TWI711622B - 雙(烷基四甲基環戊二烯)鋅、化學蒸鍍用原料、以及含鋅薄膜之製造方法 - Google Patents
雙(烷基四甲基環戊二烯)鋅、化學蒸鍍用原料、以及含鋅薄膜之製造方法 Download PDFInfo
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- TWI711622B TWI711622B TW108143602A TW108143602A TWI711622B TW I711622 B TWI711622 B TW I711622B TW 108143602 A TW108143602 A TW 108143602A TW 108143602 A TW108143602 A TW 108143602A TW I711622 B TWI711622 B TW I711622B
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- zinc
- vapor deposition
- chemical vapor
- raw material
- alkyltetramethylcyclopentadiene
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- 239000011701 zinc Substances 0.000 title claims abstract description 38
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 title claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 14
- 238000000231 atomic layer deposition Methods 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 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 4
- 239000002904 solvent Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- -1 specifically Chemical group 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
提供一種以下述式(1)所表示之雙(烷基四甲基環戊二烯)鋅(式(1)中,R1
以及R2
係表示碳數3之烷基),係用以形成含鋅薄膜之化學蒸鍍用原料,在室溫為液體故使用上容易。另外提供一種化學蒸鍍用原料,係含有以下述式(2)所表示之雙(烷基四甲基環戊二烯)鋅(式(2)中,R3
以及R4
係表示碳數2至5之烷基),以及提供一種利用化學蒸鍍法之含鋅薄膜之製造方法。
Description
本發明係關於一種化學蒸鍍用有機鋅化合物以及化學蒸鍍原料。
透明導電膜基於本身特性故適用於平板顯示器、太陽電池、觸控螢幕、熱能束反射膜、透明加熱器、透明電磁波屏蔽件以及抗帶電膜等各式各樣的用途。此等透明導電膜所使用之材料當中,在氧化鋅中摻雜了鋁、鎵、銦以及硼等金屬元素、氟等鹵素之材料,由於導電膜形成之溫度低,在電性、光學特性以及耐氫電漿特性上優異,故透明導電膜最常使用氧化鋅系薄膜。
氧化鋅系薄膜可藉由濺鍍等物理蒸鍍法(PVD)、原子層沉積法(ALD)等化學蒸鍍法(CVD)來形成。此等當中,化學蒸鍍法係使得化學蒸鍍用原料維持氣體狀態送往設置有基板的反應室,於基板上經過熱分解、化學反應、或是光化學反應等而沉積具有所期望組成之薄膜。例如,以熱分解而言,係使得化學蒸鍍用原料來和被加熱至溫度高於該原料之分解溫度的基材做接觸,於基材上形成金屬膜。因此,為使得化學蒸鍍用原料能以較基板溫度來得低的溫度產生氣化,且可於基板上形成均勻的膜,故必須為蒸氣壓相當高者。
日本特開2013-108178號公報中揭示了將二茂鋅(Zincocene)或其衍生物當作氧化鋅系薄膜之蒸鍍上所使用之前驅物。日本特開2013-108178號公報係提供一種具有優異熱穩定性以及化學穩定性以及高蒸氣壓之新穎的化學蒸鍍用原料,其中揭示了只要改變反應氣體、蒸鍍溫度等條件,則可形成碳等雜質少的高純度氧化鋅系薄膜。
