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近年来,聚硅烷导电高分子材料受到广泛重视,主要由于硅是公知的半导体,在电子工业上应用极广泛,另外硅是地球上贮量最丰富的元素,在寻找非碳功能材料时,聚硅烷自然是首选.聚硅烷的主链形成σ电子离域,通过掺杂能使这类材料的电导率在较宽的范围内变化,从而赋予他们非常独特的光化学和光物理性质,可用作导体与半导体、光导体材料、以及非线性光学材料、光致抗蚀剂、电致发光装置中的发光二级管等,有可能成为方兴未艾的信息技术所必需的集成电子器件或集成光子器件中的关键材料之一.同π共轭体系相类似,聚硅烷体系也只有在掺杂引入载流子的情况下才能导电.相比之下,对依赖于σ共轭体系的导电机理研究很少.国际上关于这类高分子的理论研究还处在刚刚起步阶段,只有少部分的理论工作是关于未掺杂聚硅烷体系的基态几何和能带结构的分析,大多集中在σ电子离域的验证上.而对于掺杂聚硅烷的理论工作更是少见报道,仅有少量的关于掺杂对聚硅烷寡聚体极子的几何结构和激发能影响的理论工作.有关掺杂后聚硅烷的电子输运性能研究国内外更是未见文献报道,因此开展这方面的理论研究工作是很必要的.本文运用密度泛函理论并结合非平衡格林函数方法,用ATK软件和Gaussian 03软件分别对未掺杂、电荷掺杂(Si12+)、B原子和P原子掺杂(Si5Bsi6和Si5PSi6)的四种聚硅烷寡聚体进行了传输性质的比较性理论研究.首先,为了更真实的模拟电场情况下的电子的性质,本文应用Gaussian程序在6-31+G(d)基组和BHHLYP泛函下,分别在电场0.0,0.68×108,1.36×108,2.03×108,2.71×108,3.38×108和4.06×108V·m-1下对四种聚硅烷进行了几何结构优化,在优化的几何构型和相同的计算方法基础上进行了TDDFT激发态光谱的计算和自然键轨道NBO的计算.然后对优化后的聚硅烷在ATK程序下用Au(111)-(3×3)电极分别计算了偏压为0.0,0.2,0.4,0.6,0.8,1.0和1.2V下的电子输运性质.计算结果表明,电荷掺杂的聚硅烷Si12+和杂原子掺杂的聚硅烷(Si5BSi6和Si5PSi6)的传输性质有着明显的差异,得到了与实验相一致的结论.即电荷掺杂的聚硅烷由于电子传输通道被破坏,所以它的导电性很差,而Si5BSi6和Si5PSi6则表现出了很好的导电性能,并且杂原子掺杂的聚硅烷还表现出了NDR效应.我们通过传输谱图、MPSH图、激发态图谱、能带和共轭效应对上述现象进行了详细讨论.由此可见,B原子和P原子掺杂的聚硅烷可以作为电子器件的优良材料. 相似文献
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以甲基苯基聚硅烷 (PhSiMe ) n为原料 ,在无水AlCl3 存在下 ,通过与酰氯、酸酐及酯的取代反应合成了氯代聚硅烷及一系列共聚物 .在乙酰氯的作用下 , (PhSiMe ) n上的苯基能够被近乎完全的取代而生成氯代聚硅烷 .一元酸酐 (乙酸酐和丙酸酐 )在用酰氧基部分取代聚硅烷上苯基的同时 ,进行得更多的还是Cl取代 .而顺丁烯二酸酐、邻苯二甲酸酐和乙酸乙酯则只进行不完全的Cl取代 ,根据分子活性的不同得到取代比率各不相同的共聚物 .初步分析了各反应的过程 ,讨论了影响反应的因素 ,同时对于各产物的荧光和紫外特性也进行了分析和讨论 相似文献
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液体聚硅烷的合成与交联 总被引:2,自引:0,他引:2
采用具有不同有机取代基的二氯硅烷与甲基二苯基氯硅烷为原料,在甲苯中以金属钠共缩合的方法,合成了可流动的聚硅烷。这些聚硅烷可用灌注、浇铸、涂敷等方法制成各种形状,并能在多乙烯基硅烷存在下,以紫外光辐照进行交联。本文还讨论了这些聚硅烷的分子量分布以及红外、紫外、核磁共振等光谱性质。 相似文献
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Yutaka Majima Yasushi Kawata Yoshihiko Nakano Shuzi Hayase 《Journal of polymer science. Part A, Polymer chemistry》1997,35(3):427-430
Large polysilane spherulites have been observed. The spherulites were prepared by controlling the removal rate of solvents from poly(n-butyl-n-pentylsilane) under a xylene atmosphere. The diameter of the spherulites was greater than 0.1 mm. The structure of the spherulites was compared with that of the polysilane powder by polarized microscopy, SEM, DSC, and x-ray diffractometry. A high photoluminescence quantum yield of 0.3 was obtained for the spherulites. © 1997 John Wiley & Sons, Inc. 相似文献
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Anubhav Saxena Michiya Fujiki Roopali Rai Sun‐Young Kim Giseop Kwak 《Macromolecular rapid communications》2004,25(20):1771-1775
Summary: This paper reports a new and simple approach for the amplified detection of fluoride ions by a polymer‐based chemosensor made of stiff fluoroalkylated polysilane, poly(3,3,3‐trifluoropropylmethylsilane). This chemosensor exhibited extreme sensitivity and selectivity towards fluoride ions by a decrease in the photoluminescence (PL) intensity with parts per billion concentrations of fluoride ions in solution in tetrahydrofuran (THF). The quenching constant for fluoride ions (K = 1.35 × 107 M −1) was found to be exceptionally high.
