is also known as volume resistivity. One of ordinary skill in the art will recognize that the bulk resistivity is measured at room temperature on the films that are typically approximately 50 nm thick. The bulk resistivity typically increases for thinner films due to changes in the electron transport mechanism. The bulk resistivity also increases at higher temperatures.
- The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the inventions described herein.
-
- In a Schlenk flask under nitrogen fitted with an addition funnel, 1-tert-butyl-3-ethylcarbodiimide (0.95 equiv, 0.038 mol, 4.79 gram) was dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to −78° C. Methyllithium (1.6 M, 0.97 equiv, 0.039 mol, 24.3 mL) in diethyl ether was added to the flask slowly. The mixture was allowed to stir for two hours and warmed to room temperature with stirring. In a separate Schleck flask a suspension of indium (III) chloride (1.0 equiv, 0.040 mol, 8.87 g) in an ethereal solvent (200 mL), preferably dimethoxyethane, was cooled to −78° C. The lithium solution was slowly added to the suspension, and the reaction was allowed to warm to room temperature and was stirred for 12 hours. At which time the solvent was removed under reduced vacuum followed by the addition of 250 mL of pentane. The reaction was filtered through Celite, and the volume was reduced under vacuum. The remaining solution was cooled, and the desired product crystalized out of solution at −20° C. The product [(Et)NC(Me)N(tBu)]In(III)Cl2 was isolated (5.84 gram, 45% yield) as a white solid which melted at 88° C. 1H-NMR (benzene-d6, δ(ppm): 0.94 (3H, t, 7.2 Hz), 1.30 (9H, s), 1.57 (3H, s), 3.29 (2H, q, 7.0 Hz). The vacuum TGA results for [(Et)NC(Me)N(tBu)]In(III)Cl2 is shown in
FIG. 1 , which shows single step evaporation with <3% residue remaining at 220° C. for [(Et)NC(Me)N(tBu)]In(III)Cl2. For a comparison purpose, the vacuum TGA result for InCl3 is also added. As shown, volatility of [(Et)NC(Me)N(tBu)]In(III)Cl2 precursor increases relative to that of InCl3. The DSC results for [(Et)NC(Me)N(tBu)]In(III)Cl2 is shown inFIG. 2 . [(Et)NC(Me)N(tBu)]In(III)Cl2 has a vapor pressure of 1 torr at 145° C.FIG. 3 is 1H NMR of [(Et)NC(Me)N(tBu)]In(III)Cl2 in C6D6. -
- The same procedure was followed for Example 1. Reagents used were N,N′-bis(1-methylethyl)methanimidamide (0.95 equiv, 0.039 mol, 5.00 g) methyllithium (0.97 equiv, 0.040 mol, 24.9 ml) and indium (III) chloride (1.0 equiv. 0.041 mol, 9.09 g). The product was isolated (6.10 g, 50% yield) as a white solid which melted at 91° C. 1H-NMR (THF-d8, δ (ppm)): 1.16 (12H, d, 6.5 Hz), 3.57 (2H, spt, 6.5 Hz), 7.69 (1H, s). The TGA results for [(iPr)NCHN(iPr)]In(III)Cl2 is shown in
FIG. 4 , which shows single step evaporation with <5% residue remaining at 210° C. for [(iPr)NCHN(iPr)]In(III)Cl2. For a comparison purpose, the vacuum TGA result for InCl3 is also added. As shown, volatility of [(iPr)NCHN(iPr)]In(III)Cl2 precursor increases relative to that of InCl3. Depending on the identity of the solvent used for acquiring 1H NMR spectra, the structure was observed as either the monomer ([(iPr)NCHN(iPr)]In(III)Cl2) or dimer ([((iPr)NC(H)N(iPr))InCl]2(μ-Cl)2). The DSC results for [(iPr)NCHN(iPr)]In(III)Cl2 is shown inFIG. 5 . [(iPr)NCHN(iPr)]In(III)Cl2 has a vapor pressure of 1 torr at 128° C.FIG. 6 is 1H NMR of [(iPr)NCHN(iPr)]In(III)Cl2 in THF-d8. -
