CN112639163A - 双(烷基四甲基环戊二烯基)锌、化学蒸镀用原料和含锌薄膜的制备方法 - Google Patents
双(烷基四甲基环戊二烯基)锌、化学蒸镀用原料和含锌薄膜的制备方法 Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 40
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 34
- 239000002994 raw material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 9
- 239000010408 film Substances 0.000 abstract description 14
- 239000010409 thin film Substances 0.000 abstract description 9
- 150000003752 zinc compounds Chemical class 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 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
- 239000002904 solvent Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000007789 gas Substances 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 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
- 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
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 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
Classifications
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- 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
- C07F17/00—Metallocenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
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- 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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- Mechanical Engineering (AREA)
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Abstract
提供:为用于形成含锌薄膜的化学蒸镀用原料,由于在室温下为液体,所以容易处理的、用下述式(1)表示的双(烷基四甲基环戊二烯基)锌(在式(1)中,R1和R2表示碳原子数为3的烷基),以及含有用下述式(2)表示的双(烷基四甲基环戊二烯基)锌(在式(2)中,R3和R4表示碳原子数为2~5的烷基)的化学蒸镀用原料;和利用化学蒸镀法的含锌薄膜的制备方法。
Description
技术领域
本发明涉及化学蒸镀用的有机锌化合物和化学蒸镀原料。
背景技术
透明导电膜由于其特性,有平板显示器、太阳能电池、触摸屏、热射线反射膜、透明加热器、透明电磁波屏障和抗静电膜等多种用途。作为用于这些透明导电膜的材料,在氧化锌中掺杂有铝、镓、铟和硼等金属元素和氟等卤素元素的材料由于导电膜成膜温度低,且电特性、光学特性和耐氢等离子体特性优异,所以最多地将氧化锌系薄膜用作透明导电膜。
氧化锌系薄膜可通过溅射等物理蒸镀法(PVD)或原子层沉积法(ALD)等化学蒸镀法(CVD)形成。其中,在化学蒸镀法中,通过将化学蒸镀用原料以气体的状态输送至设置有基板的反应室中,在基板上进行热分解、化学反应或光化学反应等,从而沉积具有所希望的组成的薄膜。例如,在热分解中,使化学蒸镀用原料与加热至比该原料的分解温度高的温度的基材接触,从而在基材上形成金属膜。因此,化学蒸镀用原料需要在比基板温度低的温度下能够气化,并且为了可在基板上形成均匀的膜,需要蒸气压充分高。
