TWI826713B - 含錫之薄膜之製造方法 - Google Patents
含錫之薄膜之製造方法 Download PDFInfo
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- TWI826713B TWI826713B TW109126411A TW109126411A TWI826713B TW I826713 B TWI826713 B TW I826713B TW 109126411 A TW109126411 A TW 109126411A TW 109126411 A TW109126411 A TW 109126411A TW I826713 B TWI826713 B TW I826713B
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- Prior art keywords
- tin
- bis
- raw material
- vapor deposition
- chemical vapor
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010409 thin film Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 49
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 41
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 31
- 238000001704 evaporation Methods 0.000 claims description 26
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 24
- 230000008020 evaporation Effects 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 abstract description 21
- 150000003606 tin compounds Chemical class 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011135 tin Substances 0.000 description 113
- 229910052718 tin Inorganic materials 0.000 description 100
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 21
- 239000002243 precursor Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 229910001887 tin oxide Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- -1 tetramethylcyclopentadiene (tin) Chemical compound 0.000 description 8
- BWJJQXMKCVYCDM-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Sn]C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Sn]C1(C=CC=C1)CC BWJJQXMKCVYCDM-UHFFFAOYSA-N 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 150000002926 oxygen Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RXKSLZOQGTWCSL-UHFFFAOYSA-N 1-(dimethylamino)-2-methylpropan-2-olate tin(2+) Chemical compound CN(CC(C)(O[Sn]OC(CN(C)C)(C)C)C)C RXKSLZOQGTWCSL-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- XTYRIICDYQTTTC-UHFFFAOYSA-N 1-(dimethylamino)-2-methylpropan-2-ol Chemical