但是,此等化合物於室溫為固體,在化學蒸鍍步驟中必須使之熔解後再使之氣化,或是從固體昇華成為氣體。因此,必須將固體加熱至熔解溫度附近而成為氣體狀,必須將到達反應室為止的配管以及反應室保持在原料溫度以上且未達熱分解溫度,操作複雜,此為問題所在。
本發明之課題在於提供一種雙(烷基四甲基環戊二烯)鋅,係用以形成含鋅薄膜之化學蒸鍍用原料,於室溫為液體,使用上容易。
本發明係用以解決上述習知技術中之課題,由以下事項所構成。
本發明之化學蒸鍍用原料之特徵在於:含有以下述式(2)所表示雙(烷基四甲基環戊二烯)鋅作為主成分。
其中,式(2)中,R3
以及R4
係表示碳數2至5之烷基。
前述化學蒸鍍用原料較佳為:於23℃為液體。
本發明之含鋅薄膜之製造方法之特徵在於:使用含有以下述式(2)所表示雙(烷基四甲基環戊二烯)鋅作為主成分、且於23℃為液體之化學蒸鍍用原料,藉由化學蒸鍍法來形成含鋅薄膜。
式(2)中,R3
以及R4
係表示碳數2至5之烷基。
前述化學蒸鍍法以原子層沉積法為佳。
本發明之式(1)或式(2)所表示雙(烷基四甲基環戊二烯)鋅由於在室溫為液體,故使用上容易,適合作為化學蒸鍍用原料。
以下,針對本發明之以下述式(1)所表示雙(烷基四甲基環戊二烯)鋅來說明。
前述式(1)中,R1
以及R2
係表示碳數3之烷基。R1
以及R2
可為相同也可為不同,但從合成之容易度而言以相同為佳。
碳數3之烷基可舉出正丙基以及異丙基,以正丙基為佳。
前述式(1)所表示雙(烷基四甲基環戊二烯)鋅在大氣壓下、23℃為液體。進而,由於具有高蒸氣壓,故適合作為化學蒸鍍用原料。
本發明之化學蒸鍍用原料係含有以下述式(2)所表示雙(烷基四甲基環戊二烯)鋅作為主成分。
前述式(2)中,R3
以及R4
係表示碳數2至5之烷基。R3
以及R4
可為相同也可為不同,從合成之容易度而言以相同為佳。
碳數2至5之烷基可舉出乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、新戊基、3-甲基丁基、1-甲基丁基、1-乙基丙基以及1,1-二甲基丙基。
此等當中,R3
以及R4
以碳數3至5之烷基為佳,具體而言,以正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基等為佳,進而,以正丙基、異丙基為佳,尤其以正丙基為佳。
以式(1)或式(2)所表示之雙(烷基四甲基環戊二烯)鋅由於較佳為在室溫為液體,故其熔點低於室溫為佳,以未達35℃為佳。更佳為未達23℃,特佳為未達20℃,尤佳為未達10℃。
上述化學蒸鍍用原料中,以式(2)所表示雙(烷基四甲基環戊二烯)鋅之含量以接近100%為佳,但在作為蒸鍍原料來使用之溫度中,也可微量含有不會和雙(烷基四甲基環戊二烯)鋅起反應、不會氣化之雜質。
使用本發明之以式(1)所表示雙(烷基四甲基環戊二烯)鋅、或是使用含有以式(2)所表示之雙(烷基四甲基環戊二烯)鋅作為主成分之化學蒸鍍用原料的薄膜形成係藉由化學蒸鍍法(CVD)來進行。化學蒸鍍法中,係對於填充有雙(烷基四甲基環戊二烯)鋅之原料容器進行加熱來氣化而供給至反應室。此時,為了將作為原料之雙(烷基四甲基環戊二烯)鋅供給直到反應室中之基板,連結原料容器與反應室的配管以及反應室必須為原料不會熱分解而保持在氣體狀態之溫度,亦即為高於原料容器之溫度(使得原料氣化之溫度)且低於原料之熱分解溫度。為此,為了提高成膜溫度(基板溫度)設定之自由度,原料容器之溫度以儘可能低為佳,使用在低溫具有充分蒸氣壓的原料為佳。
化學蒸鍍法中,有例如在基板上連續性熱分解而沉積之熱CVD法、一次一次地沉積一原子層之原子層沉積法(ALD)等,此等當中以原子層沉積法(ALD)為佳。以ALD而言,例如可交互供給作為化學蒸鍍原料之雙(烷基四甲基環戊二烯)鋅與氧化劑而藉由基板上之表面反應來以原子層之單位來控制、形成出成膜氧化鋅之薄膜。氧化劑可使用例如水蒸氣、臭氧、電漿活性化氧等。
本發明之雙(烷基四甲基環戊二烯)鋅由於在室溫為液體,故可輕易地藉由流量控制裝置來精密地控制原料氣體之供給速度。
此外,當蒸鍍原料在室溫為固體之情況,由於要利用流量控制裝置來控制原料之供給速度變得困難,故對於反應室之原料供給速度的控制精密性會顯著變差。
以下,基於實施例來更具體說明本發明,但本發明不受限於下述實施例。
[實施例1]
對於1L之四口燒瓶加入THF 400ml、金屬鉀14.4g(0.37mol)、C5
(CH3
)4
(n-C3
H7
)H 142.2g(0.87mol),使之反應52小時之後,以100ºC進行減壓餾除,得到C5