- The same procedure was followed for Example 1. Reagents used were N,N′-diisopropylcarbodiimide (0.95 equiv, 0.046 mol, 5.75 g), n-butyllithium (0.97 equiv, 0.047 mol, 29.1 ml) and indium (III) chloride (1.0 equiv. 0.048 mol, 10.64 g). The precursor [(iPr)NC(nBu)N(iPr)]In(III)Cl2 was isolated as a viscous liquid (12.91 g, 73% yield). 1H-NMR (benzene-d6, δ(ppm): 0.80 (3H, t, 7.3 Hz), 1.19 (2H, m), 1.27 (12H, d, 6.5 Hz), 1.33 (2H, m), 1.35 (2H, m), 2.05 (2H, m), 3.60 (2H, quint, 6.2 Hz). The TGA results for [(iPr)NC(nBu)N(iPr)]In(III)Cl2 is shown in
FIG. 7 , which shows single step evaporation with <3% residue remaining at 250° C. for [(iPr)NC(nBu)N(iPr)]In(III)Cl2. For a comparison purpose, the vacuum TGA result for InCl3 is also added. As shown, volatility of [(iPr)NC(nBu)N(iPr)]In(III)Cl2 precursor increases relative to that of InCl3. The DSC results for [(iPr)NC(nBu)N(iPr)]In(III)Cl2 is shown inFIG. 8 . [(iPr)NC(nBu)N(iPr)]In(III)Cl2 has a vapor pressure of 1 torr at 155° C.FIG. 9 is 1H NMR of [(iPr)NC(nBu)N(iPr)]In(III)Cl2 in C6D6. -
- The same procedure was followed for Example 1. Reagents used were 1-tert-butyl-3-ethylcarbodiimide (0.95 equiv, 0.048 mol, 5.99 g), n-butyllithium (0.97 equiv, 0.049 mol, 30.3 ml) and indium (III) chloride (1.0 equiv. 0.05 mol, 11.09 g). The precursor [(Et)NC(nBu)N(tBu)]In(III)Cl2 was isolated as a viscous liquid (12.18 g, 66% yield). 1H-NMR (benzene-d6, δ(ppm): 0.77 (3H, t, 7.3 Hz), 1.10 (3H, t, 7.2 Hz), 1.16 (2H, m), 1.30 (2H, m), 1.38 (9H, s), 2.17 (2H, m), 3.11 (2H, q, 7.0 Hz). The TGA results for [(Et)NC(nBu)N(tBu)]In(III)Cl2 is shown in
FIG. 10 , which shows single step evaporation with <8% residue remaining at 240° C. for [(Et)N(nBu)N(tBu)]In(III)Cl2. For a comparison purpose, the vacuum TGA result for InCl3 is also added. As shown, volatility of [(Et)NC(nBu)N(tBu)]In(III)-Cl2 precursor increases relative to that of InCl3.FIG. 11 is 1H NMR of [(Et)NC(nBu)N(tBu)]In(III)Cl2 in C6D6. -
- The same procedure was followed for Example 1. Reagents used were diisopropylcarbodiimide (0.95 equiv, 0.14 mol, 22.7 mL) methyllithium (0.97 equiv, 0.15 mol, 90.9 ml) and indium (III) chloride (1.0 equiv. 0.15 mol, 33.3 g). The product was isolated (25.1 g, 51% yield) as a white solid which melted at 110° C. 1H-NMR (benzene-d6, δ(ppm): 1.20 (13H, d, 6.5 Hz), 1.41 (3H, s), 3.46 (2H, spt, 6.5 Hz). The TGA results for [(iPr)NC(Me)N(iPr)]In(III)Cl2 is shown in
FIG. 12 , which shows single step evaporation with <5% residue remaining at 200° C. for [(iPr)NC(Me)N(iPr)]In(III)Cl2. For a comparison purpose, the vacuum TGA result for InCl3 is also added. As shown, volatility of [(iPr)NC(Me)N(iPr)]In(III)Cl2 precursor increases relative to that of InCl3. -
- In a Schlenk flask under nitrogen, N,N′-diisopropyl-N-(trimethylsilyl)acetimidamide (1.4 equiv, 0.31 mol, 66 grams) was dissolved in an ethereal solvent (500 mL), preferably tetrahydrofuran. In a separate Schlenk flask under nitrogen, indium (III) chloride (1.0 equiv, 0.22 mol, 48.8 grams) was dissolved in an ethereal solvent (250 mL), preferably tetrahydrofuran. With stirring, the, N,N′-diisopropyl-N-(trimethylsilyl)acetimidamide mixture was slowly added to the indium halide, and allowed to stir at room temperature for 12 hours. At which time the solvent was removed under reduced vacuum to isolate the crude product. A soxhlet extraction was performed with 800 mL of pentane to isolate the desired product from trace remaining indium (III) chloride. Upon removal of the solvent, [(iPr)NC(Me)N(iPr)]In(III)Cl2 was isolated as a white solid (56.3 grams, 83% yield). Using the ligand exchange route greatly improved the yield of [(iPr)NC(Me)N(iPr)]In(III)Cl2.