compound CN(C)CC(C)(C)O XTYRIICDYQTTTC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- WLNIUEYAQZRJFS-UHFFFAOYSA-N bis[bis(trimethylsilyl)amino]tin Chemical compound C[Si](C)(C)N([Si](C)(C)C)[Sn]N([Si](C)(C)C)[Si](C)(C)C WLNIUEYAQZRJFS-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 208000037998 chronic venous disease Diseases 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—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
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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Abstract
本發明提供一種以雙(乙基環戊二烯)錫為代表之即便於低溫仍具有高蒸氣壓的雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫、以這些有機錫化合物為主成分之化學蒸鍍用原料、以及使用該化學蒸鍍用原料之原子層沉積法所進行的含錫之薄膜之製造方法。化學蒸鍍用原料係含有以下述式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫作為主成分。
(式(1)中，R1及R2係分別獨立表示氫或碳數6以下之烷基，R3及R4係分別獨立表示碳數6以下之烷基。)
Description
本發明係關於一種能夠作為錫薄膜及錫氧化物薄膜之化學蒸鍍之前驅物的雙(乙基環戊二烯)錫、含有以雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫為主成分之化學蒸鍍用原料、及含錫之薄膜之製造方法。
透明導電膜係因具有高導電性及在可見光區域之高光穿透性，而作為太陽能電池、平板顯示器及觸控螢幕等含感光元件之各種光電轉換元件之電極受到使用。再者，由於透明導電膜在近紅外線區域中具有優異反射吸收特性，故而亦作為熱射線反射膜、透明加熱器、透明電磁波遮蔽件及抗靜電膜等而受到利用。
作為如此般之透明導電膜的材料一般而言係使用含有銻及氟等作為摻雜物之氧化錫(IV)(SnO2)、含有鋁、鎵、銦及錫等作為摻雜物之氧化鋅(ZnO)、以及含有錫、鎢及鈦等作為摻雜物之氧化銦(III)(In2O3)等。特別是含有錫作為摻雜物之氧化銦(ITO(Indium Tin Oxide))膜由於容易獲得低電阻之透明導電膜，故而在工業上受到廣泛使用。
如此般之氧化物透明導電膜的製造係使用濺鍍法、化學蒸鍍法及離子鍍覆法等。於這些方法中，例如具有像是氧化錫或氧化鋅般蒸氣壓相對較高的前驅物之金屬氧化物的薄膜係藉由原子層沉積法(ALD(Atomic Layer Deposition)法)等的化學蒸鍍法(CVD(Chemical Vapor Deposition)法)而輕易形成。
一般而言作為錫前驅物而受到廣泛使用的是作為4價之錫化合物的四烷基錫。除了四烷基錫之外，專利文獻1還揭露例如以2價之錫配位化合物、胺基烷氧化錫配位化合物來作為錫及錫氧化物薄膜用之前驅物。前述胺基烷氧化錫配位化合物中，係藉由使得二烷基胺基作為新配位基來配位至錫上，便不會產生碳或鹵素之汚染，不僅改善熱穩定性及揮發性，即便在更低之溫度仍能夠輕易形成錫及錫氧化物之薄膜。
再者，專利文獻2揭露作為錫及錫氧化物薄膜用之前驅物之雙(二異丙胺基)二甲基錫(Sn(N(iPR)2)2Me2)。進而，非專利文獻1中係使用2價之錫配位化合物之N,N’-三級丁基-1,1-二甲基乙二胺錫。
[專利文獻1]日本特開2009-227674號公報。
[專利文獻2]日本特開2018-90586號公報。
[非專利文獻1]Jung-Hoon Lee, Mi Yoo, DongHee Kang, Hyun-Mo Lee, Wan-ho Choi, Jung Woo Park, Yeonjin Yi, Hyun You Kim, and Jin-Seong Park, ACS Applied Materials & Interfaces 10(39), 33335-33342 (2018)。
