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Synthesis and Characterization of 2D Nanocrystals and Thin Films of Transition Metal Carbides (MXenes)

机译:过渡金属碳化物(MXenes)的2D纳米晶体和薄膜的合成与表征

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摘要

Two dimensional (2D) materials have received growing interest because of their unique properties compared to their bulk counterparts. Graphene is the archetype 2D solid, but other materials beyond graphene, such as MoS2 and BN have become potential candidates for several applications. Recently, a new family of 2D materials of early transition metal carbides and carbonitrides (Ti2CTx, Ti3C2Tx, Ti3CNTx, Ta4C3Tx, and more), labelled MXenes, has been discovered, where T stands for the surface-terminating groups. Before the present work, MXenes had only been synthesized in the form of exfoliated and delaminated powders, which is not suitable for electronic applications. In this thesis, I demonstrate the synthesis of MXenes as epitaxial thin films, a more suitable form for electronic and photonic applications. Results show that 2D epitaxial Ti3C2Tx films - produced by HF and NH4HF2 etching of magnetron sputter-grown Ti3AlC2 - exhibit metallic conductive behaviour down to 100 K and are 90% transparent to light in the visible-infrared range. The results from this work may open the door for MXenes as potential candidates for transparent conductive electrodes as well as in electronic, photonic and sensing applications. MXenes have been shown to intercalate cations and molecules between their layers that in turn can alter the surface termination groups. There is therefore a need to study the surface chemistries of synthetized MXenes to be able to study the effect of intercalation as well as altering the surface termination groups on the electronic structure and chemical states of the elements present in MXene layers. X-ray Photoelectron Spectroscopy (XPS) in-depth characterization was used to investigate surface chemistries of Ti3C2Tx and Ti2CTx. This thesis includes the discussion of the effect of Ar+ sputtering and the number of layers on the surface chemistry of MXenes. This study serves as a baseline for chemical modification and tailoring of the surface chemistry groups to potential uses and applications. New MXene phases, Nb2CTx and V2CTx, are shown in this thesis to be produced from HF chemical etching of Nb2AlC and V2AlC powders. Characterization of the produced MXenes was carried out using Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Transmission Electron Microscope (TEM) and XPS. Nb2CTx and V2CTx showed promising performance as electrodes for Li-ion batteries. In this thesis, electrochemical etching was used in an attempt to produce 2D metal carbides (MXene) from their ternary metal carbides, Ti3SiC2, Ti3AlC2 and Ti2AlC MAX phases. MAX phases in the form of highly dense bulk produced by Hot Isostatic Press. Several etching solutions were used such as HF, NaCl and HCl. Unlike the HF chemical etching of MAX phases, which results in MXenes, the electrochemical etching resulted in Carbide Derived Carbon (CDC). Here, I show the characterization of the produced CDC using several techniques such as XRD, TEM, Raman spectroscopy, and XPS. Electrochemical characterization was performed in the form of cyclic voltammetry, which sheds light on the etching mechanism.
机译:二维(2D)材料由于其独特的性能(与整体材料相比)而受到越来越多的关注。石墨烯是2D原型实体,但石墨烯以外的其他材料(例如MoS2和BN)已成为多种应用的潜在候选者。最近,发现了一种新的2D早期过渡金属碳化物和碳氮化物材料(Ti2CTx,Ti3C2Tx,Ti3CNTx,Ta4C3Tx等),标记为MXenes,其中T代表表面终止基团。在本工作之前,MXene仅以剥离和分层粉末的形式合成,这不适合用于电子应用。在本文中,我演示了作为外延薄膜的MXene的合成,这是一种更适合电子和光子应用的形式。结果表明,通过磁控溅射生长的Ti3AlC2的HF和NH4HF2蚀刻产生的2D外延Ti3C2Tx膜表现出低至100 K的金属导电性能,并且在可见红外范围内对光透明90%。这项工作的结果可能为MXene作为透明导电电极以及电子,光子和传感应用的潜在候选者打开大门。 MXene已显示出在其层之间插入阳离子和分子,进而可以改变表面终止基团。因此,需要研究合成的MXene的表面化学,以能够研究嵌入的影响以及改变表面终止基团对存在于MXene层中的元素的电子结构和化学状态的影响。 X射线光电子能谱(XPS)的深度表征用于研究Ti3C2Tx和Ti2CTx的表面化学性质。本文讨论了Ar +溅射的影响以及层数对MXenes表面化学的影响。这项研究为化学修饰和针对潜在用途和应用的表面化学基团的定制提供了基线。本文显示了新的MXene相Nb2CTx和V2CTx是通过Nb2AlC和V2AlC粉末的HF化学蚀刻制成的。使用扫描电子显微镜(SEM),X射线衍射(XRD),透射电子显微镜(TEM)和XPS对生成的MXene进行表征。 Nb2CTx和V2CTx作为锂离子电池的电极表现出令人鼓舞的性能。在本文中,尝试使用电化学蚀刻从三元金属碳化物Ti3SiC2,Ti3AlC2和Ti2AlC MAX相生成二维金属碳化物(MXene)。热等静压机生产的高密度散装形式的MAX相。使用了几种蚀刻溶液,例如HF,NaCl和HCl。不同于MAX相的HF化学刻蚀会生成MXene,而电化学刻蚀会生成碳化物衍生碳(CDC)。在这里,我展示了使用多种技术(例如XRD,TEM,拉曼光谱和XPS)对生成的CDC的表征。电化学表征以循环伏安法的形式进行,这为蚀刻机理提供了线索。

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  • 作者

    Halim, Joseph;

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  • 年度 2014
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  • 原文格式 PDF
  • 正文语种 eng
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