在专利文献1中,作为用于氧化锌系薄膜的蒸镀的前体,公开了二茂锌(zincocene)或其衍生物。专利文献1提供具有优异的热稳定性和化学稳定性以及高蒸气压的新的化学蒸镀用原料,公开了只改变反应气体或蒸镀温度等条件,就可形成碳等杂质少的高纯度的氧化锌系薄膜。
但是,这些化合物在室温下为固体,在化学蒸镀工序中,需要在熔化后使其气化,或由固体升华为气体。因此,必须将固体加热至熔化温度附近,来使其形成气体状,还需要将到反应室的配管和反应室保持在原料温度以上且低于热分解温度,存在操作繁琐的问题。
现有技术文献
专利文献
专利文献1:日本特开2013-108178号公报。
发明内容
发明所要解决的课题
本发明的课题在于,提供双(烷基四甲基环戊二烯基)锌,其是用于形成含锌薄膜的化学蒸镀用原料,在室温下为液体,从而容易处理。
解决课题的手段
本发明是要解决上述现有技术中的课题的发明,包含以下事项。
本发明的双(烷基四甲基环戊二烯基)锌的特征在于,用下述式(1)表示。
[化1]
其中,在式(1)中,R1和R2表示碳原子数为3的烷基。
本发明的化学蒸镀用原料的特征在于,含有用下述式(2)表示的双(烷基四甲基环戊二烯基)锌作为主成分。
[化2]
其中,在式(2)中,R3和R4表示碳原子数为2~5的烷基。
上述化学蒸镀用原料优选在23℃下为液体。
本发明的含锌薄膜的制备方法的特征在于,使用含有用下述式(2)表示的双(烷基四甲基环戊二烯基)锌作为主成分、且在23℃下为液体的化学蒸镀用原料,通过化学蒸镀法形成。
[化3]
在式(2)中,R3和R4表示碳原子数为2~5的烷基。
上述化学蒸镀法优选为原子层沉积法。
发明的效果
由于本发明的用式(1)或(2)表示的双(烷基四甲基环戊二烯基)锌在室温下为液体,所以容易处理,适合作为化学蒸镀用原料。
具体实施方式
以下,对本发明的用下述式(1)表示的双(烷基四甲基环戊二烯基)锌进行说明。
[化4]
在上述式(1)中,R1和R2表示碳原子数为3的烷基。R1和R2可相同,也可不同,但考虑到容易合成而优选相同。
在碳原子数为3的烷基中,可列举出正丙基和异丙基,优选正丙基。
用上述式(1)表示的双(烷基四甲基环戊二烯基)锌在大气压下在23℃下为液体。此外,由于具有高蒸气压,所以适合作为化学蒸镀用原料。
本发明的化学蒸镀用原料含有用下述式(2)表示的双(烷基四甲基环戊二烯基)锌作为主成分。
[化5]
在上述式(2)中,R3和R4表示碳原子数为2~5的烷基。R3和R4可相同,也可不同,但考虑到容易合成而优选相同。
在碳原子数为2~5的烷基中,可列举出乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、新戊基、3-甲基丁基、1-甲基丁基、1-乙基丙基和1,1-二甲基丙基。
其中,R3和R4优选碳原子数为3~5的烷基,具体而言,优选正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基等,进一步优选正丙基、异丙基,特别优选正丙基。
由于用式(1)或式(2)表示的双(烷基四甲基环戊二烯基)锌优选在室温下为液体,所以其熔点优选比室温低,优选低于35℃。更优选低于23℃,进一步优选低于20℃,特别优选低于10℃。
在上述化学蒸镀用原料中,用式(2)表示的双(烷基四甲基环戊二烯基)锌的含量优选接近100%,但可微量地含有在用作蒸镀原料的温度下不与双(烷基四甲基环戊二烯基)锌反应、且不气化的杂质。
使用本发明的用式(1)表示的双(烷基四甲基环戊二烯基)锌、或含有用式(2)表示的双(烷基四甲基环戊二烯基)锌作为主成分的化学蒸镀用原料的薄膜形成通过化学蒸镀法(CVD)进行。在化学蒸镀法中,将填充有双(烷基四甲基环戊二烯基)锌的原料容器加热而使其气化,并供给到反应室中。此时,为了将作为原料的双(烷基四甲基环戊二烯基)锌供给至反应室中的基板,在连接原料容器和反应室的配管和反应室中,需要使原料不热分解而保持气体的状态的温度,即比原料容器的温度(使原料气化的温度)高,且比原料的热分解温度低。因此,为了提高成膜温度(基板温度)设定的自由度,希望原料容器的温度尽可能低,并希望使用在低温下具有充分的蒸气压的原料。
在化学蒸镀法中,例如有在基板上连续地进行热分解而沉积的热CVD法,或每次沉积一个原子层的原子层沉积法(ALD)等,其中,优选原子层沉积法(ALD)。在ALD中,例如通过交替地供给作为化学蒸镀原料的双(烷基四甲基环戊二烯基)锌和氧化剂,利用基板上的表面反应,可将氧化锌的薄膜按照原子层的单位来控制而成膜。氧化剂例如可使用水蒸气、臭氧、等离子体活化氧等。
由于本发明的双(烷基四甲基环戊二烯基)锌在室温下为液体,所以容易利用流量控制装置精密地控制原料气体的供给速度。