然而，專利文獻1之胺基烷氧化錫配位化合物中，錫原子與配位基之Sn-O或Sn-N間的鍵結較強。再者，前述胺基烷氧化錫配位化合物之蒸氣壓在100℃至120℃為10-2torr(1.3Pa)，故而為了使用化學蒸鍍法來形成大面積之錫及錫氧化物薄膜，在程序的效率化之方面而言希望要更加提高蒸氣壓，以提高反應性。
再者，專利文獻2之錫配位化合物在80℃具有0.6torr(79.9Pa)之較高的蒸氣壓，但由於錫為4價，故而難以進行氧化錫(II)之成膜。由於受到廣泛使用之四烷基錫亦為4價，故而同樣地難以進行氧化錫(II)之成膜。進而，非專利文獻1之錫配位化合物之蒸氣壓在75℃為0.2torr(26.6Pa)，但該配位化合物亦與專利文獻1同樣地在錫原子與配位基之Sn-N間的鍵結較強。
本發明之目的在於提供一種雙(乙基環戊二烯)錫，在室溫為液體且具有高蒸氣壓，作為錫薄膜或錫氧化物薄膜之前驅物。
再者，本發明之目的在於提供一種即便於低溫仍具有高蒸氣壓之作為錫薄膜或錫氧化物薄膜之前驅物的雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫、以這些前驅物為主成分之化學蒸鍍用原料、以及使用該化學蒸鍍用原料之ALD法所進行的含錫之薄膜之製造方法。
本發明係含有下述事項。
本發明之雙(乙基環戊二烯)錫係以化學式Sn[C5H4(C2H5)]2所表示之化合物。
本發明之化學蒸鍍用原料係含有以下述式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫為主成分。
式(1)中，R1及R2係分別獨立表示氫或碳數6以下之烷基，R3及R4係分別獨立表示碳數6以下之烷基。
前述化學蒸鍍用原料中，式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫之含量以接近100wt%為佳。具體而言，雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫之含量較佳為在化學蒸鍍用原料中為95wt%至100wt%，更佳為99wt%至100wt%。其中，亦可於不影響本發明目的之範圍內含有在進行化學蒸鍍時讓原料氣化之溫度中不會與雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫進行反應之物質。前述化學蒸鍍用原料較佳為在23℃為液體。
具備前述構成之本發明之化學蒸鍍用原料由於具有高蒸氣壓，故而能夠適合用於使用CVD或ALD所進行之薄膜形成。
本發明之含錫之薄膜之製造方法係使用含有以前述式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫為主成分之化學蒸鍍用原料，而藉由ALD法來加以形成。
本發明之氧化錫(II)薄膜之製造方法係使用含有以前述式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫為主成分之化學蒸鍍用原料，而藉由ALD法來加以形成。
本發明之雙(乙基環戊二烯)錫係新穎的化合物，於室溫(23℃)為液體，且即便於低溫仍具有高蒸氣壓(於100℃為2.3torr(306.6Pa))，故而適合作為例如有機金屬化學氣相沉積(MOCVD；Metal-Organic Chemical Vapor Deposition)、低壓氣相沉積(LPCVD；Low-Pressure Chemical Vapor Deposition)、電漿增強氣相沉積(PECVD；Plasma Enhanced Chemical Vapor Deposition)、原子層沉積(ALD)的前驅物，特別是作為ALD之前驅物。
根據本發明，藉由使用作為具有高蒸氣壓之前驅物的雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫，並適當選擇氧化劑，便能夠以化學蒸鍍(具體而言為ALD)來高效率地形成n型或p型之錫氧化物薄膜。
由於本發明之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫為2價，故而在進行ALD之情況，能夠藉由氧化劑來區分製作出氧化錫(IV)及氧化錫(II)，特別是適於藉由ALD來形成作為p型透明導電膜之氧化錫(II)薄膜。再者，若使用還原劑，則亦可進行金屬錫之ALD。
本發明之雙(乙基環戊二烯)錫(Sn[C5H4(C2H5)]2)係以下述結構式所表示之化合物。此外，下述結構式係表示雙(乙基環戊二烯)錫之立體穩定的結構，實際上，雙(乙基環戊二烯)錫亦包含乙基環戊二烯配位基非為5配位的化合物。
[化2]
錫通常可能是2價或4價之氧化數。2價之錫化合物係離子鍵結性強並具有還原性，4價之錫化合物則共價性強。本發明之雙(乙基環戊二烯)錫係2價之錫化合物。