FIG. 13 is 1H NMR of [(iPr)NC(Me)N(iPr)]In(III)Cl2 in CD6. -
- In a Schlenk flask under nitrogen fitted with an addition funnel, 1-tert-butyl-3-ethylcarbodiimide (2.0 equiv, 0.08 mol, 10.10 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to −78° C. Methyllithium (2.0 equiv, 0.08 mol, 50 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring. In a separate Schleck flask a suspension of indium (III) chloride (1.0 equiv, 0.040 mol, 8.87 g) in an ethereal solvent (200 mL), preferably dimethoxyethane, is cooled to −78° C. The lithium solution is slowly added to the suspension, and the reaction is allowed to warm to room temperature and is stirred for 12 hours. At which time the solvent is removed under reduced vacuum followed by the addition of 250 mL of pentane. The reaction can be filtered through Celite. Following the removal of solvent [(Et)NC(Me)N(tBu)]2InCl can be further purified by crystallization or sublimation for solid materials or distillation for liquid materials.
-
- In a Schlenk flask under nitrogen fitted with an addition funnel, isopropyl-imino-2,2-dimethylpyrrolidine (1.0 equiv, 0.040 mol, 6.17 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to −78° C. Methyllithium (1.0 equiv, 0.040 mol, 25 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring. In a separate Schleck flask a suspension of indium (III) chloride (1.0 equiv, 0.040 mol, 8.87 g) in an ethereal solvent (200 mL) is cooled to −78° C. The lithium solution is slowly added to the suspension, and the reaction is allowed to warm to room temperature and stirred for 12 hours. At which time the solvent is removed under reduced vacuum followed by the addition of 250 mL of pentane. The reaction is filtered through Celite. Following the removal of solvent,
- can be further purified by crystallization or sublimation for solid materials or distillation for liquid materials.
-
- In a Schlenk flask under nitrogen fitted with an addition funnel, isopropyl-imino-2,2-dimethylpyrrolidine (2.0 equiv, 0.080 mol, 12.34 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to −78° C. Methyllithium (2.0 equiv, 0.080 mol, 50 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring. In a separate Schleck flask a suspension of indium (III) chloride (1.0 equiv, 0.040 mol, 8.87 g) in an ethereal solvent (200 mL) is cooled to −78° C. The lithium solution is slowly added to the suspension, and the reaction is allowed to warm to room temperature and stirred for 12 hours. At which time the solvent is removed under reduced vacuum followed by the addition of 250 mL of pentane. The reaction is filtered through Celite. Following the removal of solvent,
- can be further purified by crystallization or sublimation for solid materials or distillation for liquid materials.
-
- In a Schlenk flask under nitrogen fitted with an addition funnel, N,N,N′-triethylethylenediamine (1.0 equiv, 0.040 mol, 5.77 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to −78° C. Methyllithium (1.0 equiv, 0.040 mol, 25 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring. In a separate Schleck flask a suspension of indium (III) chloride (1.0 equiv, 0.040 mol, 8.87 g) in an ethereal solvent (200 mL) is cooled to −78° C. The lithium solution is slowly added to the suspension, and the reaction is allowed to warm to room temperature and stirred for 12 hours. At which time the solvent is removed under reduced vacuum followed by the addition of 250 mL of pentane. The reaction is filtered through Celite. Following the removal of solvent, [(Et2)N—CH2—CH2—N(Et)]InCl2 can be further purified by crystallization or sublimation for solid materials or distillation for liquid materials.
-
- In a Schlenk flask under nitrogen fitted with an addition funnel, N,N,N′-triethylethylenediamine (1.0 equiv, 0.080 mol, 11.54 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to −78° C. Methyllithium (1.0 equiv, 0.080 mol, 50 mL) 1.6 M in diethyl ether is added to the flask slowly. The mixture is allowed to stir for two hours and warmed to room temperature with stirring. In a separate Schleck flask a suspension of indium (III) chloride (1.0 equiv, 0.040 mol, 8.87 g) in an ethereal solvent (200 mL) is cooled to −78° C. The lithium solution is slowly added to the suspension, and the reaction is allowed to warm to room temperature and stirred for 12 hours. At which time the solvent is removed under reduced vacuum followed by the addition of 250 mL of pentane. The reaction is filtered through Celite. Following the removal of solvent, [(Et2)N—CH2—CH2—N(Et)]InCl2 can be further purified by crystallization or sublimation for solid materials or distillation for liquid materials.
