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Effects of surface states, defects and dopants on the optical and magnetic properties of low-dimensional materials.

机译:表面状态,缺陷和掺杂剂对低尺寸材料光学和磁性的影响。

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摘要

Nanomaterials have attracted the attention of researchers from various fields due to their unique features (that are otherwise absent in the bulk) such as quantum confinement, high surface to volume ratio, ability for surface modification etc. Since the discovery of fullerenes and carbon nanotubes, several synthesis techniques have been developed for nanomaterial growth. However, different control parameters in different synthesis techniques often result in nanostructures with varying defects that may alter their fundamental behavior. Such defects or disorder in the crystal lattice can lead to the disruption of lattice symmetry. The defect-induced symmetry lowering (or breaking) effects play a vital role in the determination of fundamental material characteristics. Thus, it is very important to characterize the defects in order to understand their effects on the nanomaterial properties. This thesis describes the effects of defects in low dimesional systems such as ZnO nanowires, graphene and carbon nanotubes are studied.;Firstly, it describes the synthesis and characterization of ZnO nanostructures and discusses the effects of surface states, defects and dopants on their optical and magnetic properties. An unexpected presence of ferromagnetic (FM) ordering in nanostructured nonmagnetic metal oxides has been reported previously. Though this property was attributed to the presence of defects, systematic experimental and theoretical studies to pinpoint its origin and mechanism were lacking. While it is widely believed that oxygen vacancies are responsible for FM ordering, surprisingly annealing as-prepared samples at low temperature (high temperature) in flowing oxygen actually enhances (diminishes) the FM ordering. For these reasons, we have prepared, annealed in different environments, and measured the ensuing magnetization in micrometer and nanoscale ZnO with varying crystallinity. We further find from our magnetization measurements and ab-initio calculations that a range of magnetic properties in ZnO can result, depending on the sample preparation and annealing conditions. For example, within the same ZnO sample we have observed ferro- to para- and diamagnetic responses depending on the annealing conditions. We also explored the effects of surface states on the magnetic behavior of nanoscale ZnO through detailed calculations.;In the case of grapheme, we have observed new combination modes in the range from 1650 to 2300 cm-1 in single-(SLG), bi-, few-layer and incommensurate bilayer graphene (IBLG) on silicon dioxide substrates. A peak at ∼1860 cm-1 (iTALO- ) is observed due to a combination of the in-plane transverse acoustic (iTA) and the longitudinal optical (LO) phonons. The intensity of this peak decreases with increasing number of layers and this peak is absent for bulk graphite. The overtone of the out-of-plane transverse optical (oTO) phonon at ∼1750 cm-1, also called the M band, is suppressed for both SLG and IBLG. In addition, two previously unidentified modes at ∼2200 and ∼1880 cm-1 are observed in SLG. The 2220 cm -1 (1880 cm-1) mode is tentatively assigned to the combination mode of in-plane transverse optical (iTO) and TA phonons (oTO+LO phonons) around the K point in the graphene Brillouin zone. Finally, the peak frequency of the 1880 (2220) cm-1 mode is observed to increase (decrease) linearly with increasing graphene layers.;Finally, we find that the high curvature in sub-nm SWCNTs leads to (i) an unusual S-like dispersion of the G-band frequency due to perturbations caused by the strong electron-phonon coupling, (ii) an activation of diameter-selective intermediate frequency modes that are as intense as the radial breathing modes (RBMs), and (iii) a clear observation of the IR modes.
机译:纳米材料因其独特的特征(否则就不会出现在本体中)而吸引了来自各个领域的研究人员的注意,例如量子限制,高的表面体积比,表面修饰能力等。自从发现富勒烯和碳纳米管以来,已经开发了几种用于纳米材料生长的合成技术。然而,不同合成技术中不同的控制参数通常会导致纳米结构具有变化的缺陷,从而可能改变其基本行为。晶格中的此类缺陷或无序可导致晶格对称性的破坏。缺陷引起的对称性降低(或破坏)效应在确定基本材料特性中起着至关重要的作用。因此,表征缺陷以了解其对纳米材料性能的影响非常重要。本论文描述了低维体系中的缺陷对ZnO纳米线,石墨烯和碳纳米管的影响。首先,描述了ZnO纳米结构的合成和表征,并讨论了表面态,缺陷和掺杂剂对它们的光学和光学特性的影响。磁性。先前已经报道了纳米结构的非磁性金属氧化物中铁磁(FM)有序的意外存在。尽管此特性归因于缺陷的存在,但仍缺乏系统的实验和理论研究来查明其起源和机理。尽管人们普遍认为氧空位是FM有序的原因,但令人惊讶的是,在流动的氧气中在低温(高温)下对制得的样品进行退火实际上可以增强(减少)FM的有序性。由于这些原因,我们准备了在不同环境中进行退火的材料,并在不同结晶度的微米级和纳米级ZnO中测量了随之产生的磁化强度。我们还从磁化强度测量和从头算计算中发现,取决于样品制备和退火条件,可以导致ZnO的一系列磁性。例如,在相同的ZnO样品中,我们观察到了铁,顺磁和反磁响应,具体取决于退火条件。我们还通过详细的计算探索了表面状态对纳米级ZnO磁性行为的影响;在石墨烯的情况下,我们观察到了单(SLG),双(SLG)中在1650至2300 cm-1范围内的新组合模式-二氧化硅衬底上的几层且不相称的双层石墨烯(IBLG)。由于面内横向声波(iTA)和纵向光学(LO)声子的结合,在〜1860 cm-1(iTALO-)处观察到一个峰值。该峰的强度随着层数的增加而降低,并且对于本体石墨不存在该峰。 SLG和IBLG都抑制了〜1750 cm-1的平面外横向光学(oTO)声子的泛音,也称为M波段。此外,在SLG中观察到了两个以前未发现的模式,分别位于〜2200和〜1880 cm-1。暂时将2220 cm -1(1880 cm-1)模式指定为石墨烯布里渊区K点附近的平面内横向光学(iTO)和TA声子(oTO + LO声子)的组合模式。最后,观察到1880(2220)cm-1模式的峰值频率随石墨烯层的增加而线性增加(减小)。最后,我们发现亚纳米SWCNT中的高曲率导致(i)不寻常的S由强电子-声子耦合引起的扰动引起的G频段频率类似的色散,(ii)激活与径向呼吸模式(RBM)一样强的直径选择中频模式,以及(iii)对IR模式的清晰观察。

著录项

  • 作者

    Podila, Ramakrishna.;

  • 作者单位

    Clemson University.;

  • 授予单位 Clemson University.;
  • 学科 Nanoscience.;Physics Condensed Matter.
  • 学位 Ph.D.
  • 年度 2011
  • 页码 134 p.
  • 总页数 134
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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