本發明之雙(乙基環戊二烯)錫可以各種方法進行製造。舉下述一例：雙(乙基環戊二烯)錫可對於使乙基環戊二烯及金屬鉀溶解於四氫呋喃(THF；tetrahydrofuran)之溶液，於-78℃之溫度下添加氯化錫(II)之THF溶液並進行攪拌後，藉由減壓蒸餾來以高產率獲得作為黃色液體之生成物。
若將本發明之雙(乙基環戊二烯)錫作為CVD(例如MOCVD、LPCVD、PECVD、及ALD)之前驅物而使用，能夠形成含錫之薄膜。
為了進行這些化學蒸鍍法，必須將即便於低溫仍容易蒸發之化合物用作前驅物。在這方面而言，本發明之雙(乙基環戊二烯)錫於23℃為液體。再者，由於本發明之雙(乙基環戊二烯)錫於100℃之蒸氣壓為2.3torr(306.6Pa)，故而即便於低溫仍具有高蒸氣壓。因此，前述雙(乙基環戊二烯)錫係適於使用前述之各種CVD、特別是ALD而形成薄膜。
此外，雙環戊二烯錫於室溫為固體，於80℃之蒸氣壓為0.1torr(13.3Pa)，相較於雙(乙基環戊二烯)錫低不少。
就使用將雙(乙基環戊二烯)錫作為前驅物之化學蒸鍍法所進行之薄膜形成法作為一例來進行說明。
CVD中，係將充填有雙(乙基環戊二烯)錫之原料容器加熱並氣化，而供給至反應室。氣化可以CVD中通常的有機金屬化合物之氣化方法進行、例如，在CVD裝置之原料容器中進行加熱或減壓。為了將雙(乙基環戊二烯)錫供給到反應室中之基板，從原料容器到反應室之配管及反應室係預先設為不讓作為原料之雙(乙基環戊二烯)錫產生熱分解而保持住氣體狀態的溫度，亦即比原料容器之溫度(使原料氣化之溫度)要高，但比原料之熱分解溫度要低。於使用本發明之雙(乙基環戊二烯)錫的情況，加熱溫度為23℃至200℃左右。為了提高成膜溫度(基板溫度)設定之自由度，加熱溫度盡可能越低越好。從而，於低溫具有充分的蒸氣壓之雙(乙基環戊二烯)錫可說是適於CVD。
化學蒸鍍法中具有例如MOCVD等在基板上連續性地進行熱分解而沉積之熱CVD法、或是沉積出一層層原子層的ALD法等，本發明以ALD為佳。
ALD係藉由交互供給雙(乙基環戊二烯)錫與氧化劑，而藉由基板上之表面反應以原子層之單位控制氧化錫(II)或氧化錫(IV)之薄膜以進行成膜。氧化劑可使用例如水、臭氧或電漿活性化氧等。在氧化劑使用水的情況，係形成作為p型透明導電膜之氧化錫(II)之薄膜，而在使用臭氧或電漿活性化氧的情況，則形成作為n型透明導電膜之氧化錫(IV)之薄膜。
本發明之化學蒸鍍用原料係以下述式(1)所表示之雙(烷基環戊二烯)錫或是將下述式(1)所表示之雙(烷基四甲基環戊二烯)錫作為主成分而含有。
[化3]
前述式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫係2價之錫化合物。從而，該雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫係離子鍵結性強且具有還原性。
式(1)中，R1及R2係分別獨立表示氫或碳數6以下之烷基，R3及R4係分別獨立表示碳數6以下之烷基。若碳數過多，則前驅物體積變大，而使ALD時之吸附量減少，故而本發明之R1、R2、R3及R4係碳數6以下，較佳為碳數4以下。
碳數4以下之烷基可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、及三級丁基。
R1及R2較佳係均為氫、或均為碳數為6以下且相同碳數之烷基，更佳係均為為碳數2或3之烷基，特佳係均為碳數2之乙基。
R3及R4較佳係均為碳數為6以下且相同碳數，更佳係均為碳數1至3之烷基，特佳係均為碳數1之甲基。
進而，就ALD中之吸附量之觀點而言，相較於雙(烷基四甲基環戊二烯)錫，較佳為雙(烷基環戊二烯)錫。
本發明之化學蒸鍍用原料只要是具有高蒸氣壓且於進行化學蒸鍍時容易產生氣化，則可為固體或液體，但就程序之效率化的方面而言，較佳
為於23℃中為液體。從而，作為化學蒸鍍用原料之主成分的雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫的融點係未達35℃，較佳為未達30℃，更佳為未達23℃。
此外，R1及R2為氫之雙環戊二烯錫在23℃為固體，於80℃之蒸氣壓為0.1torr(13.3Pa)，R1及R2為乙基之雙(乙基環戊二烯)錫在23℃為液體，於80℃之蒸氣壓為1.2torr(159.9Pa)，於100℃之蒸氣壓為2.3torr(306.6Pa)。
為了進行化學蒸鍍，需要使用蒸氣壓高之化合物作為前驅物。本發明之化學蒸鍍用原料較佳為在23℃中為液體，且即便低溫仍具有高蒸氣壓。本發明中之式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫之蒸氣壓在80℃為0.05torr至10torr(6.6Pa至1333.2Pa)，故而適於使用CVD、特別是ALD而形成薄膜。