- In2O3 ALD was performed using alternating exposures of [(iPr)NC(nBu)N(iPr)]In(III)Cl2 and O3 in an ALD reactor. N2 carrier gas is used to transport the vapor of [(iPr)NC(nBu)N(iPr)]In(III)Cl2 into the ALD reactor. The ALD sequences are expressed the exposure for the precursor [(iPr)NC(nBu)N(iPr)]In(III)Cl2, the purge following the precursor exposure, afterward, the exposure of the co-reactant O3, and then the purge following the exposure to 0. In2O3 ALD films may be deposited on 2 cm by 2 cm Si(100) and glass substrates. The deposition temperature may be 250° C. in 1 torr. SEM images are acquired of the resulting In2O3 film. An energy dispersive analysis of X-rays (EDAX) detector is used to acquire elemental analysis. AFM, XRD and ellipsometric measurements of the resulting In2O3 films deposited on Si(100) surfaces are performed. Other various characterization techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy dispersive analysis by X-rays (EDAX), Rutherford back-scattering analysis (RBS), and X-ray analyses are used to help understand the fundamental mechanism of the resulting In2O3 film.
- [(iPr)NC(Me)N(iPr)]In(III)Cl2 and P(SiMe3)3 are used as the In and P sources, respectively. The film deposition occurs using N2 as the carrier gas for precursor delivery. A purge step of sufficient duration occurs after each precursor is dosed into the thermal ALD reactor. The cycle is initiated by dosing the [(iPr)NC(Me)N(iPr)]In(III)Cl2 precursor into the reactor. P(SiMe3)3 is then introduced into the reactor to close the cycle. By transporting the precursors to the substrate, the precursors are adsorbed on the substrate surface. The reactive species thus diffuse at the surface to preferential sites and react in a heterogeneous phase to give rise to the formation of the InP film. The deposition may require no catalyst and may be carried out on a variety of substrates, such as thin Si or oxide substrates. The substrate temperature is maintained at approximately 150° C. The resulting InP films can then undergo further processing, such as a thermal annealing step. The InP films are characterized by various techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy dispersive analysis by X-rays (EDAX), Rutherford back-scattering analysis (RBS), and X-ray analyses, etc., which are used to help understand the fundamental mechanism of the ALD growth.
- [(iPr)NC(Me)N(iPr)]In(III)Cl2, GaCl3 and As(SiMe3)3 are used as the In, Ga and As sources, respectively. The film deposition occurs using an ACBC-type supercycle in which N2 is used as the carrier gas for precursor delivery. A purge step of sufficient duration occurs after each precursor is dosed into the thermal ALD reactor. The cycle is initiated by dosing the [(iPr)NC(Me)N(iPr)]In(III)Cl2 precursor into the reactor. As(SiMe3)3 is introduced into the reactor. GaCl3 is then dosed into the chamber. A final dose of As(SiMe3)3 closes the cycle. By transporting the precursors to the substrate, the precursors are adsorbed on the substrate surface. The reactive species thus diffuse at the surface to preferential sites and react in a heterogeneous phase to give rise to the formation of the InGaAs film. Such a cycle can be used to provide films with compositions of In0.5Ga0.5As1. The steps of thermal ALD of InGaAs can also be adjusted to provide films of varying compositions. The deposition may require no catalyst and may be carried out on a variety of substrates, such as thin Si or oxide substrates. The substrate temperature is maintained at approximately 150° C. The resulting InGaAs films can then undergo further processing, such as a thermal annealing step. The InGaAs films are characterized by various techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy dispersive analysis by X-rays (EDAX), Rutherford back-scattering analysis (RBS), and X-ray analyses, etc., which are used to help understand the fundamental mechanism of the ALD growth.
- Although the subject matter described herein may be described in the context of illustrative implementations to process one or more computing application features/operations for a computing application having user-interactive components the subject matter is not limited to these particular embodiments. Rather, the techniques described herein can be applied to any suitable type of user-interactive component execution management methods, systems, platforms, and/or apparatus.
- It will be understood that many additional changes in the details, materials, steps, and arrangement of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above and/or the attached drawings.
Claims (20)
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2,
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or
[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c)
[N((SiR1R2R3)R4)]InX2 (e)
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2,
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or
[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c)
[N((SiR1R2R3)R4)]InX2 (e)
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2,
[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or
[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c)
[N((SiR1R2R3)R4)]InX2 (e)
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KR101221861B1 (en) * | 2012-03-26 | 2013-01-14 | 솔브레인 주식회사 | Metal precursor and metal containing thin film prepared using same |
US9831446B2 (en) * | 2012-10-09 | 2017-11-28 | Merck Patent Gmbh | Metal complexes |
TW201715070A (en) * | 2015-08-03 | 2017-05-01 | 韋恩州立大學 | 6-membered cyclic dienes as strongly reducing precursors for the growth of element films by vapor phase deposition |
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US20230357281A1 (en) | 2023-11-09 |
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KR20230074580A (en) | 2023-05-30 |
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