Zhang Xu, Zhang Jie, Yan Zhao-wen, Shao Yu-bo, Zhang Fu-jia
Guang Pu Xue Yu Guang Pu Fen Xi. 2016 Nov;36(11):3714-9.
vacuum sublimation method was used to purify the homegrown 3,4,9,10 perylenetetracarboxylic dianhydride(PTCDA)powder with a purity of 98% in its sublimation point of 450 ℃. With Bill’s law and ultraviolet-visible spectrophotometer testing analysis, its purity reached to 99.8%. Meanwhile, the contents of C and H elements in the pre-and post-purified molecules were also measured by using elemental analyzer. The measured results indicate that the contents of C and H elements in the post-purified the molecules are very close to the theoretical value. H element in the molecular structure was investigated with nuclear magnetic resonance (NMR) spectroscopy and the results demonstrated that there are an equal number of H atoms in two different chemical environments and it can only be located on the aromatic ring. By discussing the chemical bond formation of PTCDA molecules, the C, H and O atoms in high purity PTCDA molecules are mainly covalent bonds. The crystalline state and crystal structure of this organic material were tested and analyzed by X-ray diffractometer. The results suggest that the post-purified PTCDA power existed α-PTCDA and β-PTCDA two phases, in which α-PTCDA phase is major component while β-PTCDA phase accounts for about one five of the total ingredients. Besides, the crystal cell belonged to bottom-centered monoclinal structure. Meanwhile, the crystal state, grain size and band structure of PTCDA single crystal thin films formed on the surface of p-type silicon in its sublimation point are investigated in detail. During the high-purity α-PTCDA forming organic single thin film on the surface of p-type single silicon, the π-electron cloud covered on the top, bottom and two sides of its thin film’s molecular layer plane. Due to the formation of delocalized bond that attributed to the overlap of the outermost valence electron orbital of C, H, O atom, the valence electrons generate co-movement and the energy level splitting for the band. The energy difference between valence band and the first tight binding is 2.2 eV which lead to this organic material possessing the properties of semiconductor conduction. In addition, this organic material with the intrinsic carrier concentration for 1014 cm-3 belong to weak p-type organic semiconductor material. This organic material combines with the surface of p-type silicon to form hetehomo-type heterojunction which is provided with excellent response for visible light to near infrared wavelengths of light.
采用真空升华法在450℃升华点对纯度为98%的国产3,4,9,10-苝四羧酸二酐(PTCDA)粉末进行提纯。通过比尔定律和紫外可见分光光度计测试分析,其纯度达到了99.8%。同时,利用元素分析仪测定了提纯前后分子中C和H元素的含量。测定结果表明,提纯后分子中C和H元素的含量与理论值非常接近。用核磁共振(NMR)光谱研究了分子结构中的H元素,结果表明在两种不同化学环境中有等量的H原子,且其仅位于芳香环上。通过讨论PTCDA分子的化学键形成,高纯度PTCDA分子中的C、H和O原子主要为共价键。用X射线衍射仪对该有机材料的晶态和晶体结构进行了测试分析。结果表明,提纯后的PTCDA粉末存在α-PTCDA和β-PTCDA两个相,其中α-PTCDA相是主要成分,而β-PTCDA相约占总成分的五分之一。此外,晶胞属于底心单斜结构。同时,详细研究了在p型硅表面于其升华点形成的PTCDA单晶薄膜的晶态、晶粒尺寸和能带结构。在高纯度α-PTCDA在p型单晶硅表面形成有机单晶薄膜过程中,其薄膜分子层平面的顶部、底部和两侧覆盖有π电子云。由于C、H、O原子最外层价电子轨道重叠形成离域键,价电子产生共同运动并导致能带能级分裂。价带与第一紧束缚之间的能量差为2.2eV,这使得该有机材料具有半导体导电特性。此外,这种本征载流子浓度为1014cm-3的有机材料属于弱p型有机半导体材料。这种有机材料与p型硅表面结合形成异质同型异质结,对可见光到近红外波长的光具有优异的响应。