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Langmuir–Blodgett (LB) films were prepared from poly(methylphenylsilane) bearing electron acceptor π-conjugated substituents. The small limiting area (0.078 nm2) per one repeating unit of polysilane (PSi) in monomolecular film and the large thickness of the film (6 nm) suggest that the polymer chains are not fully spread on water surface. The electrical and photoelectrical properties of Al/LB film/Au sandwich cells containing various numbers of the polysilane layers were studied. Holes were transported from the Al electrode through the LB film to the Au electrode when the light was absorbed by the polysilane. The highest photovoltaic effect occurred in the first monolayer of polysilane at the Al contact. The cell resistivity and the photovoltage were decreased by parallel conductance of defects in the films consisting of small numbers of PSi layers. 相似文献
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Marschner C Baumgartner J Wallner A 《Dalton transactions (Cambridge, England : 2003)》2006,(48):5667-5674
Possessing the property of sigma-bond electron delocalisation, polysilanes are a class of compounds with unique properties. In recent years major progress has been achieved in the theoretical understanding and the synthesis of polysilanes. Much insight into the connection between conformation and electronic properties has been gained from studies of defined small polysilane molecules. The transition from Wurtz type coupling reactions to the stepwise construction of polysilane molecules employing silyl anions as key intermediates has permitted access to defined compounds with a higher degree of structural complexity. Besides this, several methods have been developed to control the conformational properties and thus gain control over the electronic properties of polysilanes. 相似文献
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本文介绍了聚硅高分子的合成方法、紫外吸收、光敏性、导电性等一系列特殊性质,聚硅烷高分子的化学反应以及聚硅烷材料的应用. 相似文献
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The preparation and optical properties of the novel silicon-related material named oxygen-crosslinked polysilane were investigated. The oxygen-crosslinked polysilane was prepared by the thermal annealing of the precursor polysilane bearing alkoxyl groups. The photoluminescence consisting of a broad visible band at about 440 nm and a relatively sharp band at about 360 nm was observed at room temperature. The relative intensities of the visible emission were changed during the crosslinking. The visible emission was greatly affected by the steric hindrance of the alkoxyl groups of the precursor. The visible electroluminescene (EL) was also observed uniformly from the EL cell consisting of the oxygen-crosslinked polysilane film sandwiched between A1 electrode and indium-tin-oxide (ITO) electrode. The current densities of the EL cell increased with an increase in the oxygen-crosslinking. © 1997 John Wiley & Sons, Ltd. 相似文献