前述化學蒸鍍用原料中，以式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫之含量以接近100wt%為佳。具體而言，雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫之含量較佳為在化學蒸鍍用原料中為95wt%至100wt%，更佳為99wt%至100wt%。其中，亦可於不影響本發明目的之範圍內，含有於進行化學蒸鍍時讓原料氣化之溫度下不會與雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫進行反應且不氣化之物質。
本發明之化學蒸鍍用原料可以各種方法加以製造。例如，R1及R2為乙基之雙(乙基環戊二烯)錫之製造方法係如前述。
使用本發明之化學蒸鍍用原料的薄膜形成係藉由CVD法來進行。
CVD中，係將充填有以式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫之原料容器加熱並氣化，而供給至反應室。氣化可以CVD中之通常的有機金屬化合物之氣化方法來進行，例如，在CVD裝置之原料容器中進行加熱或減壓。繼而，將經氣化之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫供給至反應室中之基板。此時，從原料容器到反應室之配管及反應室係設為不讓作為原料之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫產生熱分解而保持住氣體狀態的溫度，亦即比原料容器之溫度(使原料氣化之溫度)要高，但比原料之熱分解溫度要低。本發明中之化學蒸鍍法之情況，加熱溫度為23℃至200℃左右。為了提高成膜溫度(基板溫度)設定之自由度，加熱溫度盡可能低為佳。從而，化學蒸鍍用原料可說是較佳為於低溫具有充分的蒸氣壓。
化學蒸鍍法具有例如MOCVD般在基板上連續性地進行熱分解而沉積之熱CVD法、或是沉積出一層層的原子層之ALD法等，本發明之化學蒸鍍用原料雖亦適於熱CVD法，但特佳為ALD法。
ALD中，係藉由交互供給化學蒸鍍用原料與氧化劑，並藉由在基板上之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫與氧化劑的反應，以原子層之單位來控制氧化錫(II)或氧化錫(IV)之薄膜以進行成膜。氧化劑可使用例如水、臭氧或電漿活性化氧等。於使用水作為氧化劑的情況，係形成作為p型透明導電膜之氧化錫(II)之薄膜，於使用臭氧或電漿活性化氧的情況，則形成作為n型透明導電膜之氧化錫(IV)之薄膜。
ALD中，係藉由反覆實施以下述步驟所構成之成膜循環來進行成膜：(i)將氣相之化學蒸鍍用原料導入至加熱器上配置有基板之腔室內，以使氣相之該原料吸附於基板上之步驟，(ii)藉由非活性氣體而將腔室內之剩餘的化學
蒸鍍用原料進行沖洗之步驟，(iii)投入氣相之氧化劑，使得基板上之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫進行反應，而形成錫氧化物之步驟，(iv)藉由非活性氣體將腔室內之剩餘的氧化劑進行沖洗之步驟。成膜循環之次數雖依據基板之面積、或含錫之薄膜之厚度而有所不同，但通常為100次至10000次。
成膜溫度係將基板溫度設為與反應溫度相同，該基板溫度係低於使所吸附之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫產生熱分解的溫度，但高至能與氧化劑充分進行反應之程度。
此外，化學蒸鍍用原料或氧化劑雖從外部以氣相來供給至設置有基板之反應室，但需要以不會凝結在基板上的方式，藉由低於基板溫度之溫度來進行昇華或蒸發。此時，若化學蒸鍍用原料於室溫為固體，則難以藉由流量控制裝置而控制氣相之供給速度，若化學蒸鍍用原料於室溫為液體，則能夠藉由流量控制裝置來精密且容易地控制氣相之供給速度，而可說是適於ALD。
以下，基於實施例來進一步地具體說明本發明，然本發明並不受下述實施例所限制。
[實施例1]雙(乙基環戊二烯)錫(Sn[C5H4(C2H5)]2)
於1L之四口燒瓶加入THF 400ml、金屬鉀21.7g(0.55mol)及乙基環戊二烯(C5H5(C2H5))70.8g(0.75mol)，反應26小時後，以40℃進行減壓蒸餾，獲得C5H4(C2H5)K。
在-78℃將THF 600ml、SnCl250.7g(0.27mol)添加於所獲得之C5H4(C2H5)K，於室溫攪拌23小時。之後，以50℃進行減壓蒸餾，獲得固形物。
