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中国物理学会期刊

过渡金属(Cr, Mn, Fe, Co)掺杂对TiO2磁性影响的第一性原理研究

CSTR: 32037.14.aps.69.20200644

First principle study of influence of transition metal (Cr, Mn, Fe, Co) doping on magnetism of TiO2

CSTR: 32037.14.aps.69.20200644
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  • 关于过渡金属掺杂TiO2是否会产生室温铁磁性及其磁性的来源存在争议, 为了解决此问题, 本文采用基于密度泛函理论下的GGA+U方法对体系Ti0.875X0.125O2 (X = Cr, Mn, Fe, Co)的磁学性质及光学性质进行了第一性原理的研究. 首先计算了铁磁和反铁磁的基态能量, 比较后推测出铁磁态为它们的基态; 分析能带结构发现Ti0.875Cr0.125O2和Ti0.875Mn0.125O2两种体系保持半导体性质, Ti0.875Fe0.125O2和Ti0.875Co0.125O2两种体系表现金属特性; 掺杂体系都产生了室温铁磁性, 磁性来源主要是过渡金属元素(Cr, Mn, Fe, Co)3d电子轨道诱导极化了周围的O-2p态自旋电子, 导致体系产生净磁矩而呈现铁磁性; 掺杂体系的吸收光谱均发生了红移, 有效扩展了对可见光的吸收范围.

     

    It is still in controversy whether the transition metal doped TiO2 will generate room temperature ferromagnetism and where its magnetism originates from. In order to solve this problem, in this paper we use the GGA+U method based on density functional theory to conduct a first-principle study of the magnetic and optical properties for each of the systems of Ti0.875X0.125O2, X = Cr, Mn, Fe, Co. We calculate the ground state energy of each system, on the supposition that they are ferromagnetic or antiferromagnetic. After comparison, the ferromagnetic state is speculated to be its ground state. The binding energy and magnetism calculation results show that Ti0.875Cr0.125O2 has the best stability in all doped systems, that the transition metal element doped TiO2 system has a net magnetic moment, and that the doped systems are ferrimagnetic. In comparison, the net magnetic moment produced by Cr, Mn and Fe doped with TiO2 are substantial, showing that these three systems have good ferromagnetic properties. The Curie temperatures of all doped systems are above room temperature, which is of great significance for the electron spin to retain the information in dilute magnetic semiconductors (DMS), and also greatly helps with the practical application of magnetic materials. The analysis of the energy band structure reveals that intrinsic TiO2 is non ferromagnet, Ti0.875Cr0.125O2 and Ti0.875Mn0.125O2 maintain semiconductor properties, and Ti0.875Fe0.125O2 and Ti0.875Co0.125O2 exhibit metal characteristics. The doped systems produce room temperature ferromagnetism, the main magnetic source is the transition metal elements (Cr, Mn, Fe, Co) 3d electron orbit induced polarization of the surrounding O-2p state spin electrons, causing the systems to produce a net magnetic moment and be ferromagnetic. The absorption spectrum of the doped system is red-shifted, which shows that the doping causes the range of its absorption spectrum to extend to the visible range. At the same time, in all the doped systems in this article, Fe and Co doped TiO2 have the best light absorption intensity, and the magnetic property of the Fe doped system is the strongest, which indicates that when the system is ferromagnetic, the spin up and spin down splitting will occur in the local magnetic field, which will change the electronic structure of TiO2 and enhance its photocatalytic performance. The calculation results in this paper are of theoretical significance for preparing TiO2 with curie temperature above room temperature by being doped with transition metal elements of Cr, Mn, Fe, and Co.

     

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