需说明的是,在蒸镀原料在室温下为固体的情况下,由于难以利用流量控制装置控制原料的供给速度,所以向反应室的原料供给速度的控制的精密性显著变差。
实施例
以下,基于实施例来更具体地说明本发明,但本发明不受下述实施例限制。
[实施例1]
在1L的四颈烧瓶中放入400ml的THF、14.4g (0.37mol)的金属钾、142.2g(0.87mol)的C5(CH3)4(n-C3H7)H,使其反应52小时后,在100℃下减压蒸馏,得到C5(CH3)4(n-C3H7)K。
在-78℃下,向得到的C5(CH3)4(n-C3H7)K中加入600ml的THF、24.7g (0.18mol)的ZnCl2,在50℃下搅拌5.5小时。然后,在50℃下减压蒸馏,得到固体成分。
将得到的固体成分装入简单蒸馏装置中,在100~150℃、0.4~0.5torr下进行2次真空蒸馏,结果得到黄色的液体。产量为37.6g (0.096mol),收率为53.3% (以ZnCl2为基准)。
对于得到的试样,进行以下(1)-(3)的分析,结果确认是Zn[C5(CH3)4(n-C3H7)]2。
(1) 组成分析
湿式分解而得到的液体的ICP发射分光分析的结果为,Zn的含量为15.9% (理论值:16.7%)。
(2) 1H-NMR
测定条件(装置:UNITY INOVA-400S (400MHz),Varian公司,溶剂:THF-d8,方法:1D)
1.87 (12H,单峰) ppm:C5(CH3)4,1.84 (12H,单峰) ppm:C5(CH3)4,2.23~2.19(4H,多重峰) ppm:CH2CH2CH3,1.24~1.19 (4H,六重峰) ppm:CH2CH2CH3,0.98~0.84 (6H,三重峰) ppm:CH2CH2CH3。
(3) 13C-NMR
测定条件(装置:UNITY INOVA-400S (100MHz),Varian公司,溶剂: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-C3H7)。
接着,在升温速度为10℃/min下进行密闭DSC测定,结果熔点为约5℃,且直至约250℃仍未热分解。另外,根据在1个气压的氩气氛中在150℃下的重量变化求得的气化速度为约50μg/min。
因此,Zn[C5(CH3)4(n-C3H7)]2在室温下为液体,可以说具有化学蒸镀所要求的热稳定性和气化性。
[比较例1]
在1L的四颈烧瓶中放入400ml THF、11.6g (0.30mol)的金属钾、42.1g (0.45mol)的C5H4(C2H5)H,使其反应21小时后,在40℃下减压蒸馏,得到C5H4(C2H5)K。
在-78℃下,向得到的C5H4(C2H5)K中加入600ml的THF、19.4g (0.14mol)的ZnCl2,在50℃下搅拌6小时。然后,在50℃下减压蒸馏,得到固体成分。
将得到的固体成分装入简单蒸馏装置中,在120~190℃、0.4~0.5torr下进行2次真空蒸馏,结果得到淡黄色的固体。产量为8.1g (0.032mol),收率为22.9% (以ZnCl2为基准)。
对于得到的试样,进行以下(1)-(3)的分析,结果确认是Zn[C5H4(C2H5)]2。
(1) 组成分析
湿式分解而得到的液体的ICP发射分光分析的结果为,Zn的含量为25.7% (理论值:26.0%)。
(2) 1H-NMR
测定条件(装置:UNITY INOVA-400S (400MHz),Varian公司,溶剂:THF-d8,方法:1D)
5.72-5.71 (4H,双重峰) ppm:C5H4,5.35-5.34 (4H,双重峰) ppm:C5H4,2.57-2.51 (4H,四重峰) ppm:CH2CH3,1.23-1.19 (6H,三重峰) ppm:CH2CH3。
(3) 13C-NMR
测定条件(装置:UNITY INOVA-400S (100MHz),Varian公司,溶剂:THF-d8,方法:1D)
138.50、138.18、109.51、109.49、99.28、99.27ppm:C5,
23.67、15.81ppm:CH2CH3。
接着,在升温速度为10℃/min下进行密闭DSC测定,结果熔点为约90℃,且从约184℃开始热分解。另外,根据在1个气压的氩气氛中在150℃下的重量变化求得的气化速度为约0.7μg/min。
这样,Zn[C5H4(C2H5)]2在室温下为固体,热稳定性和气化性也比本发明的化合物差。
Claims (5)
3.根据权利要求2所述的化学蒸镀用原料,其在23℃下为液体。
5.根据权利要求4所述的含锌薄膜的制备方法,其中,所述化学蒸镀法为原子层沉积法。
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