Platinum ω-Alkenyl Compounds as Chemical Vapor Deposition Precursors: Synthesis and Characterization of Pt[CH 2 CMe 2 CH 2 CH═CH 2 ] 2 and the Impact of Ligand Design on the Deposition Process
Platinum ω-Alkenyl Compounds as Chemical Vapor Deposition Precursors: Synthesis and Characterization of Pt[CH 2 CMe 2 CH 2 CH═CH 2 ] 2 and the Impact of Ligand Design on the Deposition Process
复制标题
铂α-烯基化合物作为化学气相沉积前驱体：Pt[CH 2 CMe 2 CH 2 CH–CH 2 ] 2 的合成和表征以及配体设计对沉积过程的影响
DOI：
10.1021/acs.chemmater.0c03226
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发表时间：
2020
影响因子：
8.6
通讯作者：
Girolami, Gregory S.
中科院分区：
文献类型：
--
作者：
Liu, Sumeng;Zhang, Zhejun;Gray, Danielle;Zhu, Lingyang;Abelson, John R.;Girolami, Gregory S.
本文报道了三种ω-烯基铂配合物Pt[CH_2CMe_2（CH_2）_xCH_CH_2]_2（其中x = 0、1或2）的合成和表征，以及一些相关的铂化合物在合成过程中的副产物。三种配合物中的ω-烯基配体均为顺式双（η1，η2- 2，2-二甲基丁-3-烯-1-基）铂（2），顺式-双（η1，η2- 2，2-二甲基-4-烯-1-基）铂（3），和顺式-双（η1，η2- 2，2-二甲基己-5-烯-1-基）铂（4）通过在配体链的一端的Pt-烷基σ键和在另一端的Pt-烯烃π相互作用与Pt结合;烯烃在溶液中从Pt中心可逆地解络合。3的良好挥发性（20 °C时为10 mTorr）、其长期储存而不分解的能力以及其对空气和水分的稳定性使其成为有吸引力的铂化学气相沉积（CVD）前体。CVD的薄膜从3显示没有成核延迟在几个不同的基板（SiO2/Si，Al 2 O3，和VN），并给出了异常平滑的膜。在330 °C下，在不存在反应性气体的情况下，前体沉积含有50%碳的铂，但在远程氧等离子体的存在下，碳的量减少到低于卢瑟福背散射光谱（RBS）检测极限，而不影响膜平滑度。在250 °C的热壁CVD条件下，在不存在共反应物的情况下，3中72%的碳原子作为氢化产物（主要是4，4-二甲基戊烯）释放，22%作为脱氢产物释放（所有这些都是骨架重排的结果），并且6%保留在膜中。从产物分布中得出了一些关于CVD机理的结论。
We describe the synthesis and characterization of three platinum(II) ω-alkenyl complexes of stoichiometry Pt[CH2CMe2(CH2)xCH═CH2]2wherexis 0, 1, or 2, as well as some related platinum(II) compounds formed as byproducts during their synthesis. The ω-alkenyl ligands in all three complexes,cis-bis(η1,η2-2,2-dimethylbut-3-en-1-yl)platinum (2),cis-bis(η1,η2-2,2-dimethylpent-4-en-1-yl)platinum (3), andcis-bis(η1,η2-2,2-dimethylhex-5-en-1-yl)platinum (4), bind to Pt by means of a Pt–alkyl sigma bond at one end of the ligand chain and a Pt–olefin pi interaction at the other; the olefins reversibly decomplex from the Pt centers in solution. The good volatility of3(10 mTorr at 20 °C), its ability to be stored for long periods without decomposition, and its stability toward air and moisture make it an attractive platinum chemical vapor deposition (CVD) precursor. CVD of thin films from3shows no nucleation delay on several different substrates (SiO2/Si, Al2O3, and VN) and gives films that are unusually smooth. At 330 °C in the absence of a reactive gas, the precursor deposits platinum containing 50% carbon, but in the presence of a remote oxygen plasma, the amount of carbon is reduced to below the Rutherford backscattering spectroscopy (RBS) detection limit without affecting the film smoothness. Under hot wall CVD conditions at 250 °C in the absence of a co-reactant, 72% of the carbon atoms in3are released as hydrogenated products (largely 4,4-dimethylpentenes), 22% are released as dehydrogenated products (all of which are the result of skeletal rearrangements), and 6% remain in the film. Some conclusions about the CVD mechanism are drawn from this product distribution.