(CH3
)4
(n-C3
H7
)K。
對於所得到之C5
(CH3
)4
(n-C3
H7
)K,在-78℃加入THF 600ml、ZnCl2
24.7g(0.18mol),以50℃攪拌5.5小時。之後,以50ºC減壓餾除,得到固形物。
將所得到之固形物裝入單蒸餾裝置中,以100℃至150℃、0.4 torr至0.5torr進行2次真空蒸餾,得到黃色液體。產量為37.6g(0.096mol),產率53.3%(ZnCl2
基準)。
針對所得試樣進行以下(1)至(3)之分析,確認為Zn[C5
(CH3
)4
(n-C3
H7
)]2
。
(1)組成分析
經濕式分解所得之液之ICP(Inductively-Coupled-Plasma,感應耦合式電漿)發光分光分析之結果,Zn之含量為15.9%(理論值:16.7%)。
(2)1
H-NMR
測定條件(裝置:UNITY INOVA-400S(400MHz),VARIAN公司,溶媒:THF-d8,方法:1D)
1.87(12H,singlet)ppm:C5
(CH3
)4
, 1.84(12H,singlet)ppm:C5
(CH3
)4
,2.23~2.19(4H,multiplet)ppm:CH2
CH2
CH3
,1.24~1.19(4H,sextet)ppm:CH2
CH2
CH3
,0.98~0.84(6H,triplet)ppm:CH2
CH2
CH3
(3)13
C-NMR
測定條件(裝置:UNITY INOVA-400S(100MHz),VARIAN公司,溶媒:THF-d8,方法:1D)
114.01、113.28、109.79ppm:C5
29.13、25.89、14.37、10.99、10.84ppm:C(CH3
)4
(n-C3
H7
)
其次,以昇溫速度10℃/min來進行密閉DSC(Differential Scanning Calorimeter;示差掃描熱分析儀)測定之結果,熔點為約5℃,直到約250℃未發生熱分解。此外,從在氬1大氣壓氛圍、150℃之重量變化所求得之氣化速度為約50μg/min。
從而,可說Zn[C5
(CH3
)4
(n-C3
H7
)]2
在室溫為液體,具有化學蒸鍍所需之熱穩定性與氣化性。
[比較例1]
對於1L之四口燒瓶加入THF 400ml、金屬鉀11.6g(0.30mol)、C5
H4
(C2
H5
)H 42.1g(0.45mol),使之反應21小時後,以40℃進行減壓餾除,得到C5
H4
(C2
H5
)K。
對於所得之C5
H4
(C2
H5
)K,在-78℃加入THF 600ml、ZnCl2
19.4g(0.14mol),以50℃攪拌6小時。之後,以50℃進行減壓餾除,得到固形物。
將所得到之固形物裝入單蒸餾裝置中,以120℃至190℃、0.4torr至0.5torr進行2次真空蒸餾,得到淡黃色固體。產量為8.1g(0.032mol),產率22.9%(ZnCl2
基準)。
針對所得試樣進行以下(1)至(3)之分析,確認為Zn[C5
H4
(C2
H5
)]2
。
(1)組成分析
經濕式分解所得之液之ICP發光分光分析之結果,Zn之含量為25.7%(理論值:26.0%)。
(2)1
H-NMR
測定條件(裝置:UNITY INOVA-400S(400MHz),VARIAN公司,溶媒:THF-d8,方法:1D)
5.72-5.71(4H,doublet)ppm:C5
H4
,5.35-5.34(4H,doublet)ppm:C5
H4
,2.57-2.51(4H,quartet)ppm:CH2
CH3
,1.23-1.19(6H,triplet)ppm:CH2
CH3
(3)13
C-NMR
測定條件(裝置:UNITY INOVA-400S(100MHz),VARIAN公司,溶媒:THF-d8,方法:1D)
138.50、138.18、109.51、109.49、99.28、99.27ppm:C5
23.67、15.81ppm:CH2
CH3
其次,以昇溫速度10℃/min來進行密閉DSC測定之結果,熔點為約90℃,從約184℃起開始熱分解。此外,從在氬1大氣壓氛圍、150℃之重量變化所求得之氣化速度為約0.7μg/min。
如此般,Zn[C5
H4
(C2
H5
)]2
在室溫為固體,熱穩定性、氣化性也劣於本發明之化合物。
無
無。
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