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Heteroatom-Doping for Carbon Dots: An Efficient Strategy to Improve Their Optoelectronic Properties

机译:碳点的杂原子 - 掺杂:提高其光电性能的有效策略

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Carbon Dots (CDs) are an emerging class of nanomaterials discovered as by-product in 2004 by Scrivens and coworkers. In recent years, they have been shown to be useful for broad applications including fluorescent probes and sensors, biolabeling and medical imaging, LED color display and optoelectronic devices. In contrast to traditional dye molecules and inorganic semiconductor quantum dots (QDs), CDs posses several advantages such as low-cost synthesis process, biocompatibility, high photostability, and excellent fluorescent properties. Despite these fascinating properties, low quantum yields (QYs) and poor solubility severely hinder their widespread applications. Recent studies have been proved that chemical heteroatoms doping is an efficient route to improve the QY, water solubility, fluorescent properties, and other physicochemical properties of CDs and thus expand their application scope. It aims to cause a significant change in electronic structures of the materials which bring to a change in their optical and electrical properties and makes them suitable for potential devices. It is believed that introducing non-metal atomic impurities and metal ions into CDs would affect the interaction between π- and n-states in CDs by the extent of orbital overlap and electron withdrawing/donating abilities of heteroatoms. Among various non-metallic dopants, generally nitrogen (N) is the hetero atom more explored because it is sufficiently electron-rich than carbon, which provides n-type doping characteristics. Sulfur (S), Phosphorous (P) and Boron (B) are also used for the same reason. Compared to most non-metallic heteroatoms, there are more electrons easy to lose and unoccupied orbitals outside of most metal ions (especially transition metal ions) and metal ions provide larger atomic radius than non-metallic ions. Nevertheless, whether the heteroatoms are doped in the rigid core or just in the functional groups on the surface of the CDs is still unclear. Furthermore the exact mechanism of fluorescence emission and its shifts upon different excitations in CDs structures endowing by doping are still under investigation. Therefore, in order to explore and enhance the doped C-Dot photosensitizing capabilities, we analysed a simple route to prepare highly fluorescent CDs by hydrothermal reactions of citric acid (CA) as carbon source and urea as N source. Among the dopants, different precursors both metal and non-metal were selected. Since CDs can be tuned by varying solvents during the synthesis, the experiments were carried out in different reaction mediums by using solvents with high and low polarity. This work would provide a platform to better understand the intricate unclear details of heteroatom-doped CDs and the influence of solvents, precursors, dopants and the surface states on their optical and other properties that is crucial and instructive to improve their performance practical applications in the future.
机译:碳点(CDS)是2004年被斯克劳斯和同事于2004年被发现的副产品的新出现的纳米材料。近年来,它们已被证明可用于广泛的应用,包括荧光探针和传感器,生物标记和医学成像,LED彩色显示器和光电器件。与传统的染料分子和无机半导体量子点(QDS)相反,Cds具有诸如低成本合成过程,生物相容性,高光稳定性和优异的荧光特性等优点。尽管这些迷人的性质,但低量子产量(Qys)和溶解度不良严重阻碍了其广泛的应用。最近的研究已经证明,化学杂原子掺杂是改善CDS的QY,水溶性,荧光特性和其他物理化学性质的有效途径,从而扩大其应用范围。它旨在引起材料的显着变化,这些材料的电子结构带来了它们的光学和电气性能的变化,并使它们适用于潜在装置。据信,将非金属原子杂质和金属离子引入CDS将在CDS中的π-和N态之间的相互作用,通过轨道重叠和杂原子的电子抽出/捐献能力。在各种非金属掺杂剂中,通常氮气(N)是杂种原子更探索,因为它比碳足够的电子,其提供n型掺杂特性。硫(S),磷(P)和硼(B)也是相同的原因。与大多数非金属杂原子相比,在大多数金属离子(特别是过渡金属离子)之外的外部有更多的电子易失去和未占用的轨道,并且金属离子提供比非金属离子更大的原子半径。然而,杂原子是掺杂在刚性芯中还是仅在CD的表面上的官能团中尚不清楚。此外,荧光发射的确切机制及其在赋予掺杂的CDS结构中的不同激发的变化仍在进行调查。因此,为了探索和增强掺杂的C点光敏能力,我们分析了一种简单的途径,通过柠檬酸(CA)作为碳源和尿素作为N个源的水热反应来制备高荧光Cds。在掺杂剂中,选择不同的前体,两种金属和非金属。由于CD可以通过在合成期间改变溶剂来调节,因此通过使用具有高和低极性的溶剂在不同的反应介质中进行实验。这项工作将提供一个平台,以更好地了解杂原子掺杂CD的错综复杂的细节以及溶剂,前体,掺杂剂和表面状态对它们的光学等特性的影响,这对于改善其性能实际应用来说至关重要和有益的性质未来。

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