將所獲得之固形物填入至單蒸餾裝置，以110℃、0.1torr(13.3Pa)進行真空蒸餾2次後，獲得黃色之液體。產量為61.3g(0.20mol)，產率為76.2%(以SnCl2為基準)。
就所獲得之試料進行以下(1)~(3)之分析，確認得到Sn[C5H4(C2H5)]2。
(1)組成分析
將濕式分解所得之液體進行ICP(Inductively Coupled Plasma；感應耦合電漿)發光分光分析之結果，Sn之含量為38.2%(理論值：38.9%)。
(2)1H-NMR
測定條件(裝置：AVANCE NEO 500(500MHz)，Bruker BioSpin，溶劑：THF-d8，方法：1D)
CH2CH3、1.15(6H，triplet)ppm：CH2CH3、2.48(4H，quartet)ppm：C5H4、5.71(4H，multiplet)ppm：C5H4、5.79(4H，multiplet)ppm
(3)13C-NMR
測定條件(裝置：AVANCE NEO 500(125MHz)，Bruker BioSpin，溶劑：THF-d8，方法：1D)
133.61、110.31、108.37ppm：C5
22.53、16.88ppm：C2H5
繼而，使用壓力計(型式：121A，廠商名：mks)，直接測定70℃至130℃中之蒸氣壓，獲得下算式。
logP(torr)=-1930/T(K)+5.54
根據上述算式，而求出80℃之蒸氣壓為1.2torr(159.9Pa)，100℃之蒸氣壓為2.3torr(306.6Pa)。
Sn[C5H4(C2H5)]2可說是蒸氣壓高，並具有化學蒸鍍所要求之揮發性。
再者，合成之Sn[C5H4(C2H5)]2於室溫與水進行反應而產生白色固體。這代表的是可使用水來作為氧化劑，而可說是能夠藉由ALD而適當地形成作為p型透明導電膜之氧化錫(II)之薄膜。
[實施例2]雙環戊二烯錫(Sn(C5H5)2)
雙環戊二烯錫亦如Christoph Janiak,Z.Anorg.Allg.Chem.2010,636,2387-2390所示般，並非為新穎物質，但卻未見有作為化學蒸鍍用原料而使用之報導。根據前述文獻，Sn(C5H5)2於常溫為固體，但可於80℃、0.1torr(13.3Pa)進行昇華精製，而具有化學蒸鍍所要求之性能。
[比較例1]雙(二甲基胺-2-甲基-2-丙氧基)錫[Sn(dmamp)2]
專利文獻1中係依照下述方法進行合成。
於250ml之舒倫克瓶(Schlenk flask)加入氯化錫(II)(SnCl2)1g(5.27mmol)及雙(三甲基矽基)醯胺化鋰(Li(btsa))1.76g(10.54mmol)，添加乙醚50ml後，於室溫攪拌3小時。過濾混合溶液以去除氯化鋰(LiCl)後，於真空下從殘留液體去除溶劑，在100℃、0.01torr(1.3Pa)進行分餾，獲得雙[雙(三甲基矽基)胺基]錫(Sn(btsa)2)。繼而，讓Sn(btsa)2 1g(2.28mmol)溶解於正己烷，而於該溶液慢慢添加2當量之1-(二甲基胺基)-2-甲基-2-丙醇0.53g(4.56mmol)，於室溫攪拌6小時。
於真空下去除溶劑後，在100℃、0.01torr(1.3Pa)進行分餾，獲得產率91%的純淨之Sn(dmamp)2配位化合物。
根據分餾時之壓力，雙(二甲基胺基-2-甲基-2-丙氧基)錫在100℃之蒸氣壓為0.01torr(1.3Pa)。雙(二甲基胺基-2-甲基-2-丙氧基)錫之蒸氣壓相較於本發明之物質為極低，而難以僅利用本身蒸氣壓來用於化學蒸鍍，需要使用起泡器等之幫助。
[比較例2]
四乙基錫係作為Sn之ALD的前驅物而受到廣泛使用，四乙基錫之蒸氣壓亦高。然而，四乙基錫存在有高毒性之問題。再者，由於四乙基錫為4價之化合物，故而難以藉由ALD而形成氧化錫(II)之薄膜。
Claims (4)
- 一種含錫之薄膜之製造方法，係藉由化學氣相蒸鍍法來進行，前述化學氣相蒸鍍法係使含有以下述式(1)所表示之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫之化學氣相蒸鍍用原料在化學蒸鍍裝置之原料容器中氣化，並將已氣化之雙(烷基環戊二烯)錫或雙(烷基四甲基環戊二烯)錫供給到反應室中之基板；
- 如請求項1所記載之含錫之薄膜之製造方法，前述化學氣相蒸鍍法為原子層沉積法。
- 如請求項2所記載之含錫之薄膜之製造方法，其中前述含錫之薄膜為氧化錫(II)薄膜。
- 如請求項3所記載之含錫之薄膜之製造方法，其中使用水來作為氧化劑。
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