Materials Science and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology, Trivandrum - 695 019, India.
Phys Chem Chem Phys. 2019 Jan 30;21(5):2519-2532. doi: 10.1039/c8cp06875e.
Dilute magnetic semiconductors based on TiO2 nanocrystals are the most promising class of materials exhibiting unique optical and magnetic properties. In the present investigation, we have performed a systematic study on the structural, morphological, optical and magnetic behavior of Ni-doped TiO2, synthesized via a simple, cost-effective sol-gel route. X-ray diffraction patterns together with Raman spectra confirmed the tetragonal anatase phase of Ni-doped TiO2. High-resolution transmission electron microscopy images indicated the formation of highly crystalline nanocrystals, and the compositional homogeneity of all the samples was confirmed from energy dispersive X-ray fluorescence spectroscopic studies. The functional groups in the samples were identified by Fourier transform infrared spectroscopy. UV-visible and photoluminescence (PL) spectroscopy were performed to provide an insight into the band-gap narrowing in the Ni-doped TiO2 nanocrystals. X-ray photoelectron spectroscopy results signified the existence of Ti4+ and Ni2+ in all the prepared samples. A decrease in coercivity was observed with Ni substitution, and at lower Ni concentration, the magnetic behavior was attributed to the bound magnetic polarons associated with the oxygen vacancy defects arising during the synthesis procedure. PL analysis revealed the presence of defects in the system and Langevin fitting was employed to estimate the concentration of bound magnetic polarons arising as a result of these defects. The band-gap narrowing and the enhanced magnetic moment observed in Ni-doped TiO2 reveal the potential of this semiconductor for advanced functional applications such as magneto-optics and spintronics.
基于 TiO2 纳米晶的稀释磁性半导体是表现出独特光学和磁学性质的最有前途的材料类别。在本研究中,我们通过简单、经济高效的溶胶-凝胶法对 Ni 掺杂 TiO2 的结构、形态、光学和磁学行为进行了系统研究。X 射线衍射图谱和拉曼光谱证实了 Ni 掺杂 TiO2 具有四方锐钛矿相。高分辨率透射电子显微镜图像表明形成了高度结晶的纳米晶,并且从能量色散 X 射线荧光光谱研究证实了所有样品的组成均匀性。通过傅里叶变换红外光谱鉴定了样品中的官能团。进行了紫外-可见和光致发光(PL)光谱研究,以深入了解 Ni 掺杂 TiO2 纳米晶中的带隙变窄。X 射线光电子能谱结果表明所有制备的样品中都存在 Ti4+和 Ni2+。随着 Ni 的取代,矫顽力降低,在较低的 Ni 浓度下,磁行为归因于与合成过程中产生的氧空位缺陷相关的束缚磁极化子。PL 分析揭示了系统中存在缺陷,并采用朗之万拟合来估计由于这些缺陷产生的束缚磁极化子的浓度。在 Ni 掺杂 TiO2 中观察到的带隙变窄和增强的磁矩表明,这种半导体在磁光和自旋电子等先进功能应用方面具有潜力。